Compound, metal complex, catalyst composition for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer

Abstract

A catalyst composition for olefin polymerization, which contains a compound represented by general formula (A) and a transition metal compound represented by general formula (E) or (F). (The definitions in the general formulae are as shown in the description. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a polymerization catalyst for producing an olefin polymer. In particular, the present invention relates to a novel compound that can be used as a ligand, a metal complex using the novel compound, an olefin polymerization catalyst composition, and an olefin polymerization catalyst. In addition, the present invention also relates to a method for producing an olefin polymer using the catalyst. Background Art

[0002] Copolymers of olefins such as ethylene and propylene, which are non-polar monomers, and polar group-containing monomers have functions and characteristics that non-polar polyethylene and polypropylene do not have. From this point of view, research on imparting functionality to polyethylene and polypropylene by copolymerizing ethylene, propylene and polar group-containing monomers is being conducted vigorously.

[0003] As a transition metal catalyst that can copolymerize ethylene, propylene and a polar group-containing monomer, a catalyst comprising a palladium complex using an α-diimine ligand has been reported (Non-Patent Document 1). As a transition metal catalyst that can copolymerize ethylene and acrylic acid ester, a so-called SHOP-based catalyst comprising a nickel complex using a ligand having a phosphorus atom and an oxygen atom as a coordinating atom has been reported (Patent Document 1, Patent Document 2, Non-Patent Document 2, Non-Patent Document 3) and a catalyst comprising a palladium complex having a phosphinosulfonic acid ligand (Patent Document 3, Non-Patent Document 4, Non-Patent Document 5).

[0004] Patent Document 4 and Non-Patent Document 6 report that: by using a nickel catalyst obtained by reacting a ligand having phosphorus and oxygen atoms as coordinating atoms with bis-1,5-cyclooctadiene nickel (Ni(cod)2) as a transition metal compound, a linear copolymer of ethylene and (meth)acrylate with few branches can be obtained. In addition, Patent Document 5 reports that ethylene and a polar group-containing monomer are copolymerized using a catalyst containing a nickel complex, wherein the nickel complex is obtained by reacting a monovalent anionic bidentate ligand having an alkylene group as a non-aromatic skeleton as a ligand skeleton and having phosphorus and oxygen atoms as coordinating atoms with an allyl nickel chloride dimer.

[0005] Non-patent document 7 reports the oligomerization of ethylene using a nickel catalyst obtained by reacting a monovalent anionic bidentate ligand having an alkylene group as a non-aromatic skeleton as a ligand skeleton and phosphorus and oxygen atoms as coordinating atoms with bis-1,5-cyclooctadiene nickel.

[0006] Non-Patent Document 8 reports the oligomerization of ethylene using a nickel catalyst obtained by reacting a monovalent anionic bidentate ligand having a non-aromatic skeleton and having phosphorus and sulfur atoms as coordinating atoms with a nickel complex.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: U.S. Patent No. 4,698,403

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 64-14217

[0011] Patent Document 3: U.S. Patent Application Publication No. 2007 / 0049712

[0012] Patent Document 4: International Publication No. 2010 / 050256

[0013] Patent Document 5: International Publication No. 2001 / 092342

[0014] Non-patent literature

[0015] Non-patent literature 1: Mecking, S.; Johnson, LK; Wang, L.; Brookhart, M. Am. Chem. Soc. 1998, 120, 888-899.

[0016] Non-patent literature 2: Ittel, SD; Johnson, LK; Brookhart, M., Chem. Rev. 2000, 100, 1169-1203.

[0017] Non-patent literature 3: Gibson, VC; Tomov, A.; White, AJP; Williams, DJ, Chem. Commun. 2001, 719-720.

[0018] Non-patent literature 4: Drent, E.; van Dijk, R.; van Ginkel, R.; van Oort, B.; Pugh, RI, Chem. Commun. 2002, 744-745.

[0019] Non-patent document 5: Kochi, T.; Yoshimura, K.; Nozaki, K., Dalton Trans. 2006, 25-27.

[0020] Non-patent literature 6: Xin.BS; Sato, N.; Tanna, A.; Oishi, Y.; Konishi, Y.; Shimizu, FJAm.Chem.Soc.2017, 139, 3611-3614.

[0021] Non-patent literature 7: Mueller, U.; Keim, W.; Krueger, C.; Betz, P. Angew. Chem. Int. Ed. Engl. 1989, 28, 1011-1013.

[0022] Non-patent document 8: H.-F. Klein et al., Inorganica Chimica Acta 358 (2005) 4394-4402 Summary of the invention

[0023] Problem that the invention aims to solve

[0024] As mentioned above, a variety of olefin polymerization catalysts are known. However, the skeletons of the ligands used in Patent Document 4 and Non-Patent Document 6 are aromatic, and there is room for improvement in the molecular weight of the copolymer in the copolymerization with acrylic esters. In addition, the catalyst of Patent Document 5 has room for improvement in catalytic performance such as activity and molecular weight. In addition, only oligomers are obtained in Non-Patent Document 7, and the polymerization activity is unclear. It should be noted that the separation of the complex is disclosed, but the separated complex does not show polymerization performance. The catalyst of Non-Patent Document 8 is known to be able to form low-density polyethylene oligomers sometimes.

[0025] Under such circumstances, the problem to be solved by the present invention is to provide a novel compound that can be used as a ligand for a catalyst that can polymerize or copolymerize olefins and has improved catalytic performance such as activity and molecular weight, and in particular, a novel compound that can be used as a ligand for a catalyst that can copolymerize at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins and a non-cyclic olefin, a metal complex using the novel compound, a catalyst composition for olefin polymerization, and a catalyst for olefin polymerization, and a method for producing an olefin-based polymer using the catalyst.

[0026] Solutions for solving problems

[0027] The present inventors have discovered a catalyst for olefin polymerization having a high level of activity or molecular weight by combining a monovalent anionic bidentate ligand containing an alkylene group having a specific structure as a ligand skeleton and having Group 15 and 16 elements, especially nitrogen atoms or phosphorus atoms and oxygen atoms, as coordinating atoms and having a specific substituent with a specific nickel compound and / or palladium compound, thereby completing the present invention.

[0028] That is, the first embodiment of the present invention relates to the following [1-1] to [1-16].

[0029] [1-1] A compound represented by the following general formula (A).

[0030]

[0031] [In formula (A),

[0032] X 1 represents an oxygen atom or a sulfur atom,

[0033] E 1 represents a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom,

[0034] Z represents a hydrogen atom, a leaving group, or a cation having a valence of 1 or more and 4 or less,

[0035] m is an integer greater than or equal to 1 and less than or equal to the valence number of Z,

[0036] n is 0, 1, 2, 3 or 4. When n is 0, E 1 With X 1 , R 5 and R 6 The bonded carbon atom is directly bonded, R 1 represents a hydrocarbon group represented by the following general formula (B) or (C),

[0037] R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, which is different from the hydrocarbon group represented by the following general formula (B) or (C) and which may contain at least one heteroatom,

[0038] l is 1 or 2. When l is 2, R 2 Does not exist.

[0039] R 3 , R 4 , R 5 and R 6 Each independently represents an atom or a group selected from the group consisting of the following (i) to (iv).

[0040] (i) Hydrogen atom

[0041] (ii) Halogen atoms

[0042] (iii) a hydrocarbon group having 1 to 30 carbon atoms and optionally containing at least one heteroatom

[0043] (iv)OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(ORb ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group (here, R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, and y represents 0, 1 or 2). 3 , R 4 , R 5 and R 6 Adjacent substituents may be linked to each other to form a 5- to 8-membered alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom.]

[0044]

[0045] [In formula (B) and formula (C),

[0046] *Indicates the same as E 1 The connection key,

[0047] R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A), R 7 , R 8 , R 9 and R 10 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom,

[0048] A 1 , A 2 , A 3 and A 4Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)- (herein, R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which optionally contains at least one heteroatom.).

[0049] in,

[0050] In formula (B), A 1 , A 2 , A 3 and A 4 At least two of them are -C(R)2-, in formula (C), A 3 and A 4 At least one of them is -C(R)2- and R 12 and R 13 At least one of them is an atom or group selected from the group consisting of (i) and (iii) above, or A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 Each of them is an atom or a group selected from the group consisting of (i) and (iii) above.

[0051] W 1 and W 2 Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8 and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R 10 Does not exist.

[0052] h and i are each independently an integer of 1 to 6, 1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R 7 , R 8 , R 9 and R 10 They may be the same or different.]

[0053] [1-2] A metal complex represented by the following general formula (D).

[0054]

[0055] [In formula (D),

[0056] X 1 represents an oxygen atom or a sulfur atom,

[0057] E 1 represents a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom,

[0058] n is 0, 1, 2, 3 or 4. When n is 0, E 1 With X 1 , R 5 and R 6 The bonded carbon atom is directly bonded, R 1 represents a hydrocarbon group represented by the following general formula (B) or (C),

[0059] R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, which is different from the hydrocarbon group represented by the following general formula (B) or (C) and which may contain at least one heteroatom,

[0060] l is 1 or 2. When l is 2, R 2 Does not exist.

[0061] R 3 , R 4 , R 5 and R 6 Each independently represents an atom or a group selected from the group consisting of the following (i) to (iv).

[0062] (i) Hydrogen atom

[0063] (ii) Halogen atoms

[0064] (iii) a hydrocarbon group having 1 to 30 carbon atoms and optionally containing at least one heteroatom

[0065] (iv)OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(ORa ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group (here, R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, and y represents 0, 1 or 2). 3 , R 4 , R 5 and R 6 Adjacent substituents may be linked to each other to form a 5- to 8-membered alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom.

[0066] M 1 represents a nickel atom or a palladium atom,

[0067] L 1 and L 2 Each independently represents the coordination in M 1 The ligand

[0068] L 1 and L 2 Optionally bonded to each other to form a 1 ring.]

[0069]

[0070] [In formula (B) and formula (C),

[0071] *Indicates the same as E 1 The connection key,

[0072] R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A), R 7 , R 8 , R 9 and R 10Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom,

[0073] A 1 , A 2 , A 3 and A 4 Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)- (herein, R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which optionally contains at least one heteroatom.).

[0074] in,

[0075] In formula (B), A 1 , A 2 , A 3 and A 4 At least two of them are -C(R)2-, in formula (C), A 3 and A 4 At least one of them is -C(R)2- and R 12 and R 13 At least one of them is an atom or group selected from the group consisting of (i) and (iii) above, or A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 Each of them is an atom or a group selected from the group consisting of (i) and (iii) above.

[0076] W 1 and W 2 Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8 and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R 10 Does not exist.

[0077] h and i are each independently an integer of 1 to 6, 1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R7 , R 8 , R 9 and R 10 They may be the same or different.]

[0078] [1-3] An olefin polymerization catalyst composition comprising the compound represented by the general formula (A) described in [1-1] above and a transition metal compound represented by the following general formula (E) or (F).

[0079]

[0080] [In formula (E) and formula (F),

[0081] M 1 represents a nickel atom or a palladium atom,

[0082] L 1 and L 2 Each independently represents the coordination in M 1 The ligand

[0083] L 1 and L 2 Optionally bonded to each other to form a 1 Ring.

[0084] M 2 and M 3 each independently represents a nickel atom or a palladium atom,

[0085] L 3 , L 4 , L 5 , L 6 , L 9 and L 10 Each independently represents the coordination in M 1 、M 2 or M 3 The ligand, L 7 and L 8 Each independently represents the coordination in M 2 and M 3 The ligand

[0086] q is 0, 1, or 2,

[0087] L 3 and L 4 Optionally bonded to each other to form a 1 The ring,

[0088] L 5 and L 6 Optionally bonded to each other to form a 2 The ring,

[0089] L9 and L 10 Optionally bonded to each other to form a 3 ring.]

[0090] [1-4] The compound according to [1-1] above, wherein R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0091] [1-5] The metal complex according to [1-2], wherein R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0092] [1-6] The olefin polymerization catalyst composition according to [1-3] above, wherein the R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0093] [1-7] The compound according to [1-1] above, wherein R 5 is an atom or group selected from the group consisting of (i) and (iii) above, and the above R 6 For a compound selected from the group consisting of (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in the group (here, R a , R b , y are as defined in [1-1] above. ).

[0094] [1-8] The metal complex according to [1-2], wherein the R 5 is an atom or group selected from the group consisting of (i) and (iii) above, and the above R 6 For a compound selected from the group consisting of (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b )2-y (R a ) y The atoms or groups in the group (here, R a , R b , y are as defined in [1-2] above. ).

[0095] [1-9] The olefin polymerization catalyst composition according to [1-3] above, wherein the R 5 is an atom or group selected from the group consisting of (i) and (iii) above, and the above R 6 For a compound selected from the group consisting of (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in the group (here, R a , R b , y are as defined in [1-1] above. ).

[0096] [1-10] The compound according to any one of [1-1], [1-4] and [1-7], wherein R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0097] [1-11] The metal complex according to any one of [1-2], [1-5] and [1-8], wherein R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0098] [1-12] The olefin polymerization catalyst composition according to any one of [1-3], [1-6] and [1-9], wherein the R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0099] [1-13] An olefin polymerization catalyst comprising the olefin polymerization catalyst composition described in any one of [1-3], [1-6], [1-9] and [1-12].

[0100] [1-14] An olefin polymerization catalyst comprising the metal complex described in any one of [1-2], [1-5], [1-8] and [1-11].

[0101] [1-15] A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst described in [1-13] or [1-14] above.

[0102] [1-16] The method for producing an olefin-based polymer according to [1-15] above, wherein the acyclic olefin is copolymerized with at least one monomer selected from the group consisting of a polar group-containing monomer and a cyclic olefin.

[0103] In addition, the second embodiment of the present invention relates to the following [2-1] to [2-16].

[0104] [2-1] A compound represented by the following general formula (A).

[0105]

[0106] [In formula (A),

[0107] X 1 represents an oxygen atom or a sulfur atom,

[0108] E 1 represents a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom,

[0109] Z represents a hydrogen atom, a leaving group, or a cation having a valence of 1 or more and 4 or less,

[0110] m is an integer greater than or equal to 1 and less than or equal to the valence number of Z,

[0111] n is 0, 1, 2, 3 or 4. When n is 0, E 1 With X 1 , R 5 and R 6 The bonded carbon atom is directly bonded, R 1 represents a hydrocarbon group represented by the following general formula (B) or (C),

[0112] R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, which is different from the hydrocarbon group represented by the following general formula (B) or (C) and which may contain at least one heteroatom,

[0113] l is 1 or 2. When l is 2, R 2 Does not exist.

[0114] R 3 , R 4 , R 5 and R6 Each independently represents an atom or a group selected from the group consisting of the following (i) to (iv).

[0115] (i) Hydrogen atom

[0116] (ii) Halogen atoms

[0117] (iii) a hydrocarbon group having 1 to 30 carbon atoms and optionally containing at least one heteroatom

[0118] (iv)OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group (here, R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, and y represents 0, 1 or 2). 3 , R 4 , R 5 and R 6 Adjacent substituents may be linked to each other to form a 5- to 8-membered alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom.]

[0119]

[0120] [In formula (B) and formula (C),

[0121] *Indicates the same as E1 The connection key,

[0122] R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A), R 7 , R 8 , R 9 and R 10 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom,

[0123] A 1 , A 2 , A 3 and A 4 Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)- (herein, R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which optionally contains at least one heteroatom.).

[0124] in,

[0125] In formula (B), A 1 , A 2 , A 3 and A 4 At least three of them are groups other than -C(R)2-,

[0126] In formula (C), A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 At least one of them is an atom or group selected from the group consisting of (ii) and (iv) above (except for epoxy-containing groups).

[0127] W 1 and W 2 Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8 and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R10 Does not exist.

[0128] h and i are each independently an integer of 1 to 6, 1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R 7 , R 8 , R 9 and R 10 They may be the same or different.]

[0129] [2-2] A metal complex represented by the following general formula (D).

[0130]

[0131] [In formula (D),

[0132] X 1 represents an oxygen atom or a sulfur atom,

[0133] E 1 represents a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom,

[0134] n is 0, 1, 2, 3 or 4. When n is 0, E 1 With X 1 , R 5 and R 6 The bonded carbon atom is directly bonded, R 1 represents a hydrocarbon group represented by the following general formula (B) or (C),

[0135] R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, which is different from the hydrocarbon group represented by the following general formula (B) or (C) and which may contain at least one heteroatom,

[0136] l is 1 or 2. When l is 2, R 2 Does not exist.

[0137] R 3 , R 4 , R 5 and R 6 Each independently represents an atom or a group selected from the group consisting of the following (i) to (iv).

[0138] (i) Hydrogen atom

[0139] (ii) Halogen atoms

[0140] (iii) a hydrocarbon group having 1 to 30 carbon atoms and optionally containing at least one heteroatom

[0141] (iv)OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group (here, R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, and y represents 0, 1 or 2). 3 , R 4 , R 5 and R 6 Adjacent substituents may be linked to each other to form a 5- to 8-membered alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom.

[0142] M 1 represents a nickel atom or a palladium atom,

[0143] L 1 and L 2 Each independently represents the coordination in M 1 The ligand,

[0144] L 1 and L 2 Optionally bonded to each other to form a 1 ring.]

[0145]

[0146] [In formula (B) and formula (C),

[0147] *Indicates the same as E 1 The connection key,

[0148] R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A), R 7 , R 8 , R 9 and R 10 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom,

[0149] A 1 , A 2 , A 3 and A 4 Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)- (herein, R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which optionally contains at least one heteroatom.).

[0150] in,

[0151] In formula (B), A 1 , A 2 , A 3 and A 4 At least three of them are groups other than -C(R)2-,

[0152] In formula (C), A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 At least one of them is an atom or group selected from the group consisting of (ii) and (iv) above (except for epoxy-containing groups).

[0153] W 1 and W 2 Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R 10 Does not exist.

[0154] h and i are each independently an integer of 1 to 6, 1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R 7 , R 8 , R 9 and R 10 They may be the same or different.]

[0155] [2-3] An olefin polymerization catalyst composition comprising the compound represented by the general formula (A) described in [2-1] above and a transition metal compound represented by the following general formula (E) or (F).

[0156]

[0157] [In formula (E) and formula (F),

[0158] M 1 represents a nickel atom or a palladium atom,

[0159] L 1 and L 2 Each independently represents the coordination in M 1 The ligand,

[0160] L 1 and L 2 Optionally bonded to each other to form a 1 Ring.

[0161] M 2 and M 3 each independently represents a nickel atom or a palladium atom,

[0162] L 3 , L 4 , L 5 , L 6 , L 9 and L 10 Each independently represents the coordination in M 1 、M 2 or M 3 The ligand, L 7 and L 8Each independently represents the coordination in M 2 and M 3 The ligand

[0163] q is 0, 1, or 2,

[0164] L 3 and L 4 Optionally bonded to each other to form a 1 The ring,

[0165] L 5 and L 6 Optionally bonded to each other to form a 2 The ring,

[0166] L 9 and L 10 Optionally bonded to each other to form a 3 ring.]

[0167] [2-4] The compound according to [2-1] above, wherein R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0168] [2-5] The metal complex according to [2-2], wherein the R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0169] [2-6] The olefin polymerization catalyst composition according to [2-3] above, wherein the R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0170] [2-7] The compound according to [2-1], wherein R 5 is an atom or group selected from the group consisting of (i) and (iii) above, and the above R 6 For a compound selected from the group consisting of (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in the group (here, Ra , R b , y are as defined in [2-1] above. ).

[0171] [2-8] The metal complex according to [2-2], wherein the R 5 is an atom or group selected from the group consisting of (i) and (iii) above, and the above R 6 For a compound selected from the group consisting of (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in the group (here, R a , R b , y are as defined in [2-2] above. ).

[0172] [2-9] The olefin polymerization catalyst composition according to [2-3] above, characterized in that the R 5 is an atom or group selected from the group consisting of (i) and (iii) above, and the above R 6 For a compound selected from the group consisting of (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in the group (here, R a , R b , y are as defined in [2-1] above. ).

[0173] [2-10] The compound according to any one of [2-1], [2-4] and [2-7], wherein R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0174] [2-11] The metal complex according to any one of [2-2], [2-5] and [2-8], wherein R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0175] [2-12] The olefin polymerization catalyst composition according to any one of [2-3], [2-6] and [2-9], wherein the R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above.

[0176] [2-13] An olefin polymerization catalyst comprising the olefin polymerization catalyst composition described in any one of [2-3], [2-6], [2-9] and [2-12].

[0177] [2-14] An olefin polymerization catalyst comprising the metal complex described in any one of [2-2], [2-5], [2-8] and [2-11] above.

[0178] [2-15] A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst described in [2-13] or [2-14] above.

[0179] [2-16] The method for producing an olefin-based polymer according to [2-15] above, wherein the acyclic olefin is copolymerized with at least one monomer selected from the group consisting of a polar group-containing monomer and a cyclic olefin.

[0180] Effects of the Invention

[0181] According to the present invention, there can be provided a novel compound which can be used as a ligand of a catalyst which can polymerize or copolymerize olefins and has improved catalytic properties such as activity and molecular weight, and in particular a novel compound which can be used as a ligand of a catalyst which can copolymerize at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins with a non-cyclic olefin, a metal complex using the novel compound, a catalyst composition for olefin polymerization, and a catalyst for olefin polymerization, and a method for producing an olefin-based polymer using the catalyst. DETAILED DESCRIPTION

[0182] Hereinafter, the novel compound that can be used as a ligand in the first embodiment and the second embodiment of the present invention, the metal complex using the novel compound, the catalyst composition for olefin polymerization and the catalyst for olefin polymerization, and the method for producing an olefin-based polymer using the catalyst are described in detail item by item.

[0183] In this specification, "polymerization" is a general term for homopolymerization of one monomer and copolymerization of multiple monomers, and when there is no need to distinguish between the two, they are simply referred to as "polymerization." In addition, in the specification, "(meth)acrylate" includes both acrylate and methacrylate.

[0184] In addition, in this specification, "to" which shows a numerical range is used to mean that the numerical values ​​described before and after it are included as a lower limit and an upper limit.

[0185] In the present specification, "Ph" represents a phenyl group, "Me" represents a methyl group, "Et" represents an ethyl group, "Pr" represents a propyl group, "Bu" represents a butyl group, "Py" represents a pyridyl group or pyridine, "acac" represents acetylacetone, "DMP" represents 2,6-dimethoxyphenyl, and "TMS" represents trimethylsilyl.

[0186] In addition, in the prefix of the structural isomer of the alkyl group, "i" represents iso, "n" represents normal, "s" represents secondary, and "t" represents tertiary. It should be noted that when the prefix of the structural isomer is not described in the alkyl group, it represents the normal structure.

[0187] I. First Embodiment

[0188] I-1. Compounds

[0189] The compound according to the first embodiment of the present invention is a compound represented by the following general formula (A).

[0190]

[0191] [In formula (A), each symbol is as defined in [1-1] above.]

[0192] Hereinafter, R in formula (A) 1 ~R 6 、E 1 , X 1 , Z, l, n and m are used for explanation.

[0193] In the above general formula (A), X 1 represents an oxygen atom or a sulfur atom. That is, the compound represented by the above general formula (A) can be used as a ligand having one Group 16 element as a monovalent anionic coordinating atom. From the perspective of the rich variety of compounds used as ligands, X 1 Preferred is an oxygen atom.

[0194] In the above general formula (A), E 1represents a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom. That is, the compound represented by the general formula (A) can be used as a ligand having one Group 15 element as a neutral coordinating atom. Since there are a variety of compounds used as ligands and the coordination property with transition metal elements later in the period such as nickel or palladium is good, E 1 Preferred is a nitrogen atom or a phosphorus atom.

[0195] In the above general formula (A), R 3 , R 4 , R 5 and R 6 Each independently represents an atom or a group selected from the group consisting of the following (i) to (iv).

[0196] (i) Hydrogen atom

[0197] (ii) Halogen atoms

[0198] (iii) a hydrocarbon group having 1 to 30 carbon atoms and optionally containing at least one heteroatom

[0199] (iv)OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group (here, R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, and y represents 0, 1 or 2). 3 , R4 , R 5 and R 6 Adjacent substituents may be linked to each other to form a 5- to 8-membered alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom.

[0200] Examples of the (ii) halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom is preferred.

[0201] Examples of the (iii) hydrocarbon group having 1 to 30 carbon atoms which may contain at least one hetero atom include a hydrocarbon group and a hydrocarbon group in which at least one hydrogen atom is substituted with a substituent containing a hetero atom.

[0202] Examples of the hetero atom in (iii) include oxygen, nitrogen, phosphorus, sulfur, silicon, and halogen atoms. The hetero atom as a substituent may be a halogen atom, and the halogen atom may be the same as that in (ii) above.

[0203] Examples of the heteroatom-containing substituent in (iii) include the same substituents as those exemplified in (iv) described later. Examples of the heteroatom-containing substituent in (iii) include an alkoxy group, an aryloxy group, an alkoxycarbonyl group, or an acyloxy group.

[0204] Examples of the hydrocarbon group having 1 to 30 carbon atoms in (iii) include linear, branched, cyclic saturated or unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. More specifically, examples of the hydrocarbon group having 1 to 30 carbon atoms include linear alkyl groups having 1 to 30 carbon atoms, branched acyclic alkyl groups having 3 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms which may have a side chain, aryl groups having 6 to 30 carbon atoms, arylalkyl groups having 7 to 30 carbon atoms, and alkylaryl groups having 7 to 30 carbon atoms.

[0205] Examples of the straight-chain alkyl group having 1 to 30 carbon atoms include a straight-chain alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl, and may include a straight-chain alkyl group having 1 to 4 carbon atoms.

[0206] The branched non-cyclic alkyl group having 3 to 30 carbon atoms may be isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl (3-methylbutyl), tert-pentyl (1,1-dimethylpropyl), sec-pentyl (1-methylbutyl), 2-methylbutyl, neopentyl (2,2-dimethylpropyl), 1,2-dimethylpropyl, isohexyl (4-methylpentyl), or the like. The branched non-cyclic alkyl group having 3 to 10 carbon atoms may be used.

[0207] Examples of the alkenyl group having 2 to 30 carbon atoms include vinyl, allyl, butenyl, pentenyl, hexenyl, styryl, and cinnamyl. Examples of the alkenyl group include alkenyl groups having 3 to 8 carbon atoms such as allyl, butenyl, pentenyl, hexenyl, and styryl, and alkenyl groups having 4 to 8 carbon atoms such as butenyl, pentenyl, hexenyl, and styryl.

[0208] The cycloalkyl group having 3 to 30 carbon atoms and optionally having a side chain may be a cycloalkyl group having 3 to 10 carbon atoms and optionally having a side chain, such as cyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, cyclooctyl, decahydronaphthyl (bicyclo[4,4,0]decyl), or a cycloalkyl group having 3 to 6 carbon atoms and optionally having a side chain.

[0209] Examples of the aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, azulenyl, biphenyl, anthracenyl, terphenyl, phenanthryl, triphenylene, The aryl group having 6 to 18 carbon atoms may be an aryl group having 6 to 12 carbon atoms, such as phenenyl, pyrenyl and naphthacene.

[0210] Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, phenethyl (2-phenylethyl), 9-fluorenyl, naphthylmethyl, 1-tetralinyl (tetralinyl), l ) group, and may be an arylalkyl group having 7 to 15 carbon atoms.

[0211] The alkylaryl group having 7 to 30 carbon atoms may be an alkylaryl group having 7 to 20 carbon atoms such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, etc.; and the alkylaryl group having 7 to 15 carbon atoms such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, etc.

[0212] (iii) with R 3 ~R 6 The total carbon number of the corresponding substituent is preferably 1-30, more preferably 2-25, and even more preferably 4-20.

[0213] Examples of (iii) include: (iii-A) a linear alkyl group having 1 to 30 carbon atoms, a branched non-cyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, and an alkylaryl group having 7 to 30 carbon atoms; (iii-B) a group in which each group in (iii-A) is substituted with one or two or more of the above-mentioned heteroatoms; (iii-C) a group in which each group in (iii-A) is substituted with one or two or more of the above-mentioned substituents containing heteroatoms; and (iii-D) a group in which each group in (iii-A) is substituted with one or two or more of the above-mentioned heteroatoms and with one or two or more of the substituents containing heteroatoms. Examples of (iii-C) include, for example, an alkyl group substituted with an alkoxy group, and an aryl group substituted with an alkoxycarbonyl group or an acyloxy group.

[0214] Examples of the (iii) hydrocarbon group having 1 to 30 carbon atoms which may contain at least one hetero atom include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, 2,4,6-triphenylphenyl, 2,6-diisopropylphenyl, 9-anthryl, pentafluoroethyl, pentafluorophenyl, phenyl and benzyl.

[0215] (iv) is a substituent containing a heteroatom, selected from OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group (here, R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R bEach independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, and y represents 0, 1 or 2).

[0216] Examples of the above-mentioned (iv) include hydroxyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, phenoxy, p-methylphenoxy, p-methoxyphenoxy, ethoxycarbonyl, tert-butoxycarbonyl, phenoxycarbonyl, dimethylamide, acetyl, benzoyl, acetoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, tert-butylthio, phenylthio, methylsulfonyl, phenylsulfonyl, methylsulfonyloxy, phenylsulfonyloxy, penta-butylthio, methylsulfonyloxy ... Fluorosulfur group (SF5), dimethyl phosphate group, cyano group, amino group (NH2), methylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, cyclohexylamino group, methylethylamino group, methyl-n-propylamino group, methylcyclohexylamino group, carbazolyl group, piperidinyl group, trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, trimethoxysilyl group, triethoxysilyl group, trimethylsiloxy group, trimethoxysiloxy group, sodium carboxylate group, sodium sulfonate group, potassium sulfonate group, sodium phosphate group, potassium phosphate group, etc.

[0217] In addition, R 3 , R 4 , R 5 and R 6 Adjacent substituents are optionally linked to each other to form a 5-8 membered, alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from oxygen, nitrogen or sulfur atoms. In the formed ring structure, the condensed ring optionally contains an aromatic ring. Examples of the formed ring include 1,2-cyclopentene, 1,2-cyclohexene, 1-oxo-2,3-cyclopentene, 1-oxo-2,3-cyclohexene, 1,2-dihydroacenaphthene, 9,10-dihydroanthracene, etc.

[0218] Among them, from the viewpoint of ligand stability, the above R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above, and more preferably R 5 is an atom or group selected from the group consisting of (i) and (iii) above, and R 6 For a compound selected from the group consisting of (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a) y The atoms or groups in a group.

[0219] In particular, when with X 1 The adjacent R 5 and R 6 When at least one of X is an electron-withdrawing group, the performance as an olefin polymerization catalyst is further improved, which is preferred. 1 The adjacent R 5 and R 6 Both of them may be electron-withdrawing groups. As the electron-withdrawing group, trifluoromethyl, pentafluorophenyl, methoxycarbonyl, phenoxycarbonyl, SF5, toluenesulfonyl, mesyl, nitro, methylcarbonyl, phenylcarbonyl and the like are preferably used.

[0220] In addition, from the perspective of synthesis difficulty and economic rationality, the above R 3 and R 4 At least one of them may be an atom or group selected from the group consisting of (i), (iii) and (iv) above, and the above R 3 and the above R 4 At least one of them may be a hydrogen atom.

[0221] n is 0, 1, 2, 3 or 4. When n is 0, E 1 With X 1 , R 5 and R 6 The carbon atoms to which they are bonded are directly bonded. The value of n is related to the connection E 1 and X 1 From the perspective of structural stability of the complex, n can be 0, 1 or 2. The structure of the complex is stable when a 5-membered ring is formed, so n is preferably 1.

[0222] In the above general formula (A), R 1 It represents a hydrocarbon group represented by the following general formula (B) or (C).

[0223]

[0224] [In formula (B) and formula (C),

[0225] *Indicates the same as E 1 The connection key,

[0226] R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A), R 7 , R 8 , R 9 and R 10 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom,

[0227] A 1 , A 2 , A 3 and A 4 Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)- (herein, R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which optionally contains at least one heteroatom.).

[0228] in,

[0229] In formula (B), A 1 , A 2 , A 3 and A 4 At least two of them are -C(R)2-,

[0230] In formula (C), A 3 and A 4 At least one of them is -C(R)2- and R 12 and R 13 At least one of them is an atom or group selected from the group consisting of (i) and (iii) above, or A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 Each of them is an atom or a group selected from the group consisting of (i) and (iii) above.

[0231] W 1 and W 2 Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8 and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R 10 Does not exist.

[0232] h and i are each independently an integer of 1 to 6,1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R 7 , R 8 , R 9 and R 10 They may be the same or different.]

[0233] In formula (B) and formula (C), A 1 , A 2 , A 3 and A 4 Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)- (herein, R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may optionally contain at least one heteroatom.). The hydrocarbon group having 1 to 20 carbon atoms which may optionally contain at least one heteroatom in the above R may be the same as the hydrocarbon group having 1 to 20 carbon atoms which may optionally contain at least one heteroatom in the above (iii). From the viewpoint of ease of synthesis and economic rationality, the above R may be a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, may be a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, may be a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, or may be a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

[0234] In formula (B) and formula (C), W 1 and W 2 Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8 and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R 10 Does not exist.

[0235] In formula (B) and formula (C), W 1 and W 2 From the viewpoint of ligand stability, each independently may be a carbon atom or a silicon atom, and may be a carbon atom.

[0236] In formula (B) and formula (C), R 7 , R 8 , R 9 , R 10 , R 11 , R12 and R 13 Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A).

[0237] From the perspective of synthesis difficulty and economic rationality, R 7 , R 8 , R 9 , R 10 and R 11 Each independently may be an atom or a group selected from the group consisting of (i), (iii) and (iv) above. 7 , R 8 , R 9 , R 10 and R 11 The above (iii) may be an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, particularly from the viewpoint of ease of synthesis and economic rationality.

[0238] In addition, R 7 , R 8 , R 9 and R 10 Each independently optionally adjacent substituent is bonded to each other and to the W to which they are bonded 1 or W 2 together to form a 5- to 8-membered, alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom. 1 or W 2 When there are 2, R 7 , R 8 , R 9 and R 10 Each independently optionally adjacent substituent is connected to each other and to the two W to which they are bonded 1 or 2 Ws 2 Together they form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring.

[0239] R 7 , R 8 , R 9 and R 10 can be bonded to W 1 or W 2 Together they form an alicyclic ring, and may be an alkylene group having 4 to 7 carbon atoms formed by connecting adjacent substituents to each other. 7 and R 8 can be the W to which they are bonded 1 An alkylene group having 5 carbon atoms such as forming a 6-membered ring. 7 , R 8 , R9 and R 10 The aryl groups of the adjacent substituents are each independently connected to each other and to the W to which they are bonded. 1 or W 2 For example, adjacent R 7 and R 8 can be the W to which they are bonded 1 In this case, W 1 When it is a carbon atom, through W 1 and R 7 and R 8 To form a fluorenylene group.

[0240] In addition, R 7 , R 8 , R 9 and R 10 The two Ws they bond to 1 or 2 Ws 2 They may be alkylene groups having 3 to 6 carbon atoms, or alkylene groups having 3 or 4 carbon atoms, such as forming a 5- or 6-membered ring. 7 , R 8 , R 9 and R 10 The two Ws they bond to 1 or 2 Ws 2 Together they form an aromatic ring having 6 to 12 carbon atoms.

[0241] Furthermore, it may be a heterocyclic ring in which at least one carbon atom of the above-mentioned alicyclic ring or aromatic ring is substituted with a heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom.

[0242] In addition, R 7 , R 8 , R 9 and R 10 The alicyclic ring, aromatic ring or heterocyclic ring formed in the above formula (A) may further have an atom or group selected from the group consisting of (ii) to (iv) defined in the above formula (A) as a substituent, and the substituent may be a halogen atom.

[0243] From the perspective of synthesis difficulty and economic rationality, R 11 It may be a hydrogen atom.

[0244] In addition, from the perspective of synthesis difficulty and economic rationality, R 12 and R 13 Each independently may be an atom or a group selected from the group consisting of (i), (iii) and (iv) above. 12 and R 13In the above (iii), from the viewpoint of ease of synthesis and economic rationality, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms may be used. 12 and R 13 From the perspective of synthesis difficulty and economic rationality, the above (iv) can be used for OR b 、C(O)OR b 、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x Or NO2, etc.

[0245] In formula (B) and formula (C), h and i are each independently an integer of 1 to 6, and W 1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R 7 , R 8 , R 9 and R 10 They may be the same or different.

[0246] From the perspective of ease of synthesis and economic rationality, h and i can each independently be an integer of 1 to 3, can be 1 or 2, or can be 1.

[0247] Among them, in formula (B), A 1 , A 2 , A 3 and A 4 At least two of them are -C(R)2-.

[0248] In formula (B), the group other than -C(R)2- may be an oxygen atom, a sulfur atom or -N(R)-, and may be an oxygen atom, from the viewpoint of ease of synthesis and economic rationality.

[0249] Wherein, A in formula (B) may be 1 , A 2 , A 3 and A 4 Two of them are -C(R)2- and two of them are groups other than -C(R)2-, which can be A 2 and A 4 is -C(R)2- and A 1 and A 3 is a group other than -C(R)2-.

[0250] Among them, in formula (C), A 3 and A 4 At least one of them is -C(R)2- and R 12 and R 13 At least one of A is an atom or group selected from the group consisting of (i) and (iii) above, or 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 Each of them is an atom or a group selected from the group consisting of (i) and (iii) above.

[0251] In the formula (C), the group other than -C(R)2- may be an oxygen atom, a sulfur atom or -N(R)-, and may be an oxygen atom, from the viewpoint of ease of synthesis and economic rationality.

[0252] Wherein, A in formula (C) may be 3 and A 4 One of them is -C(R)2- and the other is a group other than -C(R)2-, and R 12 and R 13 One of them is (i) a hydrogen atom or (iii) a hydrocarbon group having 1 to 30 carbon atoms which optionally contains at least one heteroatom and the other is (iv) a group containing a heteroatom as described above; or it may be A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 are (i) a hydrogen atom or (iii) a hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom. 3 is a group other than -C(R)2-, A 4 -C(R)2-, R 12 is the group containing a heteroatom as described above (iv) and R13 It is (i) a hydrogen atom or (iii) a hydrocarbon group having 1 to 30 carbon atoms which may contain at least one hetero atom.

[0253] In the above general formula (A), R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, which is different from the hydrocarbon group represented by the above general formula (B) or (C) and which optionally contains at least one heteroatom, and l is 1 or 2. When l is 2, R 2 Does not exist.

[0254] As R 2 The hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom in (iii) may be the same as the hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom in (iii) above.

[0255] As R 2 , can be a hydrocarbon group having 3 to 20 carbon atoms, for example, n-propyl, isopropyl, isobutyl, tert-butyl, 3-pentyl, 2,6-dimethyl-4-heptyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantyl, (1R,2S,5R)-2-isopropyl-5-methylcyclohexane-1-yl (menthyl), phenyl, 2-methoxyphenyl, 2,6-diethylphenyl (DEP), 2,6-dimethoxyphenyl (DMP), 2',6'-dimethoxy[1,1'-biphenyl]-2-yl, (1R,2S,5R)-2-isopropyl-5-methylcyclohexane-1-yl, etc. are preferably used.

[0256] From the perspective of synthesis difficulty and economic rationality, l can be 2.

[0257] In the above general formula (A), Z is a hydrogen atom, a leaving group, or a cation having a valence of 1 or more and 4 or less, and m is an integer of 1 or more and less than the valence of Z. When m is 1, Z may be exemplified by a hydrogen atom, a lithium ion, a sodium ion, a potassium ion, etc. When m is 2, Z may be exemplified by a magnesium ion, a calcium ion, a zinc ion, etc. As leaving groups, hydrogen atoms, R b S(O)2 group (here, R b represents a hydrocarbon group having 1 to 20 carbon atoms), C(F) 3 S(O)2 group, R b S(O)2-based, TiOR b As cations, specifically, ammonium, quaternary ammonium or phosphonium, and metal ions of Groups 1 to 14 of the periodic table can be cited. Among these, hydrogen atoms, NH 4+ , (R b )4N + (Here, R b As mentioned above, the 4 Rs b They may be the same or different. The same shall apply to the following. )、(R b)4P + , Li + 、Na + , K + , Cu + 、Ag + 、Au + ,Mg 2+ , Ca 2+ 、Al 3+ , more preferably a hydrogen atom, (R b )4N + , Li + 、Na + , K + 、Ag + .

[0258] Specific examples of the compound represented by the general formula (A) include the following compounds, but are not limited to these.

[0259]

[0260]

[0261]

[0262] (In the formula, R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom.)

[0263] The compound represented by the above general formula (A) can be synthesized based on a known synthesis method. 1 H(R 1 ) l (R 2 ) 2-l In the presence of alkali or acid, 1 H(R 1 ) l (R 2 ) 2-l The compound represented by the above general formula (A) can be synthesized by reacting E in the presence of a base. 1 CH3(R 1 ) l (R 2 ) 2-l The above general formula (A) is synthesized by reacting with a ketone. Representative references include Patent Document 5, Non-Patent Document 7, Journal of Fluorine Chemistry 2002, 117, P121-129, and the like.

[0264] E 1 H(R 1 ) l (R2 ) 2-l The compounds shown can be appropriately selected from commercial products. When commercial products are not available, E can be synthesized by reacting a phosphine halide with a nucleophilic agent such as an organic lithium or organic magnesium. 1 X(R 1 ) l (R 2 ) 2-l (X is a halogen atom) and then a hydride reducing agent such as lithium aluminum hydride is allowed to act to synthesize. Representative references include Japanese Patent Application Laid-Open No. 2021-113174.

[0265] For R 1 The compound into which the substituent represented by the above general formula (B) or (C) is introduced can be appropriately selected and commercially available. When commercially available products are not available, they can be synthesized by intermolecular or intramolecular cyclization reactions. Examples of such cyclization reactions include nucleophilic substitution reactions of dihalogen molecules, Friedel-Crafts reactions, cyclization reactions using transition metals, and the like. Representative references include RSC Advances 2014, 4, P16312-16319, Bioorg. Med. Chem. Lett. 2014, 24, P2379-2382., Chem. Eur. J. 2013, 19, P17349-17357., Org. Biomol. Chem. 2018, 16, P8976-8983., and the like.

[0266] The compound represented by the general formula (A) acts as a ligand capable of forming a complex with the transition metal compound represented by the general formula (E) or (F) described later. 1 is an oxygen atom and E 1 The compound represented by the general formula (A) which is a phosphorus atom has a structure in which phosphorus and oxygen are bonded via an alkylene group, and thus such a group of compounds is sometimes referred to as an alkylene-linked phosphine alkoxide (ALPHA) ligand.

[0267] I-2. Catalyst composition for olefin polymerization

[0268] The olefin polymerization catalyst composition according to the first embodiment of the present invention contains the compound represented by the above-mentioned general formula (A) and a transition metal compound represented by the following general formula (E) or (F).

[0269]

[0270] [In formula (E) and formula (F),

[0271] M 1、M 2 and M 3 Each independently represents a nickel atom or a palladium atom, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 9 and L 10 Each independently represents the coordination in M 1 、M 2 or M 3 The ligand, L 7 and L 8 Indicates coordination with M 2 and M 3 The ligand

[0272] q is 0, 1, or 2,

[0273] L 1 and L 2 Optionally bonded to each other to form a 1 The ring,

[0274] L 3 and L 4 Optionally bonded to each other to form a 1 The ring,

[0275] L 5 and L 6 Optionally bonded to each other to form a 2 The ring,

[0276] L 9 and L 10 Optionally bonded to each other to form a 3 ring.]

[0277] In the olefin polymerization catalyst composition according to the first embodiment of the present invention, the compound represented by the general formula (A) may be the same as the compound represented by the general formula (A) according to the first embodiment, and thus the description thereof is omitted here.

[0278] In the compound represented by the above general formula (A), the phosphorus atom or the like 1 The upper bond has as R 1 In the hydrocarbon groups represented by the above general formula (B) or (C), relative to the phosphorus atom, E 1 Substituents in the ortho position to the bonded carbon atom (A 1 and A 3) forms a ring structure, thereby inhibiting the free rotation of the substituent at the ortho position. On the other hand, the hydrocarbon group represented by the general formula (B) or (C) has a suitable volume. We believe that when two phenyl groups having freely rotatable substituents at the ortho positions are bonded to E1, when the compound is used as a ligand, the steric hindrance near the active center, i.e., the transition metal, becomes too high, and the activity is easily reduced. It is also believed that the unsubstituted phenyl group bonded to E 1 In the case of using the compound as a ligand, the steric hindrance near the transition metal is insufficient, making it difficult to increase the molecular weight. We believe that when the compound represented by the general formula (A) is used as a ligand of a transition metal compound, appropriate steric hindrance can be maintained near the transition metal, thereby maintaining a high molecular weight and improving the activity of the catalyst.

[0279] In addition, it is considered that in the compound represented by the above general formula (A), phosphorus atoms such as E 1 The substituent of the phenyl group bonded thereto is a substituent containing a heteroatom such as an oxygen atom in the ring structure, thereby further improving the coordination force of the heteroatom such as the oxygen atom to the catalyst center metal, thereby increasing the catalyst activity and further increasing the molecular weight of the obtained polymer.

[0280] In the above general formula (E) or (F), M 1 、M 2 and M 3 Each independently represents a nickel atom or a palladium atom. Here, the valence of M refers to the formal oxidation number used in organometallic chemistry.

[0281] That is, the number of charges remaining on the atoms of a certain element when the electron pair in the bond formed by the element is assigned to an element with a high electronegativity. Nickel atoms are preferred because they are available at a low cost.

[0282] In the above general formula (E) or (F), L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 9 and L 10 Each independently represents the coordination in M 1 、M 2 or M 3 The ligand represents a -1 valent electron-donating ligand or a neutral electron-donating ligand.

[0283] The -1-valent electron-donating ligand is an electronegative ligand that forms a σ bond with the central metal, i.e., M, or a ligand that donates delocalized π electrons to three or more carbon atoms. An example of a neutral electron-donating ligand is an electrically neutral ligand that can form a coordination bond by coordinating an unpaired electron to M. The ligand is a molecule containing an atom having an unpaired electron, and examples of the atom having an unpaired electron include nitrogen atoms, phosphorus atoms, arsenic atoms, oxygen atoms, sulfur atoms, and selenium. In addition, other examples of neutral electron-donating ligands include molecules such as ethylene and cyclooctadiene (cod) that form a π coordination bond by donating π electrons, and molecules such as dibenzylideneacetone (dba) that have both an olefin and a heteroatom coordinated to a metal. As a ligand that can be used as L 1 ~L 6 , L 9 , L 10 As the ligand, acetonitrile, isonitrile, carbon monoxide, ethylene, tetrahydrofuran, etc., which are known as neutral ligands for metal complexes, and ligands that provide π electrons, such as allyl and cyclopentadienyl, can be used. 2 R'R"R"' or X 2 The molecule shown by R'R" acts as a ligand. Here, E 2 Indicates N, P or As, X 2 represents O, S or Se, R', R" and R'" each independently represent a hydrogen atom; an optionally substituted alkyl group, alicyclic group, alkoxy group, aryl group or aryloxy group having 1 to 30 carbon atoms; or, each independently represents an amino group or a silyl group in which at least one hydrogen atom is substituted by a hydrocarbon group having 1 to 30 carbon atoms, R' and R" are optionally connected to form a heterocyclic structure, and R', R" and R'" optionally contain E 2 And bond to form an aromatic heterocyclic structure. 1 With L 2 , L 3 With L 4 , L 5 With L 6 , L 9 With L 10 Optionally bonded to each other to form a 2 or M 3 When these groups form a ring, the minimum number of ring members of the ring including M is 5-membered ring to 10-membered ring.

[0284] L 1 ~L 6 , L 9 , L 10The electron-donating ligand optionally having a valence of -1 is preferably selected so that the valence of the metal complex becomes 1 or 2 in order to facilitate the reaction of forming the metal complex. 1 ~L 6 , L 9 , L 10 The number of -1-valent electron-donating ligands in the moiety is preferably 0 to 2.

[0285] L as a -1 electron-donating ligand 1 ~L 6 , L 9 , L 10 , may be a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms and optionally containing at least one hetero atom, the structure of the hydrocarbon part may be any of a straight chain, a branched chain, or a cyclic structure, and may optionally form a ring containing a hetero atom. The preferred carbon number is 1 to 16, and more preferably 1 to 10.

[0286] L as a -1 electron-donating ligand 1 ~L 6 , L 9 , L 10 Specific examples of include, independently, hydride group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, neopentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group, benzyl group, trimethylsilylmethyl group, phenyl group, p-methylphenyl group, p-fluorophenyl group, fluoride group, chloride group, bromide group, iodide group, etc. Preferred examples include hydride group, methyl group, neopentyl group, benzyl group, trimethylsilylmethyl group, phenyl group, p-fluorophenyl group, chloride group, bromide group, iodide group, etc.

[0287] In addition, as L 1 ~L 6 , L 9 , L 10 Preferred examples include phosphines, pyridines, piperidines, alkyl ethers, aryl ethers, alkyl aryl ethers, cyclic ethers, alkyl nitrile derivatives, aryl nitrile derivatives, alcohols, amides, aliphatic esters, aromatic esters, amines, cyclic unsaturated hydrocarbons, etc. Further preferred examples include phosphines, pyridines, cyclic ethers, aliphatic esters, aromatic esters, cyclic olefins, and particularly preferred examples include trialkylphosphines, triarylphosphines, pyridine, lutidine, picoline, R b C(O)O - (Here, R b As defined above). It should be noted that, as L 1 With L 2 , L 3 With L4 , L 5 With L 6 , L 9 With L 10 Optionally bonded to each other to form a 2 or M 3 Examples of the ring include a cyclooct-1-enyl group, an acetylacetonyl group, a tetramethylethylenediamino group, and a 1,2-dimethoxyethane group, which are also preferred embodiments.

[0288] L 7 and L 8 Indicates coordination with M 2 and M 3 ligands, respectively with M 2 and M 3 The bond is called a three-center four-electron bond. 7 or L 8 Examples of the ligand of L include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkoxy group having 1 to 6 carbon atoms, a hydrocarbon-substituted amino group having 1 to 6 carbon atoms, and an acetyl group. 7 and L 8 Preferred examples include a fluoride group, a chloride group, a bromide group, an iodide group, a methyl group, an ethyl group, a propyl group, a methoxy group, a phenoxy group, a dimethylamide group, a hydride group, a thiomethoxy group, a thiophenoxy group, and an acetyl group. More preferred examples include a fluoride group, a chloride group, a bromide group, an iodide group, a methyl group, a methoxy group, a phenoxy group, a hydride group, a thiomethoxy group, a thiophenoxy group, and an acetyl group. Further preferred examples include a chloride group, a bromide group, an iodide group, a methoxy group, a phenoxy group, and an acetyl group.

[0289] In the above general formula (E), q is a value of 0, 1 or 2.

[0290] As specific examples of the compounds represented by the above general formula (E) or formula (F), the following compounds can be listed, but are not limited to these. In addition, Ni(CH2C(H)CH2)2, Ni(CH2C(Me)CH2)2, Ni(CH2Si(Me)3)2(Py)2(hereinafter, Py represents pyridine.), Ni(CH2Si(Me)3)2(Lut)2(hereinafter, Lut represents 2,6-dimethylpyridine.), NiPh2(Py)2, NiPh2(Lut)2, Pd(OC(O)CH3)2, etc. can be listed.

[0291] These compounds are considered to form complexes with the compound represented by the general formula (A).

[0292]

[0293] The compound represented by the general formula (A) can be used as a catalyst for olefin polymerization in the form of a composition with the transition metal compound represented by the general formula (E) or (F) or in the form of a reaction product with the transition metal compound, i.e., a metal complex. In the olefin polymerization reaction, the product used as a catalyst can be used after the compound represented by the general formula (A) and the transition metal compound represented by the general formula (E) or (F) are reacted, or the product can be used directly in the polymerization reaction without separating and washing the product from the reaction system. The method for reacting these compounds can use a method known in the synthesis of metal complexes. The operation is preferably carried out under an inert gas. The reaction is carried out in a uniform solvent, and as a solvent, a common hydrocarbon reaction solvent can be used, preferably toluene. The concentration of the transition metal compound in the reaction solvent can be freely set with the saturation concentration as the upper limit, preferably in the range of 1 mM to 50 mM. There is no restriction on the mixing order of the compound represented by the general formula (A) (ligand) and the transition metal compound represented by the general formula (E) or (F). A solvent may be added to a mixture of a solid ligand and a solid transition metal compound, or a dissolved transition metal compound may be added to the solid ligand. The mixing ratio of the ligand to the transition metal compound is preferably set in the range of ligand:metal=1:1 to 1:10. The mixing temperature may be appropriately set within the range of 20°C or above with the boiling point of the solvent as the upper limit. The mixing temperature is preferably in the range of 35°C to 45°C. The time required for mixing may preferably be set in the range of 1 minute to 24 hours, more preferably 10 minutes to 30 minutes. One embodiment of the present invention is a method for producing a catalyst for olefin polymerization, comprising a step of reacting a compound represented by the above-mentioned general formula (A) with a transition metal compound represented by the above-mentioned general formula (E) or (F).

[0294] I-3. Metal complex

[0295] In another aspect, a first embodiment of the present invention provides a metal complex represented by the following general formula (D).

[0296]

[0297] [In formula (D),

[0298] X 1 、E 1 ,n,R 1 , R 2 , l, R 3 , R 4 , R 5 and R 6 As defined in the above-mentioned [1-1], that is, in the compound represented by the general formula (A) of the above-mentioned first embodiment,

[0299] M 1, L 1 and L 2 As defined in the transition metal compound represented by the above general formula (E) or (F).]

[0300] Specific examples of the metal complex represented by the general formula (D) include the following complexes: However, these are for illustration only, and the complexes in the method of the present invention are not limited to these specific examples.

[0301]

[0302]

[0303] (In the formula, R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0304]

[0305] The metal complex represented by the above general formula (D) of the present invention can be prepared by a method including a step of reacting the compound represented by the above general formula (A) with the transition metal compound represented by the above general formula (E) or (F), or by a known method. Those skilled in the art can prepare the metal complex represented by the above general formula (D) of the present invention based on a known complex preparation method and by making appropriate changes such as raw material changes.

[0306] For example, when the metal complex represented by the general formula (D) is produced, when the compound represented by the general formula (A) is reacted with the transition metal compound represented by the general formula (E) or (F), the L in the general formula (D) may also be present. 1 , L 2 Coordination compounds and covalent compounds in which substitution is carried out at the site.

[0307] When nickel or palladium is used as M in the present invention, the stability of the generated metal complex may be increased by allowing a Lewis basic coordination compound to coexist in the system. In this case, the coordination compound may coexist as long as it does not inhibit the polymerization reaction or copolymerization reaction of the present invention.

[0308] The coordination compound used in the present invention can be a hydrocarbon compound having 1 to 20 carbon atoms and having at least one selected from the group consisting of oxygen atoms, nitrogen atoms, phosphorus atoms, arsenic atoms, sulfur atoms and selenium atoms as an atom capable of forming a coordination bond, or a hydrocarbon compound having a carbon-carbon unsaturated bond capable of coordinating with a transition metal and optionally containing a heteroatom, which can be used together with the above-mentioned L 1 The neutral electron donating ligands in the above have the same meaning.

[0309] In addition, the above covalent compound used in the present invention refers to a compound in which the ligand derived from the transition metal compound is replaced by the above L in the metal complex represented by the general formula (D). 1 The above covalent compound may be an organometallic compound.

[0310] As a monovalent electron-donating ligand, a hydrocarbon group having 1 to 20 carbon atoms and optionally containing at least one heteroatom can be incorporated into the polymer as a starting terminal of the polymerization reaction and greatly contributes to the initial rate of the polymerization reaction. Therefore, when preparing the metal complex represented by the general formula (D), it is preferred to use a covalent compound for introducing a hydrocarbon group having 1 to 20 carbon atoms and optionally containing at least one heteroatom in combination according to the circumstances.

[0311] As the above-mentioned covalent compound, there can be mentioned organic lithium compounds, which can be R 14 Li (here, R 14 The organic lithium compound may be an organic lithium compound having a hydrocarbon group having 1 to 20 carbon atoms and optionally containing a hetero atom. Examples of the organic lithium compound having a hydrocarbon group having 1 to 10 carbon atoms include methyl lithium, n-butyl lithium, phenyl lithium, neopentyl lithium, benzyl lithium, trimethylsilyl methyl lithium, and p-fluorophenyl lithium. Among them, methyl lithium and phenyl lithium are preferred, and methyl lithium is more preferred.

[0312] I-4. Catalyst for olefin polymerization

[0313] The olefin polymerization catalyst according to the first embodiment of the present invention includes the olefin polymerization catalyst composition according to the first embodiment of the present invention.

[0314] Furthermore, the olefin polymerization catalyst according to the first embodiment of the present invention contains the metal complex represented by the general formula (D) according to the first embodiment.

[0315] The olefin polymerization catalyst of the present invention comprises a metal complex which is a product of a compound represented by the above general formula (A) and a transition metal compound represented by the above general formula (E) or (F) during the polymerization reaction of olefins, or a metal complex represented by the above general formula (D) (hereinafter, these may be collectively referred to as "metal complex catalysts").

[0316] In the olefin polymerization catalyst of the first embodiment of the present invention, the olefin polymerization catalyst composition of the first embodiment of the present invention and the metal complex represented by the general formula (D) of the first embodiment may be the same as described above, and thus description thereof is omitted here.

[0317] As shown in the examples described below, the olefin polymerization catalyst of the present invention can be used as it is without any purification, using the olefin polymerization catalyst composition of the present invention and the metal complex represented by the general formula (D) as a catalyst for olefin polymerization.

[0318] In the olefin polymerization catalyst of the present invention, the compound represented by the above general formula (A) and the transition metal compound represented by the following general formula (E) or (F) of the olefin polymerization catalyst composition may be used alone or in combination of multiple components. In addition, the olefin polymerization catalyst composition may optionally contain a metal complex represented by the above general formula (D).

[0319] The metal complex represented by the general formula (D) contained in the olefin polymerization catalyst of the present invention may be a single type or a mixture of two or more types.

[0320] In the catalyst for olefin polymerization of the present invention, a co-catalyst may be added in addition to the metal complex catalyst. As the co-catalyst, for example, an organometallic compound containing an element of Group 1, 2 or 13 of the periodic table may be mentioned. In particular, a compound represented by the following general formula (1), a compound represented by the general formula (2) or an organoaluminum-oxy compound may be mentioned. A plurality of types of these compounds may be included in the catalyst composition.

[0321] General formula (1): Q(R 20 )(R 21 )R 22

[0322] The compound represented by the general formula (1) is Q(R 20 )(R 21 )R 22 A boron or aluminum compound represented by (wherein Q represents boron (B) or aluminum (Al), R 20 , R 21 and R 22 Each independently represents a hydrogen atom; an optionally substituted alkyl group, alicyclic group, alkoxy group, aryl group or aryloxy group having 1 to 30 carbon atoms; or each independently represents an amino group or a silyl group in which one or more hydrogen atoms are substituted by a hydrocarbon group having 1 to 30 carbon atoms.

[0323] As R 20 ~R 22 , the above R applies 3 The examples described in the description of etc. are preferably hydrocarbon groups such as alkyl groups and aryl groups, or alkyl groups or aryl groups substituted with halogen (particularly fluorine) such as trifluoromethyl and perfluorophenyl groups, from the viewpoint of the ease of preparation and availability of the compounds.

[0324] Examples of the compound represented by the general formula (1) are trimethylborane, trimethoxyborane, perfluoromethylborane, triphenylborane, tri(perfluorophenyl)borane, triphenoxyborane, tri(dimethylamino)borane, tri(diphenylamino)borane, trimethylaluminum, triethylaluminum, tri(n-propyl)aluminum, tri(n-butyl)aluminum, triisobutylaluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, tri(n-decyl)aluminum, diethylaluminum hydride, diethylethoxyaluminum, dimethylamide diethylaluminum, diisobutylaluminum hydride, and the like, but are not limited thereto.

[0325] The above general formula (2): [C(R 23 )(R 24 )R 25 ] + [Q(R 26 )(R 27 )(R 28 )R 29 ] -

[0326] The compound represented by the general formula (2) is [C(R 23 )(R 24 )R 25 ] + [Q(R 26 )(R 27 )(R 28 )R 29 ] - A salt of boron or aluminum with a carbon cation represented by 23 ~R 29 Independently, and R 20 Same meaning.)

[0327] As R 23 ~R 29 , the above R applies 3 From the examples described in the description of etc., hydrocarbon groups such as alkyl and aryl are preferred from the perspective of easy preparation and availability of the compound, and bulky hydrocarbon groups such as tert-butyl and aryl are more preferred from the perspective of easy availability of carbocations.

[0328] Examples of the compound represented by the general formula (2) include, but are not limited to, trityltetramethylborate, trityltetra(perfluoromethyl)borate, trityltetraphenylborate, trityltetra(perfluorophenyl)borate, and trityltetra(di(trifluoromethyl)phenyl)borate.

[0329] The compound represented by the general formula (1) or (2) may be obtained by using commercially available products or by appropriately modifying a known method according to the substituents possessed by the compound.

[0330] In addition to the compound represented by the general formula (1) or (2), an organic aluminum oxide compound may be added to the catalyst for olefin polymerization of the present invention. Examples of organic aluminum compounds include methylaluminoxane (MAO) and modified methylaluminoxane (MMAO), and commercial products may be used. MMAO is preferred because it is easily available and has good operability. Commercial products may be used for MAO and MMAO, and there is no limitation on the grade.

[0331] In addition to the compounds containing Group 13 elements exemplified above, compounds containing Group 1 metals represented by alkyl lithiums such as methyl lithium and n-butyl lithium, compounds containing Group 2 metals such as Grignard reagents, and conventionally known organometallic compounds can be used as co-catalysts. These compounds can also be commercially available products, and there is no limitation on the grade, etc.

[0332] These co-catalysts can be used under the same conditions as the above-mentioned metal complex catalysts, preferably in an inert gas atmosphere and away from oxygen and moisture. The amount used when added can be appropriately determined by those skilled in the art.

[0333] Furthermore, the contact between the metal complex catalyst and the co-catalyst can be carried out not only during the preparation of the catalyst but also during the prepolymerization of olefin or during the polymerization of olefin.

[0334] The contact between the metal complex catalyst and the co-catalyst is preferably carried out in an inert gas such as nitrogen in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene, etc. The contact can be carried out at a temperature between -20°C and the boiling point of the solvent, and is particularly preferably carried out at a temperature between room temperature and the boiling point of the solvent.

[0335] I-5. Method for producing olefin polymer

[0336] The method for producing an olefin-based polymer according to the first embodiment of the present invention is characterized by polymerizing or copolymerizing olefin in the presence of the olefin polymerization catalyst according to the first embodiment of the present invention.

[0337] The olefin in the present invention may be an acyclic olefin or a cyclic olefin, and may be at least one selected from the group consisting of an acyclic olefin having 2 to 22 carbon atoms and a cyclic olefin having 4 to 20 carbon atoms.

[0338] As the acyclic olefin in the present invention, the general formula: CH2=CHR 30 Here, R 30 R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may have a branch, a ring and / or an unsaturated bond. 30When the carbon number of R is greater than 20, sufficient polymerization activity tends to be not exhibited. 30 Preferred olefins are olefins which are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms.

[0339] Examples of acyclic olefins other than α-olefins include 2-butene, 2-pentene, and 2-hexene.

[0340] Examples of the cyclic olefin having 4 to 20 carbon atoms include cyclobutene, cyclopentene, cyclohexene, cycloheptene, norbornene, and norbornadiene.

[0341] As preferred olefins, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, vinylcyclohexene, styrene, 4-methylstyrene and norbornene can be cited. From the perspective of the manufacturing efficiency of the polymer, it is particularly preferred to be selected from one or more of the group consisting of ethylene, propylene, 1-butene and norbornene, and ethylene is further preferred. It should be noted that as an olefin, only one olefin may be used, or two or more olefins may be used simultaneously.

[0342] Examples of polar group-containing monomers include monomers obtained by introducing polar functional groups (polar groups) into acyclic olefins and cyclic olefins. Examples of monomers obtained by introducing polar groups into α-olefins among acyclic olefins include monomers of the general formula: CH2=C(R 30 )(R 31 ) is a polar group-containing monomer. A preferred example of a polar group-containing monomer is (meth)acrylate. Here, R 30 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 31 Represents -C(O)OR 32 (Here, R 32 represents a hydrocarbon group having 1 to 20 carbon atoms), -C(O)N(-R 32’ )2(Here, R 32’ Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms), a cyano group or an optionally substituted aryl group. 30 It is preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. 30 More preferably, it is a hydrogen atom or a methyl group. 31 , as long as it is the above-mentioned substituent, there is no particular limitation, but -C(O)OR 32 or aromatic. In this case, R 32 When the carbon number of R exceeds 20, the polymerization activity tends to decrease. 32 It is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 8 carbon atoms.

[0343] In addition, as R 32 , preferably composed of carbon atoms and hydrogen atoms, but R 32 It may also contain heteroatoms such as oxygen atoms, sulfur atoms, selenium atoms, phosphorus atoms, nitrogen atoms, silicon atoms, fluorine atoms, and boron atoms. Among these heteroatoms, oxygen atoms, silicon atoms, and fluorine atoms are preferred, and oxygen atoms are more preferred. 32’ The preferred range and examples of R 32 same.

[0344] Examples of monomers in which a polar functional group is introduced into a non-cyclic olefin other than α-olefin or a cyclic olefin include monomers in which the above-mentioned R is introduced into any position of the exemplary compounds of the non-cyclic olefin other than α-olefin or the cyclic olefin. 31 Compounds having the substituents shown.

[0345] In addition, as the polar group-containing monomer, vinylene carbonate (1,3-dioxol-2-one) may be mentioned.

[0346] Further preferred examples of the polar group-containing monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluoyl (meth)acrylate, benzyl (meth)acrylate, hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. -aminoethyl ester, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, glycidyl (meth)acrylate, trifluoromethyl (meth)acrylate, 3,3,3-trifluoropropyl (meth)acrylate, perfluoroethyl (meth)acrylate, (meth)acrylamide, (meth)acryloyldimethylamide, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acrylonitrile, methyl 10-undecenoate, 4-acetoxystyrene, vinyl anisole, methyl 5-norbornene-2-carboxylate, tert-butyl 5-norbornene-2-carboxylate, 5-norbornene-2-methanol, 5-norbornene-2-methylamine, 5-norbornene-2-methylpivalamide, 5-norbornene-2-yl acetate, vinylene carbonate, and the like. More preferably, it is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, acrylonitrile, methyl 10-undecenoate, 4-acetoxystyrene, 4-nitrostyrene, vinyl anisole, methyl 5-norbornene-2-carboxylate, tert-butyl 5-norbornene-2-carboxylate, 5-norbornene-2-methylpivalamide, 5-norbornene-2-yl acetate, and vinylene carbonate.

[0347] As the comonomer used for the copolymerization of acyclic olefins such as ethylene, at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins is preferably used.

[0348] As a further preferred example, it is at least one selected from the group consisting of tert-butyl acrylate, methyl acrylate, methyl methacrylate, methyl 10-undecenoate, 4-methylstyrene, 4-acetoxystyrene, norbornene, tert-butyl 5-norbornene-2-carboxylate, 9-decenyl acetate, 1,2-epoxy-9-decene, and vinylene carbonate.

[0349] These monomers may be used alone or in combination of two or more.

[0350] The type of the above monomers can be appropriately selected according to the physical property required for the obtained polymer. In addition, the composition copolymerization of two or more monomers can also be made, and the composition copolymerization consisting of two or more polar group-containing monomers can also be made. The amount of the monomers mixed, the amount ratio between each monomer can be appropriately set according to the physical property required for the obtained multipolymer.

[0351] The method for producing an olefin polymer of the present invention performs polymerization in the presence of the olefin polymerization catalyst of the present invention, and is therefore suitable for a method for copolymerizing at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins with an acyclic olefin.

[0352] In addition, as the copolymerization reaction of the present invention, copolymerization of an olefin and a (meth)acrylic acid ester is mentioned as a preferred embodiment from the viewpoint of polymerization activity.

[0353] In the method for producing olefin polymers of the present invention, an olefin polymerization catalyst comprising the above-mentioned metal complex catalyst is used as a catalyst for polymerization or copolymerization of olefins. Each metal complex catalyst can be used after separation or supported on a carrier. Such support can be carried out in the reactor used for polymerization of olefins, copolymerization of olefins and (meth) acrylic esters, etc., in the presence or absence of these monomers, or in other containers outside the reactor.

[0354] As a usable carrier, any carrier can be used as long as it does not violate the main purpose of the present invention. Usually, inorganic oxides and polymer carriers can be appropriately used. As inorganic oxides, specifically, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc. or mixtures thereof can be listed, and mixed oxides such as SiO2-Al2O3, SiO2-V2O5, SiO2-TiO2, SiO2-MgO, SiO2-Cr2O3 can also be used. In addition, as a carrier, inorganic silicates, polyethylene carriers, polypropylene carriers, polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylate carriers, polyester carriers, polyamide carriers, polyimide carriers, etc. can be used. For these carriers, particle size, particle size distribution, pore volume, specific surface area, etc. are not particularly limited, and any one can be used.

[0355] As inorganic silicates, clay, clay minerals, zeolites, diatomaceous earth, etc. can be used. These may be synthetic products, or naturally occurring minerals may be used. Specific examples of clay and clay minerals include allophane group such as allophane; kaolin group such as dickite, nacrite, kaolinite, and anthracite; halloysite group such as metahalloysite and halloysite; serpentine group such as chrysotile, lizardite, and antigorite; montmorillonite such as sauconite, beidellite, nontronite, saponite, and hectorite; vermiculite minerals such as vermiculite; mica minerals such as illite, sericite, and glauconite; attapulgite, sepiolite, palygorskite, bentonite, wood clay, gairome clay, ferrosilicon, pyrophyllite, and chlorite group.

[0356] These may form a mixed layer. Examples of the artificially synthesized material include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic tapered mica.

[0357] Among these specific examples, preferably listed are kaolinite, nacrite, kaolinite, annularite and other kaolin family; halloysite family such as metahalloyite and halloysite; serpentine family such as chrysotile, lizardite, antigorite; smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite; vermiculite minerals such as vermiculite; mica minerals such as illite, sericite, glauconite; synthetic mica, synthetic hectorite, synthetic saponite, synthetic taenia, and particularly preferably listed are smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite; vermiculite minerals such as vermiculite; synthetic mica, synthetic hectorite, synthetic saponite, synthetic taenia.

[0358] These carriers can be used directly, or can be treated with hydrochloric acid, nitric acid, sulfuric acid, etc. and / or treated with salts such as LiCl, NaCl, KCl, CaCl2, MgCl2, Li2SO4, MgSO4, ZnSO4, Ti(SO4)2, Zr(SO4)2, Al2(SO4)3. In this treatment, the corresponding acid and base can be mixed to generate salts in the reaction system for treatment. In addition, shape control such as pulverization and granulation and drying treatment can be performed.

[0359] In the method for producing an olefin polymer of the present invention, the polymerization reaction can be carried out in the presence or absence of a known additive in addition to the above-mentioned cocatalyst. As the additive, an additive having the effect of stabilizing the generated polymer is preferred. For example, quinone derivatives, hindered phenol derivatives, etc. can be cited as examples of preferred additives.

[0360] Specifically, hydroquinone monomethyl ether, 2,6-di-tert-butyl 4-methylphenol (BHT), a reaction product of trimethylaluminum and BHT, a reaction product of tetravalent titanium alkoxide and BHT, and the like can be used.

[0361] In addition, inorganic fillers and / or organic fillers may be used as additives, and polymerization may be carried out in the presence of these fillers or with the addition of an ionic liquid.

[0362] As a preferred additive in the present invention, Lewis bases can be cited. By selecting a suitable Lewis base, the activity, molecular weight, and copolymerizability of acrylate can be improved. As the amount of Lewis base, relative to the transition metal M in the catalyst component present in the polymerization system, it is 0.0001 equivalents to 1000 equivalents, preferably 0.1 equivalents to 100 equivalents, and more preferably 0.3 equivalents to 30 equivalents. There is no particular restriction on the method of adding Lewis base to the polymerization system, and any method can be used. For example, it can be added to the catalyst for olefin polymerization of the present invention, it can be mixed with the monomer and added, and it can be added to the polymerization system independently of the catalyst component and the monomer. In addition, a variety of Lewis bases can be used in combination.

[0363] Examples of the Lewis base include aromatic amines, aliphatic amines, alkyl ethers, aryl ethers, alkyl aryl ethers, cyclic ethers, alkyl nitriles, aryl nitriles, alcohols, amides, aliphatic esters, aromatic esters, phosphates, phosphites, thiophenes, thianthracenes, thiazoles, oxazoles, morpholines, and cyclic unsaturated hydrocarbons.

[0364] Among these, particularly preferred Lewis bases are aromatic amines, aliphatic amines, cyclic ethers, aliphatic esters, and aromatic esters, and particularly preferred Lewis bases are pyridine derivatives, pyrimidine derivatives, piperidine derivatives, imidazole derivatives, aniline derivatives, piperidine derivatives, triazine derivatives, pyrrole derivatives, and furan derivatives.

[0365] Specific examples of the Lewis base compound include pyridine, pentafluoropyridine, 2,6-lutidine, 2,4-lutidine, 3,5-lutidine, pyrimidine, N,N-dimethylaminopyridine, N-methylimidazole, 2,2′-bipyridine, aniline, piperidine, 1,3,5-triazine, 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, 2,4,6-tris(2-pyridyl)-s-triazine, quinoline, 8-methylquinoline, phenazine, 1,10-phenanthroline, N-methylpyrrole, 1,8-diazabicyclo-[5.4.0]-undecyl-1,1-dihydro ... carbon-7-ene, 1,4-diazabicyclo-[2,2,2]-octane, triethylamine, benzonitrile, methylpyridine, triphenylamine, N-methyl-2-pyrrolidone, 4-methylmorpholine, benzoxazole, benzothiazole, furan, 2,5-dimethylfuran, dibenzofuran, xanthene, 1,4-dioxane, 1,3,5-trioxane, dibenzothiophene, thianthrene, triphenylphosphoniumcyclopentadienide, triphenyl phosphite, triphenyl phosphate, tripyrrolidinephosphine, etc.

[0366] In the present invention, the polymerization form is not particularly limited. As the polymerization form, it is preferred to use solution polymerization in which all generated polymers are dissolved in a medium, slurry polymerization in which at least a portion of the generated polymers become a slurry in a medium, bulk polymerization with liquefied monomers themselves as a medium, gas phase polymerization carried out in gasified monomers, or high-pressure ion polymerization in which at least a portion of the generated polymers are dissolved in a monomer liquefied under high temperature and high pressure, etc. In addition, it can be any form in intermittent polymerization, semi-intermittent polymerization, and continuous polymerization. As an environment for carrying out polymerization reaction, it is preferably used under an inert gas atmosphere such as under a nitrogen atmosphere. The metal complex catalyst can be used under conventional polymerization conditions, and its use conditions are not particularly limited. The amount of the metal complex catalyst used is not particularly limited as long as it is suitable for the scope of being used as a catalyst, and those skilled in the art can set it appropriately.

[0367] Regarding the polymerization reaction in the present invention, when using a monomer suitable for polymerization in a liquid phase, the reaction is carried out in the presence or absence of a hydrocarbon solvent such as n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, a liquid such as a liquefied olefin, a halogenated hydrocarbon solvent such as chlorobenzene, 1,2-dichlorobenzene, or a polar solvent such as ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropanol, ethylene glycol, etc. In addition, a mixture of liquid compounds described herein can be used as a solvent. Liquefied olefins can also be used as monomers for bulk polymerization. Furthermore, ionic liquids can also be used as solvents. It should be noted that in terms of obtaining high polymerization activity and high molecular weight, it is more preferred to use the above-mentioned hydrocarbon solvents and ionic liquids.

[0368] Unreacted monomers and medium can be separated from the produced copolymer and recycled.

[0369] During the cycle, these monomers and media may be purified and reused, or may be directly reused without purification. The separation of the generated copolymer from the unreacted monomers and the media may be carried out using existing known methods. For example, methods such as filtration, centrifugal separation, solvent extraction, and reprecipitation using a poor solvent may be used.

[0370] The polymerization temperature, polymerization pressure and polymerization time are not particularly limited, and can usually be appropriately set in the following ranges in consideration of productivity and process capability. That is, the polymerization temperature is usually -20°C to 290°C, preferably 0°C to 250°C, more preferably 0°C to 200°C, further preferably 10°C to 150°C, and particularly preferably 20°C to 100°C. The copolymerization pressure is 0.1 MPa to 300 MPa, preferably 0.3 MPa to 200 MPa, more preferably 0.5 MPa to 150 MPa, further preferably 1.0 MPa to 100 MPa, and particularly preferably 1.3 MPa to 50 MPa. The polymerization time can be selected from the range of 0.1 minute to 100 hours, preferably 0.5 minute to 70 hours, and further preferably 1 minute to 60 hours.

[0371] In the present invention, polymerization is usually carried out in an inert gas atmosphere. For example, nitrogen or argon atmosphere can be used, preferably nitrogen atmosphere. It should be noted that a small amount of oxygen or air can be mixed. When a monomer that is a gas at room temperature, such as ethylene, is used, polymerization can be carried out after the reaction system is filled with ethylene.

[0372] There is no particular limitation on the supply of catalyst and monomer to the polymerization reactor, and various supply methods can be adopted according to the purpose. For example, in the case of intermittent polymerization, a method of supplying a predetermined amount of monomer to the polymerization reactor in advance and supplying the catalyst thereto can be adopted. In this case, additional monomer and additional catalyst can be supplied to the polymerization reactor.

[0373] Regarding the control of the composition of the copolymer, a method of supplying multiple monomers to the reactor and changing the supply ratio can usually be used for control. In addition, there can be listed: a method of controlling the copolymer composition by utilizing the difference in monomer reactivity ratio caused by the different structures of the catalyst, and a method of controlling the copolymer composition by utilizing the polymerization temperature dependence of the monomer reactivity ratio. In the present invention, when at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins is copolymerized with acyclic olefins, the total content ratio of the acyclic olefin monomer in all the copolymerized monomers can be appropriately selected according to the desired physical properties, relative to 100 mol% of all monomers, the lower limit can usually be 60.00 mol% or more, can be 70.00 mol% or more, can be 80.00 mol% or more, can be 85.00 mol% or more, can be 90.00 mol% or more. On the other hand, the upper limit can usually be 99.90 mol% or less, can be 99.80 mol% or less, can be 99.70 mol% or less, can be 99.60 mol% or less, can be 99.50 mol% or less. By setting it as this range, affinity with a coating material, adhesion, etc. can be imparted without significantly impairing the original properties of polyolefin such as heat resistance, and physical properties can be controlled.

[0374] The molecular weight of the polymer can be controlled by a conventionally known method, and for example, the following method can be mentioned.

[0375] 1) Control polymerization temperature

[0376] 2) Control monomer concentration

[0377] 3) Controlling the ligand structure in transition metal complexes

[0378] 4) Use of known chain transfer agents such as hydrogen and alkyl metals

[0379] The weight average molecular weight (Mw) of the olefin polymer obtained by the method for producing an olefin polymer of the present invention is not particularly limited. The lower limit of the weight average molecular weight (Mw) of the olefin polymer may be 5,000 or more, and may be 10,000 or more. In addition, the upper limit of the weight average molecular weight (Mw) of the olefin polymer may be 1,000,000 or less, and may be 500,000 or less.

[0380] The weight average molecular weight (Mw) of the olefin polymer is determined by gel permeation chromatography (GPC). The GPC measurement in the present invention can be performed by the method described in the examples described later.

[0381] When the olefin polymer obtained by the method for producing an olefin polymer of the present invention is an ethylene polymer, the ethylene polymer is 13 The degree of methyl branching calculated by C-NMR is not particularly limited, but may be 10 or less, or 5 or less per 1,000 carbon atoms.

[0382] In addition, the measurement of the number of methyl branches in the present invention can be carried out by the method described in the Examples described later.

[0383] The method for producing an olefin polymer of the present invention can provide an olefin polymer or copolymer with high activity, and in particular can provide a copolymer of at least one monomer selected from the group consisting of a polar group-containing monomer and a cyclic olefin and an acyclic olefin, and thus can be used as a method for providing a polymer having various characteristics. In addition, the catalytic performance of the catalyst used in the method of the present invention is balanced, and not only a high molecular weight (co)polymer is obtained with high activity, but also as a catalyst, it can be used efficiently for the synthesis of olefin polymers without separation.

[0384] II. Second Embodiment

[0385] II-1. Compound

[0386] The compound according to the second embodiment of the present invention is a compound represented by the following general formula (A).

[0387]

[0388] [In formula (A), each symbol is as defined in [2-1] above.]

[0389] Hereinafter, R in formula (A) 1 ~R 6 、E 1 , X 1 , Z, l, n and m are used for explanation.

[0390] In the above general formula (A), X 1 represents an oxygen atom or a sulfur atom. That is, the compound represented by the above general formula (A) can be used as a ligand having one Group 16 element as a monovalent anionic coordinating atom. From the perspective of the rich variety of compounds used as ligands, X 1 Preferred is an oxygen atom.

[0391] In the above general formula (A), E 1 represents a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom. That is, the compound represented by the general formula (A) can be used as a ligand having one Group 15 element as a neutral coordinating atom. Since there are a variety of compounds used as ligands and the coordination property with transition metal elements later in the period such as nickel or palladium is good, E 1 Preferred is a nitrogen atom or a phosphorus atom.

[0392] In the above general formula (A), R 3 , R 4 , R 5 and R 6 Each independently represents an atom or a group selected from the group consisting of the following (i) to (iv).

[0393] (i) Hydrogen atom

[0394] (ii) Halogen atoms

[0395] (iii) a hydrocarbon group having 1 to 30 carbon atoms and optionally containing at least one heteroatom

[0396] (iv)OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b )2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group (here, R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, and y represents 0, 1 or 2). 3 , R 4 , R 5 and R 6 Adjacent substituents may be linked to each other to form a 5- to 8-membered alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom.

[0397] Examples of the (ii) halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom is preferred.

[0398] Examples of the (iii) hydrocarbon group having 1 to 30 carbon atoms which may contain at least one hetero atom include a hydrocarbon group and a hydrocarbon group in which at least one hydrogen atom is substituted with a substituent containing a hetero atom.

[0399] Examples of the hetero atom in (iii) include oxygen, nitrogen, phosphorus, sulfur, silicon, and halogen atoms. The hetero atom as a substituent may be a halogen atom, and the halogen atom may be the same as that in (ii) above.

[0400] Examples of the heteroatom-containing substituent in (iii) include the same substituents as those exemplified in (iv) described later. Examples of the heteroatom-containing substituent in (iii) include an alkoxy group, an aryloxy group, an alkoxycarbonyl group, or an acyloxy group.

[0401] Examples of the hydrocarbon group having 1 to 30 carbon atoms in (iii) include linear, branched, cyclic saturated or unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. More specifically, examples of the hydrocarbon group having 1 to 30 carbon atoms include linear alkyl groups having 1 to 30 carbon atoms, branched acyclic alkyl groups having 3 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, cycloalkyl groups having 3 to 30 carbon atoms which may have a side chain, aryl groups having 6 to 30 carbon atoms, arylalkyl groups having 7 to 30 carbon atoms, and alkylaryl groups having 7 to 30 carbon atoms.

[0402] Examples of the straight-chain alkyl group having 1 to 30 carbon atoms include a straight-chain alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl, and may include a straight-chain alkyl group having 1 to 4 carbon atoms.

[0403] The branched non-cyclic alkyl group having 3 to 30 carbon atoms may be isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl (3-methylbutyl), tert-pentyl (1,1-dimethylpropyl), sec-pentyl (1-methylbutyl), 2-methylbutyl, neopentyl (2,2-dimethylpropyl), 1,2-dimethylpropyl, isohexyl (4-methylpentyl), or the like. The branched non-cyclic alkyl group having 3 to 10 carbon atoms may be used.

[0404] Examples of the alkenyl group having 2 to 30 carbon atoms include vinyl, allyl, butenyl, pentenyl, hexenyl, styryl, and cinnamyl. Examples of the alkenyl group include alkenyl groups having 3 to 8 carbon atoms such as allyl, butenyl, pentenyl, hexenyl, and styryl, and alkenyl groups having 4 to 8 carbon atoms such as butenyl, pentenyl, hexenyl, and styryl.

[0405] The cycloalkyl group having 3 to 30 carbon atoms and optionally having a side chain may be a cycloalkyl group having 3 to 10 carbon atoms and optionally having a side chain, such as cyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, cyclooctyl, decahydronaphthyl (bicyclo[4,4,0]decyl), or a cycloalkyl group having 3 to 6 carbon atoms and optionally having a side chain.

[0406] Examples of the aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, azulenyl, biphenyl, anthracenyl, terphenyl, phenanthryl, triphenylene, The aryl group having 6 to 18 carbon atoms may be an aryl group having 6 to 12 carbon atoms, such as phenenyl, pyrenyl and naphthacene.

[0407] Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, phenethyl (2-phenylethyl), 9-fluorenyl, naphthylmethyl, 1-tetrahydronaphthalene (t e t r aliny l) group, and may be an arylalkyl group having 7 to 15 carbon atoms.

[0408] The alkylaryl group having 7 to 30 carbon atoms may be an alkylaryl group having 7 to 20 carbon atoms such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, etc.; and the alkylaryl group having 7 to 15 carbon atoms such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, etc.

[0409] (iii) with R 3 ~R 6 The total carbon number of the corresponding substituent is preferably 1-30, more preferably 2-25, and even more preferably 4-20.

[0410] Examples of (iii) include: (iii-A) a linear alkyl group having 1 to 30 carbon atoms, a branched non-cyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a side chain, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, and an alkylaryl group having 7 to 30 carbon atoms; (iii-B) a group in which each group in (iii-A) is substituted with one or two or more of the above-mentioned heteroatoms; (iii-C) a group in which each group in (iii-A) is substituted with one or two or more of the above-mentioned substituents containing heteroatoms; and (iii-D) a group in which each group in (iii-A) is substituted with one or two or more of the above-mentioned heteroatoms and with one or two or more of the substituents containing heteroatoms. Examples of (iii-C) include, for example, an alkyl group substituted with an alkoxy group, and an aryl group substituted with an alkoxycarbonyl group or an acyloxy group.

[0411] Examples of the (iii) hydrocarbon group having 1 to 30 carbon atoms which may contain at least one hetero atom include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, 2,4,6-triphenylphenyl, 2,6-diisopropylphenyl, 9-anthryl, pentafluoroethyl, pentafluorophenyl, phenyl and benzyl.

[0412] (iv) is a substituent containing a heteroatom, selected from OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group (here, R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, and y represents 0, 1 or 2).

[0413] Examples of the above-mentioned (iv) include hydroxyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, phenoxy, p-methylphenoxy, p-methoxyphenoxy, ethoxycarbonyl, tert-butoxycarbonyl, phenoxycarbonyl, dimethylamide, acetyl, benzoyl, acetoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, tert-butylthio, phenylthio, methylsulfonyl, phenylsulfonyl, methylsulfonyloxy, phenylsulfonyloxy, penta-butylthio, methylsulfonyloxy ... Fluorosulfur group (SF5), dimethyl phosphate group, cyano group, amino group (NH2), methylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, cyclohexylamino group, methylethylamino group, methyl-n-propylamino group, methylcyclohexylamino group, carbazolyl group, piperidinyl group, trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, trimethoxysilyl group, triethoxysilyl group, trimethylsiloxy group, trimethoxysiloxy group, sodium carboxylate group, sodium sulfonate group, potassium sulfonate group, sodium phosphate group, potassium phosphate group, etc.

[0414] In addition, R 3 , R 4 , R 5 and R 6 Adjacent substituents are optionally linked to each other to form a 5-8 membered, alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from oxygen, nitrogen or sulfur atoms. In the formed ring structure, the condensed ring optionally contains an aromatic ring. Examples of the formed ring include 1,2-cyclopentene, 1,2-cyclohexene, 1-oxo-2,3-cyclopentene, 1-oxo-2,3-cyclohexene, 1,2-dihydroacenaphthene, 9,10-dihydroanthracene, etc.

[0415] Among them, from the viewpoint of ligand stability, the above R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv) above, and more preferably R 5 is an atom or group selected from the group consisting of (i) and (iii) above, and R 6 For a compound selected from the group consisting of (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in a group.

[0416] In particular, when with X 1 The adjacent R 5 and R 6 When at least one of X is an electron-withdrawing group, the performance as an olefin polymerization catalyst is further improved, which is preferred. 1 The adjacent R 5 and R 6 Both of them may be electron-withdrawing groups. As the electron-withdrawing group, trifluoromethyl, pentafluorophenyl, methoxycarbonyl, phenoxycarbonyl, SF5, toluenesulfonyl, mesyl, nitro, methylcarbonyl, phenylcarbonyl and the like are preferably used.

[0417] In addition, from the perspective of synthesis difficulty and economic rationality, the above R 3 and R 4 At least one of them may be an atom or group selected from the group consisting of (i), (iii) and (iv) above, and the above R 3 and the above R 4 At least one of them may be a hydrogen atom.

[0418] n is 0, 1, 2, 3 or 4. When n is 0, E 1 With X 1 , R 5 and R 6 The carbon atoms to which they are bonded are directly bonded. The value of n is related to the connection E 1 and X 1 From the perspective of structural stability of the complex, n can be 0, 1 or 2. The structure of the complex is stable when a 5-membered ring is formed, so n is preferably 1.

[0419] In the above general formula (A), R1 It represents a hydrocarbon group represented by the following general formula (B) or (C).

[0420]

[0421] [In formula (B) and formula (C),

[0422] *Indicates the same as E 1 The connection key,

[0423] R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A), R 7 , R 8 , R 9 and R 10 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom,

[0424] A 1 , A 2 , A 3 and A 4 Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)- (herein, R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which optionally contains at least one heteroatom.).

[0425] in,

[0426] In formula (B), A 1 , A 2 , A 3 and A 4 At least three of them are groups other than -C(R)2-,

[0427] In formula (C), A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 At least one of them is an atom or group selected from the group consisting of (ii) and (iv) above (except for epoxy-containing groups).

[0428] W 1 and W 2Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8 and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R 10 Does not exist.

[0429] h and i are each independently an integer of 1 to 6, 1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R 7 , R 8 , R 9 and R 10 They may be the same or different.]

[0430] In formula (B) and formula (C), A 1 , A 2 , A 3 and A 4 Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)- (herein, R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may optionally contain at least one heteroatom.). The hydrocarbon group having 1 to 20 carbon atoms which may optionally contain at least one heteroatom in the above R may be the same as the hydrocarbon group having 1 to 20 carbon atoms which may optionally contain at least one heteroatom in the above (iii). From the viewpoint of ease of synthesis and economic rationality, the above R may be a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, may be a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, may be a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, or may be a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

[0431] In formula (B) and formula (C), W 1 and W 2 Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8 and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R10 Does not exist.

[0432] In formula (B) and formula (C), W 1 and W 2 From the viewpoint of ligand stability, each independently may be a carbon atom or a silicon atom, and may be a carbon atom.

[0433] In formula (B) and formula (C), R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A).

[0434] From the perspective of synthesis difficulty and economic rationality, R 7 , R 8 , R 9 , R 10 and R 11 Each independently may be an atom or group selected from the group consisting of (i) and (iii) above. 7 , R 8 , R 9 , R 10 and R 11 The above (iii) may be an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, particularly from the viewpoint of ease of synthesis and economic rationality.

[0435] In addition, R 7 , R 8 , R 9 and R 10 Each independently optionally adjacent substituent is bonded to each other and to the W to which they are bonded 1 or W 2 together to form a 5- to 8-membered, alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom. 1 or W 2 When there are 2, R 7 , R 8 , R 9 and R 10 Each independently optionally adjacent substituent is connected to each other and to the two W to which they are bonded 1 or 2 Ws 2 Together they form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring.

[0436] R 7 , R8 , R 9 and R 10 can be bonded to W 1 or W 2 Together they form an alicyclic ring, and may be an alkylene group having 4 to 7 carbon atoms formed by connecting adjacent substituents to each other. 7 and R 8 can be the W to which they are bonded 1 An alkylene group having 5 carbon atoms such as forming a 6-membered ring. 7 , R 8 , R 9 and R 10 The aryl groups of the adjacent substituents are each independently connected to each other and to the W to which they are bonded. 1 or W 2 For example, adjacent R 7 and R 8 can be the W to which they are bonded 1 In this case, W 1 When it is a carbon atom, through W 1 and R 7 and R 8 To form a fluorenylene group.

[0437] In addition, R 7 , R 8 , R 9 and R 10 The two Ws they bond to 1 or 2 Ws 2 They may be alkylene groups having 3 to 6 carbon atoms, or alkylene groups having 3 or 4 carbon atoms, such as forming a 5- or 6-membered ring. 7 , R 8 , R 9 and R 10 The two Ws they bond to 1 or 2 Ws 2 Together they form an aromatic ring having 6 to 12 carbon atoms.

[0438] Furthermore, it may be a heterocyclic ring in which at least one carbon atom of the above-mentioned alicyclic ring or aromatic ring is substituted with a heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom.

[0439] In addition, R 7 , R 8 , R 9 and R 10The alicyclic ring, aromatic ring or heterocyclic ring formed in the above formula (A) may further have an atom or group selected from the group consisting of (ii) to (iv) defined in the above formula (A) as a substituent, and the substituent may be a halogen atom.

[0440] From the perspective of synthesis difficulty and economic rationality, R 11 It may be a hydrogen atom.

[0441] In addition, from the perspective of synthesis difficulty and economic rationality, R 12 and R 13 Each independently may be an atom or a group selected from the group consisting of (i), (iii) and (iv) above. 12 and R 13 In the above (iii), from the viewpoint of ease of synthesis and economic rationality, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms may be used. 12 and R 13 From the perspective of synthesis difficulty and economic rationality, the above (iv) can be used for OR b 、C(O)OR b 、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x Or NO2, etc.

[0442] In formula (B) and formula (C), h and i are each independently an integer of 1 to 6, and W 1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R 7, R 8 , R 9 and R 10 They may be the same or different.

[0443] From the perspective of ease of synthesis and economic rationality, h and i can each independently be an integer of 1 to 3, can be 1 or 2, or can be 1.

[0444] Among them, in formula (B), A 1 , A 2 , A 3 and A 4 At least three of them are groups other than -C(R)2-. That is, in formula (B), A 1 , A 2 , A 3 and A 4 At least three of them are oxygen atoms, sulfur atoms, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)-.

[0445] In formula (B), the group other than -C(R)2- may be an oxygen atom, a sulfur atom or -N(R)-, and may be an oxygen atom, from the viewpoint of ease of synthesis and economic rationality.

[0446] Among them, in formula (B), A 1 , A 2 , A 3 and A 4 Four of them may be groups other than -C(R)2-, and four of them may be oxygen atoms.

[0447] Among them, in formula (C), A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 At least one of them is an atom or group selected from the group consisting of (ii) and (iv) above (except for groups containing epoxy). That is, in formula (C), A 3 and A 4 are oxygen atoms, sulfur atoms, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)-, R 12 and R 13 At least one of them is an atom or group selected from the group consisting of (ii) and (iv) above (except for epoxy-containing groups).

[0448] In the formula (C), the group other than -C(R)2- may be an oxygen atom, a sulfur atom or -N(R)-, and may be an oxygen atom, from the viewpoint of ease of synthesis and economic rationality.

[0449] In formula (C), R 12 and R 13 The atom or group selected from the group consisting of (ii) and (iv) above (except for the group containing epoxy) may be a fluorine atom, OR b , SR b 、N(H)R a 、N(R b )2、or OSi(OR a ) 3-x (R a ) x , which can be OR b In addition, as R 12 and R 13 OR b , for example, it may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, or phenoxy.

[0450] Among them, from the perspective of activity, A in the above general formula (C) can be 3 and A 4 are oxygen atoms, nitrogen atoms, phosphorus atoms or sulfur atoms and R 12 is an atom or group selected from the group consisting of (ii) and (iv) above (except for groups containing epoxy), and may also be A in the above general formula (C) 3 and A 4 are all oxygen atoms and R 12 It is an atom or group selected from the group consisting of the above (ii) and (iv) (except for groups containing epoxy).

[0451] In the above general formula (A), R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, which is different from the hydrocarbon group represented by the above general formula (B) or (C) and which optionally contains at least one heteroatom, and l is 1 or 2. When l is 2, R 2 Does not exist.

[0452] As R 2 The hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom in (iii) may be the same as the hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom in (iii) above.

[0453] As R 2, can be a hydrocarbon group having 3 to 20 carbon atoms, for example, n-propyl, isopropyl, isobutyl, tert-butyl, 3-pentyl, 2,6-dimethyl-4-heptyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantyl, (1R,2S,5R)-2-isopropyl-5-methylcyclohexane-1-yl (menthyl), phenyl, 2-methoxyphenyl, 2,6-diethylphenyl (DEP), 2,6-dimethoxyphenyl (DMP), 2',6'-dimethoxy[1,1'-biphenyl]-2-yl, (1R,2S,5R)-2-isopropyl-5-methylcyclohexane-1-yl, etc. are preferably used.

[0454] From the perspective of synthesis difficulty and economic rationality, l can be 2.

[0455] In the above general formula (A), Z is a hydrogen atom, a leaving group, or a cation having a valence of 1 or more and 4 or less, and m is an integer of 1 or more and less than the valence of Z. When m is 1, Z may be exemplified by a hydrogen atom, a lithium ion, a sodium ion, a potassium ion, etc. When m is 2, Z may be exemplified by a magnesium ion, a calcium ion, a zinc ion, etc. As leaving groups, hydrogen atoms, R b S(O)2 group (here, R b represents a hydrocarbon group having 1 to 20 carbon atoms), C(F) 3 S(O)2 group, R b S(O)2、TiOR b As cations, specifically, ammonium, quaternary ammonium or phosphonium, and metal ions of Groups 1 to 14 of the periodic table can be cited. Among these, hydrogen atoms, NH 4+ , (R b )4N + (Here, R b As mentioned above, the 4 Rs b They may be the same or different. The same shall apply to the following. )、(R b )4P + , Li + 、Na + , K + , Cu + 、Ag + 、Au + ,Mg 2+ , Ca 2+ 、Al 3+ , more preferably a hydrogen atom, (R b )4N + , Li + 、Na + , K + 、Ag + .

[0456] Specific examples of the compound represented by the general formula (A) include the following compounds, but are not limited to these.

[0457]

[0458]

[0459] (In the formula, R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom.)

[0460] The compound represented by the above general formula (A) can be synthesized based on a known synthesis method. 1 H(R 1 ) l (R 2 ) 2-l In the presence of alkali or acid, 1 H(R 1 ) l (R 2 ) 2-l The compound represented by the above general formula (A) can be synthesized by reacting E in the presence of a base. 1 CH3(R 1 ) l (R 2 ) 2-l The above general formula (A) is synthesized by reacting with a ketone. Representative references include Patent Document 5, Non-Patent Document 7, Journal of Fluorine Chemistry 2002, 117, P121-129.

[0461] E 1 H(R 1 ) l (R 2 ) 2-l The compounds shown can be appropriately selected from commercial products. When commercial products are not available, E can be synthesized by reacting a phosphine halide with a nucleophilic agent such as an organic lithium or organic magnesium. 1 X(R 1 ) l (R 2 ) 2-l (X is a halogen atom) and then a hydride reducing agent such as lithium aluminum hydride is allowed to act to synthesize. Representative references include Japanese Patent Application Laid-Open No. 2021-113174.

[0462] For R 1The compound into which the substituent represented by the above general formula (B) or (C) is introduced can be appropriately selected and commercially available. When commercially available products are not available, they can be synthesized by intermolecular or intramolecular cyclization reactions. Examples of such cyclization reactions include nucleophilic substitution reactions of dihalogen molecules, Friedel-Crafts reactions, cyclization reactions using transition metals, and the like. Representative references include RSC Advances 2014, 4, P16312-16319, Bioorg. Med. Chem. Lett. 2014, 24, P2379-2382., Chem. Eur. J. 2013, 19, P17349-17357., Org. Biomol. Chem. 2018, 16, P8976-8983., and the like.

[0463] The compound represented by the general formula (A) acts as a ligand capable of forming a complex with the transition metal compound represented by the general formula (E) or (F) described later. 1 is an oxygen atom and E 1 The compound represented by the general formula (A) which is a phosphorus atom has a structure in which phosphorus and oxygen are bonded via an alkylene group, and thus such a group of compounds is sometimes referred to as an alkylene-linked phosphine alkoxide (ALPHA) ligand.

[0464] II-2. Catalyst composition for olefin polymerization

[0465] The olefin polymerization catalyst composition according to the second embodiment of the present invention contains the compound represented by the above-mentioned general formula (A) and a transition metal compound represented by the following general formula (E) or (F).

[0466]

[0467] [In formula (E) and formula (F),

[0468] M 1 、M 2 and M 3 Each independently represents a nickel atom or a palladium atom, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 9 and L 10 Each independently represents the coordination in M 1 、M 2 or M 3 The ligand, L 7 and L 8Indicates coordination with M 2 and M 3 The ligand

[0469] q is 0, 1, or 2,

[0470] L 1 and L 2 Optionally bonded to each other to form a 1 The ring,

[0471] L 3 and L 4 Optionally bonded to each other to form a 1 The ring,

[0472] L 5 and L 6 Optionally bonded to each other to form a 2 The ring,

[0473] L 9 and L 10 Optionally bonded to each other to form a 3 ring.]

[0474] In the olefin polymerization catalyst composition according to the second embodiment of the present invention, the compound represented by the general formula (A) may be the same as the compound represented by the general formula (A) according to the second embodiment, and thus the description thereof is omitted here.

[0475] In the compound represented by the above general formula (A), the phosphorus atom or the like 1 The upper bond has as R 1 In the hydrocarbon groups represented by the above general formula (B) or (C), relative to the phosphorus atom, E 1 Substituents in the ortho position to the bonded carbon atom (A 1 and A 3 ) forms a ring structure, thereby inhibiting the free rotation of the substituent at the ortho position. On the other hand, the hydrocarbon group represented by the general formula (B) or (C) has a suitable volume. We believe that when two phenyl groups having freely rotatable substituents at the ortho positions are bonded to E1, when the compound is used as a ligand, the steric hindrance near the active center, i.e., the transition metal, becomes too high, and the activity is easily reduced. It is also believed that the unsubstituted phenyl group bonded to E 1 In the case of using the compound as a ligand, the steric hindrance near the transition metal is insufficient, making it difficult to increase the molecular weight. We believe that when the compound represented by the general formula (A) is used as a ligand of a transition metal compound, appropriate steric hindrance can be maintained near the transition metal, thereby maintaining a high molecular weight and improving the activity of the catalyst.

[0476] In addition, it is considered that in the compound represented by the above general formula (A), phosphorus atoms such as E 1 The substituent of the phenyl group bonded thereto is a substituent containing a heteroatom such as an oxygen atom in the ring structure, thereby further improving the coordination force of the heteroatom such as the oxygen atom to the catalyst center metal, thereby increasing the catalyst activity and further increasing the molecular weight of the obtained polymer.

[0477] In the above general formula (E) or (F), M 1 、M 2 and M 3 Each independently represents a nickel atom or a palladium atom. Here, the valence of the metal M refers to the formal oxidation number used in organometallic chemistry.

[0478] That is, the number of charges remaining on the atoms of a certain element when the electron pair in the bond formed by the element is assigned to an element with high electronegativity. Nickel atoms are preferred because they are available at low cost.

[0479] In the above general formula (E) or (F), L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 9 and L 10 Each independently represents the coordination in M 1 、M 2 or M 3 The ligand represents a -1 valent electron-donating ligand or a neutral electron-donating ligand.

[0480] The -1-valent electron-donating ligand is an electronegative ligand that forms a σ bond with the central metal, i.e., M, or a ligand that donates delocalized π electrons to three or more carbon atoms. An example of a neutral electron-donating ligand is an electrically neutral ligand that can form a coordination bond by coordinating an unpaired electron to M. The ligand is a molecule containing an atom having an unpaired electron, and examples of the atom having an unpaired electron include nitrogen atoms, phosphorus atoms, arsenic atoms, oxygen atoms, sulfur atoms, and selenium. In addition, as another example of a neutral electron-donating ligand, there are molecules such as ethylene and cyclooctadiene (cod) that form a π coordination bond by donating π electrons, and molecules such as dibenzylideneacetone (dba) that have both an olefin and a heteroatom coordinated to the metal. As molecules that can be used as L 1 ~L 6 , L 9 , L 10As the ligand, acetonitrile, isonitrile, carbon monoxide, ethylene, tetrahydrofuran, etc., which are known as neutral ligands for metal complexes, and ligands that provide π electrons, such as allyl and cyclopentadienyl, can be used. 2 R'R"R"' or X 2 The molecule shown by R'R" acts as a ligand. Here, E 2 Indicates N, P or As, X 2 represents O, S or Se, R', R" and R'" each independently represent a hydrogen atom; an optionally substituted alkyl group, alicyclic group, alkoxy group, aryl group or aryloxy group having 1 to 30 carbon atoms; or, each independently represents an amino group or a silyl group in which at least one hydrogen atom is substituted by a hydrocarbon group having 1 to 30 carbon atoms, R' and R" are optionally connected to form a heterocyclic structure, and R', R" and R'" optionally contain E 2 And bond to form an aromatic heterocyclic structure. 1 With L 2 , L 3 With L 4 , L 5 With L 6 , L 9 With L 10 Optionally bonded to each other to form a 2 or M 3 When these groups form a ring, the minimum number of ring members of the ring including M is 5-membered ring to 10-membered ring.

[0481] L 1 ~L 6 , L 9 , L 10 The electron-donating ligand optionally having a valence of -1 is preferably selected so that the valence of the metal complex becomes 1 or 2 in order to facilitate the reaction of forming the metal complex. 1 ~L 6 , L 9 , L 10 The number of -1-valent electron-donating ligands in the moiety is preferably 0 to 2.

[0482] L as a -1 electron-donating ligand 1 ~L 6 , L 9 , L 10 , may be a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms and optionally containing at least one hetero atom, the structure of the hydrocarbon part may be any of a straight chain, a branched chain, or a cyclic structure, and may optionally form a ring containing a hetero atom. The preferred carbon number is 1 to 16, and more preferably 1 to 10.

[0483] L as a -1 electron-donating ligand 1 ~L6 , L 9 , L 10 Specific examples of include, independently, hydride group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, neopentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group, benzyl group, trimethylsilylmethyl group, phenyl group, p-methylphenyl group, p-fluorophenyl group, fluoride group, chloride group, bromide group, iodide group, etc. Preferred examples include hydride group, methyl group, neopentyl group, benzyl group, trimethylsilylmethyl group, phenyl group, p-fluorophenyl group, chloride group, bromide group, iodide group, etc.

[0484] In addition, as L 1 ~L 6 , L 9 , L 10 Preferred examples include phosphines, pyridines, piperidines, alkyl ethers, aryl ethers, alkyl aryl ethers, cyclic ethers, alkyl nitrile derivatives, aryl nitrile derivatives, alcohols, amides, aliphatic esters, aromatic esters, amines, cyclic unsaturated hydrocarbons, etc. Further preferred examples include phosphines, pyridines, cyclic ethers, aliphatic esters, aromatic esters, cyclic olefins, and particularly preferred examples include trialkylphosphines, triarylphosphines, pyridine, lutidine, picoline, R b C(O)O - (Here, R b As defined above). It should be noted that, as L 1 With L 2 , L 3 With L 4 , L 5 With L 6 , L 9 With L 10 Optionally bonded to each other to form a 2 or M 3 Examples of the ring include a cyclooct-1-enyl group, an acetylacetonyl group, a tetramethylethylenediamino group, and a 1,2-dimethoxyethane group, which are also preferred embodiments.

[0485] L 7 and L 8 Indicates coordination to the metal atom M 2 and M 3 ligands, respectively with M 2 and M 3 The bond is called a three-center four-electron bond. 7 or L 8Examples of the ligand of L include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkoxy group having 1 to 6 carbon atoms, a hydrocarbon-substituted amino group having 1 to 6 carbon atoms, and an acetyl group. 7 and L 8 Preferred examples include a fluoride group, a chloride group, a bromide group, an iodide group, a methyl group, an ethyl group, a propyl group, a methoxy group, a phenoxy group, a dimethylamide group, a hydride group, a thiomethoxy group, a thiophenoxy group, and an acetyl group. More preferred examples include a fluoride group, a chloride group, a bromide group, an iodide group, a methyl group, a methoxy group, a phenoxy group, a hydride group, a thiomethoxy group, a thiophenoxy group, and an acetyl group. Further preferred examples include a chloride group, a bromide group, an iodide group, a methoxy group, a phenoxy group, and an acetyl group.

[0486] In the above general formula (E), q is a value of 0, 1 or 2.

[0487] As specific examples of the compounds represented by the above general formula (E) or formula (F), the following compounds can be listed, but are not limited to these. In addition, Ni(CH2C(H)CH2)2, Ni(CH2C(Me)CH2)2, Ni(CH2Si(Me)3)2(Py)2(hereinafter, Py represents pyridine.), Ni(CH2Si(Me)3)2(Lut)2(hereinafter, Lut represents 2,6-dimethylpyridine.), NiPh2(Py)2, NiPh2(Lut)2, Pd(OC(O)CH3)2, etc. can be listed.

[0488] These compounds are considered to form complexes with the compound represented by the general formula (A).

[0489]

[0490] The compound represented by the general formula (A) can be used as a catalyst for olefin polymerization in the form of a composition with the transition metal compound represented by the general formula (E) or (F) or in the form of a reaction product with the transition metal compound, i.e., a metal complex. In the olefin polymerization reaction, the product used as a catalyst can be used after the compound represented by the general formula (A) and the transition metal compound represented by the general formula (E) or (F) are reacted, or the product can be used directly in the polymerization reaction without separating and washing the product from the reaction system. The method for reacting these compounds can use a method known in the synthesis of metal complexes. The operation is preferably carried out under an inert gas. The reaction is carried out in a uniform solvent, and as a solvent, a common hydrocarbon reaction solvent can be used, preferably toluene. The concentration of the transition metal compound in the reaction solvent can be freely set with the saturation concentration as the upper limit, preferably in the range of 1 mM to 50 mM. There is no restriction on the mixing order of the compound represented by the general formula (A) (ligand) and the transition metal compound represented by the general formula (E) or (F). A solvent may be added to a mixture of a solid ligand and a solid transition metal compound, or a dissolved transition metal compound may be added to the solid ligand. The mixing ratio of the ligand to the transition metal compound is preferably set in the range of ligand:metal=1:1 to 1:10. The mixing temperature may be appropriately set within the range of 20°C or above with the boiling point of the solvent as the upper limit. The mixing temperature is preferably in the range of 35°C to 45°C. The time required for mixing may preferably be set in the range of 1 minute to 24 hours, more preferably 10 minutes to 30 minutes. One embodiment of the present invention is a method for producing a catalyst for olefin polymerization, comprising a step of reacting a compound represented by the above-mentioned general formula (A) with a transition metal compound represented by the above-mentioned general formula (E) or (F).

[0491] II-3. Metal complexes

[0492] In another embodiment, a second aspect of the present invention provides a metal complex represented by the following general formula (D).

[0493]

[0494] [In formula (D),

[0495] X 1 、E 1 ,n,R 1 , R 2 , l, R 3 , R 4 , R 5 and R 6 As defined in the above-mentioned [2-1], that is, in the compound represented by the general formula (A) of the above-mentioned second embodiment,

[0496] M 1, L 1 and L 2 As defined in the transition metal compound represented by the above general formula (E) or (F).]

[0497] Specific examples of the metal complex represented by the general formula (D) include the following complexes: However, these are for illustration only, and the complexes in the method of the present invention are not limited to these specific examples.

[0498]

[0499]

[0500]

[0501]

[0502] (In the formula, R represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0503] The metal complex represented by the above general formula (D) of the present invention can be prepared by a method including a step of reacting the compound represented by the above general formula (A) with the transition metal compound represented by the above general formula (E) or (F), or by a known method. Those skilled in the art can prepare the metal complex represented by the above general formula (D) of the present invention based on a known complex preparation method and by making appropriate changes such as raw material changes.

[0504] For example, when the metal complex represented by the general formula (D) is produced, when the compound represented by the general formula (A) is reacted with the transition metal compound represented by the general formula (E) or (F), the L in the general formula (D) may also be present. 1 , L 2 Coordination compounds and covalent compounds in which substitution is carried out at the site.

[0505] When nickel or palladium is used as M in the present invention, the stability of the generated metal complex may be increased by allowing a Lewis basic coordination compound to coexist in the system. In this case, the coordination compound may coexist as long as it does not inhibit the polymerization reaction or copolymerization reaction of the present invention.

[0506] The coordination compound used in the present invention can be a hydrocarbon compound having 1 to 20 carbon atoms and having at least one selected from the group consisting of oxygen atoms, nitrogen atoms, phosphorus atoms, arsenic atoms, sulfur atoms and selenium atoms as an atom capable of forming a coordination bond, or a hydrocarbon compound having a carbon-carbon unsaturated bond capable of coordinating with a transition metal and optionally containing a heteroatom, which can be used together with the above-mentioned L 1 The neutral electron donating ligands in the above have the same meaning.

[0507] In addition, the above covalent compound used in the present invention refers to a compound in which the ligand derived from the transition metal compound is replaced by the above L in the metal complex represented by the general formula (D). 1 The above covalent compound may be an organometallic compound.

[0508] As a monovalent electron-donating ligand, a hydrocarbon group having 1 to 20 carbon atoms and optionally containing at least one heteroatom can be incorporated into the polymer as a starting terminal of the polymerization reaction and greatly contributes to the initial rate of the polymerization reaction. Therefore, when preparing the metal complex represented by the general formula (D), it is preferred to use a covalent compound for introducing a hydrocarbon group having 1 to 20 carbon atoms and optionally containing at least one heteroatom in combination according to the circumstances.

[0509] As the above-mentioned covalent compound, there can be mentioned organic lithium compounds, which can be R 14 Li (here, R 14 The organic lithium compound may be an organic lithium compound having a hydrocarbon group having 1 to 20 carbon atoms and optionally containing a hetero atom. Examples of the organic lithium compound having a hydrocarbon group having 1 to 10 carbon atoms include methyl lithium, n-butyl lithium, phenyl lithium, neopentyl lithium, benzyl lithium, trimethylsilyl methyl lithium, and p-fluorophenyl lithium. Among them, methyl lithium and phenyl lithium are preferred, and methyl lithium is more preferred.

[0510] II-4. Catalyst for olefin polymerization

[0511] The olefin polymerization catalyst according to the second embodiment of the present invention includes the olefin polymerization catalyst composition according to the second embodiment of the present invention.

[0512] Furthermore, the olefin polymerization catalyst according to the second embodiment of the present invention contains the metal complex represented by the general formula (D) according to the second embodiment.

[0513] The olefin polymerization catalyst of the present invention comprises a metal complex which is a product of a compound represented by the above general formula (A) and a transition metal compound represented by the above general formula (E) or (F) during the polymerization reaction of olefins, or a metal complex represented by the above general formula (D) (hereinafter, these may be collectively referred to as "metal complex catalysts").

[0514] In the olefin polymerization catalyst of the second embodiment of the present invention, the olefin polymerization catalyst composition of the second embodiment of the present invention and the metal complex represented by the general formula (D) of the second embodiment may be the same as described above, and thus description thereof is omitted here.

[0515] As shown in the examples described below, the olefin polymerization catalyst of the present invention can be used as it is without any purification, using the olefin polymerization catalyst composition of the present invention and the metal complex represented by the general formula (D) as a catalyst for olefin polymerization.

[0516] In the olefin polymerization catalyst of the present invention, the compound represented by the above general formula (A) and the transition metal compound represented by the following general formula (E) or (F) of the olefin polymerization catalyst composition may be used alone or in combination of multiple components. In addition, the olefin polymerization catalyst composition may optionally contain a metal complex represented by the above general formula (D).

[0517] The metal complex represented by the general formula (D) contained in the olefin polymerization catalyst of the present invention may be a single type or a mixture of two or more types.

[0518] In the catalyst for olefin polymerization of the present invention, a co-catalyst may be added in addition to the metal complex catalyst. As the co-catalyst, for example, an organometallic compound containing an element of Group 1, 2 or 13 of the periodic table may be mentioned. In particular, a compound represented by the following general formula (1), a compound represented by the general formula (2) or an organoaluminum-oxy compound may be mentioned. A plurality of types of these compounds may be included in the catalyst composition.

[0519] General formula (1): Q(R 20 )(R 21 )R 22

[0520] The compound represented by the general formula (1) is Q(R 20 )(R 21 )R 22 A boron or aluminum compound represented by (wherein Q represents boron (B) or aluminum (Al), R 20 , R 21 and R 22 Each independently represents a hydrogen atom; an optionally substituted alkyl group, alicyclic group, alkoxy group, aryl group or aryloxy group having 1 to 30 carbon atoms; or each independently represents an amino group or a silyl group in which one or more hydrogen atoms are substituted by a hydrocarbon group having 1 to 30 carbon atoms.

[0521] As R 20 ~R 22 , the above R applies 3 The examples described in the description of etc. are preferably hydrocarbon groups such as alkyl groups and aryl groups, or alkyl groups or aryl groups substituted with halogen (particularly fluorine) such as trifluoromethyl and perfluorophenyl groups, from the viewpoint of the ease of preparation and availability of the compounds.

[0522] Examples of the compound represented by the general formula (1) are trimethylborane, trimethoxyborane, perfluoromethylborane, triphenylborane, tri(perfluorophenyl)borane, triphenoxyborane, tri(dimethylamino)borane, tri(diphenylamino)borane, trimethylaluminum, triethylaluminum, tri(n-propyl)aluminum, tri(n-butyl)aluminum, triisobutylaluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, tri(n-decyl)aluminum, diethylaluminum hydride, diethylethoxyaluminum, dimethylamide diethylaluminum, diisobutylaluminum hydride, and the like, but are not limited thereto.

[0523] The above general formula (2): [C(R 23 )(R 24 )R 25 ] + [Q(R 26 )(R 27 )(R 28 )R 29 ] -

[0524] The compound represented by the general formula (2) is [C(R 23 )(R 24 )R 25 ] + [Q(R 26 )(R 27 )(R 28 )R 29 ] - A salt of boron or aluminum with a carbon cation represented by 23 ~R 29 Independently, and R 20 Same meaning.)

[0525] As R 23 ~R 29 , the above R applies 3 From the examples described in the description of etc., hydrocarbon groups such as alkyl and aryl are preferred from the perspective of easy preparation and availability of the compound, and bulky hydrocarbon groups such as tert-butyl and aryl are more preferred from the perspective of easy availability of carbocations.

[0526] Examples of the compound represented by the general formula (2) include, but are not limited to, trityltetramethylborate, trityltetra(perfluoromethyl)borate, trityltetraphenylborate, trityltetra(perfluorophenyl)borate, and trityltetra(di(trifluoromethyl)phenyl)borate.

[0527] The compound represented by the general formula (1) or (2) may be obtained by using commercially available products or by appropriately modifying a known method according to the substituents possessed by the compound.

[0528] In addition to the compound represented by the general formula (1) or (2), an organic aluminum oxide compound may be added to the catalyst for olefin polymerization of the present invention. Examples of organic aluminum compounds include methylaluminoxane (MAO) and modified methylaluminoxane (MMAO), and commercial products may be used. MMAO is preferred because it is easily available and has good operability. Commercial products may be used for MAO and MMAO, and there is no limitation on the grade.

[0529] In addition to the compounds containing Group 13 elements exemplified above, compounds containing Group 1 metals represented by alkyl lithiums such as methyl lithium and n-butyl lithium, compounds containing Group 2 metals such as Grignard reagents, and conventionally known organometallic compounds can be used as co-catalysts. These compounds can also be commercially available products, and there is no limitation on the grade, etc.

[0530] These co-catalysts can be used under the same conditions as the above-mentioned metal complex catalysts, preferably in an inert gas atmosphere and away from oxygen and moisture. The amount used when added can be appropriately determined by those skilled in the art.

[0531] Furthermore, the contact between the metal complex catalyst and the co-catalyst can be carried out not only during the preparation of the catalyst but also during the prepolymerization of olefin or during the polymerization of olefin.

[0532] The contact between the metal complex catalyst and the co-catalyst is preferably carried out in an inert gas such as nitrogen in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene, etc. The contact can be carried out at a temperature between -20°C and the boiling point of the solvent, and is particularly preferably carried out at a temperature between room temperature and the boiling point of the solvent.

[0533] II-5. Method for producing olefin polymer

[0534] The method for producing an olefin-based polymer according to the second embodiment of the present invention is characterized by polymerizing or copolymerizing olefin in the presence of the olefin polymerization catalyst according to the second embodiment of the present invention.

[0535] The olefin in the present invention may be an acyclic olefin or a cyclic olefin, and may be at least one selected from the group consisting of an acyclic olefin having 2 to 22 carbon atoms and a cyclic olefin having 4 to 20 carbon atoms.

[0536] As the acyclic olefin in the present invention, the general formula: CH2=CHR 30 Here, R 30 R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may have a branch, a ring and / or an unsaturated bond. 30When the carbon number of R is greater than 20, sufficient polymerization activity tends to be not exhibited. 30 Preferred olefins are olefins which are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms.

[0537] Examples of acyclic olefins other than α-olefins include 2-butene, 2-pentene, and 2-hexene.

[0538] Examples of the cyclic olefin having 4 to 20 carbon atoms include cyclobutene, cyclopentene, cyclohexene, cycloheptene, norbornene, and norbornadiene.

[0539] As preferred olefins, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, vinylcyclohexene, styrene, 4-methylstyrene and norbornene can be cited. From the perspective of the manufacturing efficiency of the polymer, it is particularly preferred to be selected from one or more of the group consisting of ethylene, propylene, 1-butene and norbornene, and ethylene is further preferred. It should be noted that as an olefin, only one olefin may be used, or two or more olefins may be used simultaneously.

[0540] Examples of polar group-containing monomers include monomers obtained by introducing polar functional groups (polar groups) into acyclic olefins and cyclic olefins. Examples of monomers obtained by introducing polar groups into α-olefins among acyclic olefins include monomers of the general formula: CH2=C(R 30 )(R 31 ) is a polar group-containing monomer. A preferred example of a polar group-containing monomer is (meth)acrylate. Here, R 30 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 31 Represents -C(O)OR 32 (Here, R 32 represents a hydrocarbon group having 1 to 20 carbon atoms), -C(O)N(-R 32’ )2(Here, R 32’ Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms), a cyano group or an optionally substituted aryl group. 30 It is preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. 30 More preferably, it is a hydrogen atom or a methyl group. 31 , as long as it is the above-mentioned substituent, there is no particular limitation, but -C(O)OR 32 or aromatic. In this case, R 32 When the carbon number of R exceeds 20, the polymerization activity tends to decrease. 32 It is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 8 carbon atoms.

[0541] In addition, as R 32 , preferably composed of carbon atoms and hydrogen atoms, but R 32 It may also contain heteroatoms such as oxygen atoms, sulfur atoms, selenium atoms, phosphorus atoms, nitrogen atoms, silicon atoms, fluorine atoms, and boron atoms. Among these heteroatoms, oxygen atoms, silicon atoms, and fluorine atoms are preferred, and oxygen atoms are more preferred. 32’ The preferred range and examples of R 32 same.

[0542] Examples of monomers in which a polar functional group is introduced into a non-cyclic olefin other than α-olefin or a cyclic olefin include monomers in which the above-mentioned R is introduced into any position of the exemplary compounds of the non-cyclic olefin other than α-olefin or the cyclic olefin. 31 Compounds having the substituents shown.

[0543] In addition, as the polar group-containing monomer, vinylene carbonate (1,3-dioxol-2-one) may be mentioned.

[0544] Further preferred examples of the polar group-containing monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluoyl (meth)acrylate, benzyl (meth)acrylate, hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. -aminoethyl ester, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, glycidyl (meth)acrylate, trifluoromethyl (meth)acrylate, 3,3,3-trifluoropropyl (meth)acrylate, perfluoroethyl (meth)acrylate, (meth)acrylamide, (meth)acryloyldimethylamide, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acrylonitrile, methyl 10-undecenoate, 4-acetoxystyrene, vinyl anisole, methyl 5-norbornene-2-carboxylate, tert-butyl 5-norbornene-2-carboxylate, 5-norbornene-2-methanol, 5-norbornene-2-methylamine, 5-norbornene-2-methylpivalamide, 5-norbornene-2-yl acetate, vinylene carbonate, and the like. More preferably, it is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, tert-butyl methacrylate, acrylonitrile, methyl 10-undecenoate, 4-acetoxystyrene, 4-nitrostyrene, vinyl anisole, methyl 5-norbornene-2-carboxylate, tert-butyl 5-norbornene-2-carboxylate, 5-norbornene-2-methylpivalamide, 5-norbornene-2-yl acetate, and vinylene carbonate.

[0545] As the comonomer used for the copolymerization of acyclic olefins such as ethylene, at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins is preferably used.

[0546] As a further preferred example, it is at least one selected from the group consisting of tert-butyl acrylate, methyl acrylate, methyl methacrylate, methyl 10-undecenoate, 4-methylstyrene, 4-acetoxystyrene, norbornene, tert-butyl 5-norbornene-2-carboxylate, 9-decenyl acetate, 1,2-epoxy-9-decene, and vinylene carbonate.

[0547] These monomers may be used alone or in combination of two or more.

[0548] The type of the above monomers can be appropriately selected according to the physical property required for the obtained polymer. In addition, the composition copolymerization of two or more monomers can also be made, and the composition copolymerization consisting of two or more polar group-containing monomers can also be made. The amount of the monomers mixed, the amount ratio between each monomer can be appropriately set according to the physical property required for the obtained multipolymer.

[0549] The method for producing an olefin polymer of the present invention performs polymerization in the presence of the olefin polymerization catalyst of the present invention, and is therefore suitable for a method for copolymerizing at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins with an acyclic olefin.

[0550] In addition, as the copolymerization reaction of the present invention, copolymerization of an olefin and a (meth)acrylic acid ester is mentioned as a preferred embodiment from the viewpoint of polymerization activity.

[0551] In the method for producing olefin polymers of the present invention, an olefin polymerization catalyst comprising the above-mentioned metal complex catalyst is used as a catalyst for polymerization or copolymerization of olefins. Each metal complex catalyst can be used after separation or supported on a carrier. Such support can be carried out in the reactor used for polymerization of olefins, copolymerization of olefins and (meth) acrylic esters, etc., in the presence or absence of these monomers, or in other containers outside the reactor.

[0552] As a usable carrier, any carrier can be used as long as it does not violate the main purpose of the present invention. Usually, inorganic oxides and polymer carriers can be appropriately used. As inorganic oxides, specifically, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc. or mixtures thereof can be listed, and mixed oxides such as SiO2-Al2O3, SiO2-V2O5, SiO2-TiO2, SiO2-MgO, SiO2-Cr2O3 can also be used. In addition, as a carrier, inorganic silicates, polyethylene carriers, polypropylene carriers, polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylate carriers, polyester carriers, polyamide carriers, polyimide carriers, etc. can be used. For these carriers, particle size, particle size distribution, pore volume, specific surface area, etc. are not particularly limited, and any one can be used.

[0553] As inorganic silicates, clay, clay minerals, zeolites, diatomaceous earth, etc. can be used. These may be synthetic products, or naturally occurring minerals may be used. Specific examples of clay and clay minerals include allophane group such as allophane; kaolin group such as dickite, nacrite, kaolinite, and anthracite; halloysite group such as metahalloysite and halloysite; serpentine group such as chrysotile, lizardite, and antigorite; montmorillonite such as sauconite, beidellite, nontronite, saponite, and hectorite; vermiculite minerals such as vermiculite; mica minerals such as illite, sericite, and glauconite; attapulgite, sepiolite, palygorskite, bentonite, wood clay, gairome clay, ferrosilicon, pyrophyllite, and chlorite group.

[0554] These may form a mixed layer. Examples of artificially synthesized materials include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic tapered mica.

[0555] Among these specific examples, preferably listed are kaolinite, nacrite, kaolinite, annularite and other kaolin family; halloysite family such as metahalloyite and halloysite; serpentine family such as chrysotile, lizardite, antigorite; smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite; vermiculite minerals such as vermiculite; mica minerals such as illite, sericite, glauconite; synthetic mica, synthetic hectorite, synthetic saponite, synthetic taenia, and particularly preferably listed are smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite; vermiculite minerals such as vermiculite; synthetic mica, synthetic hectorite, synthetic saponite, synthetic taenia.

[0556] These carriers can be used directly, or can be treated with hydrochloric acid, nitric acid, sulfuric acid, etc. and / or treated with salts such as LiCl, NaCl, KCl, CaCl2, MgCl2, Li2SO4, MgSO4, ZnSO4, Ti(SO4)2, Zr(SO4)2, Al2(SO4)3. In this treatment, the corresponding acid and base can be mixed to generate salts in the reaction system for treatment. In addition, shape control such as pulverization and granulation and drying treatment can be performed.

[0557] In the method for producing an olefin polymer of the present invention, the polymerization reaction can be carried out in the presence or absence of a known additive in addition to the above-mentioned cocatalyst. As the additive, an additive having the effect of stabilizing the generated polymer is preferred. For example, quinone derivatives, hindered phenol derivatives, etc. can be cited as examples of preferred additives.

[0558] Specifically, hydroquinone monomethyl ether, 2,6-di-tert-butyl 4-methylphenol (BHT), a reaction product of trimethylaluminum and BHT, a reaction product of tetravalent titanium alkoxide and BHT, and the like can be used.

[0559] In addition, inorganic fillers and / or organic fillers may be used as additives, and polymerization may be carried out in the presence of these fillers or with the addition of an ionic liquid.

[0560] As a preferred additive in the present invention, Lewis bases can be cited. By selecting a suitable Lewis base, the activity, molecular weight, and copolymerizability of acrylate can be improved. As the amount of Lewis base, relative to the transition metal M in the catalyst component present in the polymerization system, it is 0.0001 equivalents to 1000 equivalents, preferably 0.1 equivalents to 100 equivalents, and more preferably 0.3 equivalents to 30 equivalents. There is no particular restriction on the method of adding Lewis base to the polymerization system, and any method can be used. For example, it can be added to the catalyst for olefin polymerization of the present invention, it can be mixed with the monomer and added, and it can be added to the polymerization system independently of the catalyst component and the monomer. In addition, a variety of Lewis bases can be used in combination.

[0561] Examples of the Lewis base include aromatic amines, aliphatic amines, alkyl ethers, aryl ethers, alkyl aryl ethers, cyclic ethers, alkyl nitriles, aryl nitriles, alcohols, amides, aliphatic esters, aromatic esters, phosphates, phosphites, thiophenes, thianthracenes, thiazoles, oxazoles, morpholines, and cyclic unsaturated hydrocarbons.

[0562] Among these, particularly preferred Lewis bases are aromatic amines, aliphatic amines, cyclic ethers, aliphatic esters, and aromatic esters, and particularly preferred Lewis bases are pyridine derivatives, pyrimidine derivatives, piperidine derivatives, imidazole derivatives, aniline derivatives, piperidine derivatives, triazine derivatives, pyrrole derivatives, and furan derivatives.

[0563] Specific examples of the Lewis base compound include pyridine, pentafluoropyridine, 2,6-lutidine, 2,4-lutidine, 3,5-lutidine, pyrimidine, N,N-dimethylaminopyridine, N-methylimidazole, 2,2′-bipyridine, aniline, piperidine, 1,3,5-triazine, 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, 2,4,6-tris(2-pyridyl)-s-triazine, quinoline, 8-methylquinoline, phenazine, 1,10-phenanthroline, N-methylpyrrole, 1,8-diazabicyclo-[5.4.0]-undecyl-1,1-dihydro ... carbon-7-ene, 1,4-diazabicyclo-[2,2,2]-octane, triethylamine, benzonitrile, methylpyridine, triphenylamine, N-methyl-2-pyrrolidone, 4-methylmorpholine, benzoxazole, benzothiazole, furan, 2,5-dimethylfuran, dibenzofuran, xanthene, 1,4-dioxane, 1,3,5-trioxane, dibenzothiophene, thianthrene, triphenylphosphoniumcyclopentadienide, triphenyl phosphite, triphenyl phosphate, tripyrrolidinephosphine, etc.

[0564] In the present invention, the polymerization form is not particularly limited. As the polymerization form, it is preferred to use solution polymerization in which all generated polymers are dissolved in a medium, slurry polymerization in which at least a portion of the generated polymers become a slurry in a medium, bulk polymerization with liquefied monomers themselves as a medium, gas phase polymerization carried out in gasified monomers, or high-pressure ion polymerization in which at least a portion of the generated polymers are dissolved in a monomer liquefied under high temperature and high pressure, etc. In addition, it can be any form in intermittent polymerization, semi-intermittent polymerization, and continuous polymerization. As an environment for carrying out polymerization reaction, it is preferably used under an inert gas atmosphere such as under a nitrogen atmosphere. The metal complex catalyst can be used under conventional polymerization conditions, and its use conditions are not particularly limited. The amount of the metal complex catalyst used is not particularly limited as long as it is suitable for the scope of being used as a catalyst, and those skilled in the art can set it appropriately.

[0565] Regarding the polymerization reaction in the present invention, when using a monomer suitable for polymerization in a liquid phase, the reaction is carried out in the presence or absence of a hydrocarbon solvent such as n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, a liquid such as a liquefied olefin, a halogenated hydrocarbon solvent such as chlorobenzene, 1,2-dichlorobenzene, or a polar solvent such as ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropanol, ethylene glycol, etc. In addition, a mixture of liquid compounds described herein can be used as a solvent. Liquefied olefins can also be used as monomers for bulk polymerization. Furthermore, ionic liquids can also be used as solvents. It should be noted that in terms of obtaining high polymerization activity and high molecular weight, it is more preferred to use the above-mentioned hydrocarbon solvents and ionic liquids.

[0566] Unreacted monomers and medium can be separated from the produced copolymer and recycled.

[0567] During the cycle, these monomers and media may be purified and reused, or may be directly reused without purification. The separation of the generated copolymer from the unreacted monomers and the media may be carried out using existing known methods. For example, methods such as filtration, centrifugal separation, solvent extraction, and reprecipitation using a poor solvent may be used.

[0568] The polymerization temperature, polymerization pressure and polymerization time are not particularly limited, and can usually be appropriately set in the following ranges in consideration of productivity and process capability. That is, the polymerization temperature is usually -20°C to 290°C, preferably 0°C to 250°C, more preferably 0°C to 200°C, further preferably 10°C to 150°C, and particularly preferably 20°C to 100°C. The copolymerization pressure is 0.1 MPa to 300 MPa, preferably 0.3 MPa to 200 MPa, more preferably 0.5 MPa to 150 MPa, further preferably 1.0 MPa to 100 MPa, and particularly preferably 1.3 MPa to 50 MPa. The polymerization time can be selected from the range of 0.1 minute to 100 hours, preferably 0.5 minute to 70 hours, and further preferably 1 minute to 60 hours.

[0569] In the present invention, polymerization is usually carried out in an inert gas atmosphere. For example, nitrogen or argon atmosphere can be used, preferably nitrogen atmosphere. It should be noted that a small amount of oxygen or air can be mixed. When a monomer that is a gas at room temperature, such as ethylene, is used, polymerization can be carried out after the reaction system is filled with ethylene.

[0570] There is no particular limitation on the supply of catalyst and monomer to the polymerization reactor, and various supply methods can be adopted according to the purpose. For example, in the case of intermittent polymerization, a method of supplying a predetermined amount of monomer to the polymerization reactor in advance and supplying the catalyst thereto can be adopted. In this case, additional monomer and additional catalyst can be supplied to the polymerization reactor.

[0571] Regarding the control of the composition of the copolymer, a method of supplying multiple monomers to the reactor and changing the supply ratio can usually be used for control. In addition, there can be listed: a method of controlling the copolymer composition by utilizing the difference in monomer reactivity ratio caused by the different structures of the catalyst, and a method of controlling the copolymer composition by utilizing the polymerization temperature dependence of the monomer reactivity ratio. In the present invention, when at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins is copolymerized with acyclic olefins, the total content ratio of the acyclic olefin monomer in all the copolymerized monomers can be appropriately selected according to the desired physical properties, relative to 100 mol% of all monomers, the lower limit can usually be 60.00 mol% or more, can be 70.00 mol% or more, can be 80.00 mol% or more, can be 85.00 mol% or more, can be 90.00 mol% or more. On the other hand, the upper limit can usually be 99.90 mol% or less, can be 99.80 mol% or less, can be 99.70 mol% or less, can be 99.60 mol% or less, can be 99.50 mol% or less. By setting it as this range, affinity with a coating material, adhesion, etc. can be imparted without significantly impairing the original properties of polyolefin such as heat resistance, and physical properties can be controlled.

[0572] The molecular weight of the polymer can be controlled by a conventionally known method, and for example, the following method can be mentioned.

[0573] 1) Control polymerization temperature

[0574] 2) Control monomer concentration

[0575] 3) Controlling the ligand structure in transition metal complexes

[0576] 4) Use of known chain transfer agents such as hydrogen and alkyl metals

[0577] The weight average molecular weight (Mw) of the olefin polymer obtained by the method for producing an olefin polymer of the present invention is not particularly limited. The lower limit of the weight average molecular weight (Mw) of the olefin polymer may be 5,000 or more, and may be 10,000 or more. In addition, the upper limit of the weight average molecular weight (Mw) of the olefin polymer may be 1,000,000 or less, and may be 500,000 or less.

[0578] The weight average molecular weight (Mw) of the olefin polymer is determined by gel permeation chromatography (GPC). The GPC measurement in the present invention can be performed by the method described in the examples described later.

[0579] When the olefin polymer obtained by the method for producing an olefin polymer of the present invention is an ethylene polymer, the ethylene polymer is 13 The degree of methyl branching calculated by C-NMR is not particularly limited, but may be 10 or less, or 5 or less per 1,000 carbon atoms.

[0580] In addition, the measurement of the number of methyl branches in the present invention can be carried out by the method described in the Examples described later.

[0581] The method for producing an olefin polymer of the present invention can provide an olefin polymer or copolymer with high activity, and in particular can provide a copolymer of at least one monomer selected from the group consisting of a polar group-containing monomer and a cyclic olefin and an acyclic olefin, and thus can be used as a method for providing a polymer having various characteristics. In addition, the catalytic performance of the catalyst used in the method of the present invention is balanced, and not only a high molecular weight (co)polymer is obtained with high activity, but also as a catalyst, it can be used efficiently for the synthesis of olefin polymers without separation.

[0582] Example

[0583] The present invention is described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples. The synthesis and polymerization of the ligands and metal complexes in the following synthesis examples and embodiments were all carried out under nitrogen or argon atmosphere unless otherwise stated.

[0584] The following terms used in the examples are explained.

[0585] tBA: tert-butyl acrylate

[0586] MA: Methyl acrylate

[0587] VC: Vinylene carbonate

[0588] NB: Norbornene

[0589] TNOA: Tri-n-octyl aluminum

[0590] MU: 10-Undecenoic acid methyl ester

[0591] [Structural Analysis Method in Synthesis Example]

[0592] The structures of the compounds disclosed in the synthesis examples were determined using a JNM-ECS400 NMR apparatus manufactured by JEOL, an Avance400 NMR apparatus manufactured by Bruker, or an Avance500 NMR apparatus manufactured by Bruker. 1 H-NMR, 13 C-NMR, 19 F-NMR and 31 P{ 1 The specific measurement method is as follows.

[0593] [Sample preparation]

[0594] 5 to 20 mg of the sample is dissolved in 0.6 mL of deuterated chloroform (CDCl3) containing no tetramethylsilane, 0.6 mL of deuterated chloroform containing 0.03% (v / v) tetramethylsilane, 0.6 mL of deuterated toluene (C6D5CD3) containing 0.03% (v / v) tetramethylsilane, or 0.6 mL of dimethyl sulfoxide (DMSO)-d6 containing no tetramethylsilane, and added to an NMR sample tube with an inner diameter of 5 mmφ.

[0595] [ 1 H-NMR measurement conditions]

[0596] Probe: 5mmφ probe

[0597] Sample temperature: room temperature

[0598] Pulse angle: 45°

[0599] Pulse interval: 2.8 seconds

[0600] Cumulative times: 8 times

[0601] Chemical shift: For chemical shift when deuterated chloroform is used as a solvent, the proton signal of tetramethylsilane is set to 0 ppm or the proton signal of chloroform is set to 7.26 ppm, and the chemical shifts of other proton signals are based on this. For chemical shift when deuterated toluene is used as a solvent, the proton signal of tetramethylsilane is set to 0 ppm, and the chemical shifts of other proton signals are based on this. When dimethyl sulfoxide-d6 is used as a solvent, the proton signal of dimethyl sulfoxide-d5 is set to 2.50 ppm, and the chemical shifts of other proton signals are based on this.

[0602] [ 19 F-NMR]

[0603] Probe: 5mmφ probe

[0604] Sample temperature: room temperature

[0605] Pulse angle: 45°

[0606] Pulse interval: 1.8 seconds

[0607] Cumulative times: 8 times

[0608] Chemical shift: CFCl3 was used as an external standard, and the chemical shift was set to 0 ppm. The chemical shifts of other fluorine signals were based on this standard.

[0609] [ 31 P{ 1 H}-NMR]

[0610] Probe: 5mm φ probe

[0611] Sample temperature: room temperature

[0612] Pulse angle: 30°

[0613] Pulse interval: 0.5 seconds

[0614] Cumulative times: 64-256 times

[0615] Chemical shift: 85% phosphoric acid aqueous solution was used as an external standard, and the chemical shift was set to 0 ppm. The chemical shifts of other phosphorus signals were based on this standard.

[0616] [Structural analysis method of polymer]

[0617] The results were obtained by using a Bruker Biospin AV400 NMR instrument. 1 H-NMR and 13The structure of the polymer obtained in the example was determined by C-NMR analysis. The specific determination method is as follows.

[0618] [Sample preparation]

[0619] 100 to 500 mg of a sample, 2.4 ml of a mixed solution of o-dichlorobenzene (ODCB) and deuterated bromobenzene (C6D5Br) (volume ratio: ODCB / C6D5Br=3 / 1), and hexamethyldisiloxane as a chemical shift reference substance are added to an NMR sample tube with an inner diameter of 10 mmφ, and dissolved until uniform using a block heater at 150°C.

[0620] [ 1 H-NMR measurement conditions]

[0621] Probe: 10mmφ cryoprobe

[0622] Sample temperature: 120℃

[0623] Pulse angle: 4.5°

[0624] Pulse interval: 2 seconds

[0625] Cumulative times: 256-1024 times

[0626] Chemical shift: The chemical shift of the proton signal of hexamethyldisiloxane was set to 0.09 ppm, and the chemical shifts of the signals of other protons were based on this.

[0627] [ 13 C-NMR measurement conditions]

[0628] <Ethylene / tBA>

[0629] <Ethylene / MA>

[0630] <Acrylic / MU>

[0631] Probe: 10mmφ cryoprobe

[0632] Sample temperature: 120℃

[0633] Pulse angle: 90°

[0634] Pulse interval: 51.5 seconds

[0635] Cumulative times: 256-768 times

[0636] Decoupling conditions: Anti-gating decoupling method

[0637] Chemical shift: Hexamethyldisiloxane 13 The chemical shift of the C signal was set to 1.98 ppm, and the other 13The chemical shift of the C signal is based on this.

[0638] <Ethylene (E) homopolymer>

[0639] Probe: 10mmφ cryoprobe

[0640] Sample temperature: 120℃

[0641] Pulse angle: 45°

[0642] Pulse interval: 27.5 seconds

[0643] Cumulative times: 768-1024 times

[0644] Decoupling conditions: broadband decoupling method

[0645] Chemical shift: Hexamethyldisiloxane 13 The chemical shift of the C signal was set to 1.98 ppm, and the other 13 The chemical shift of the C signal is based on this.

[0646] <Ethylene (E) / NB copolymer>

[0647] <Propylene (P) homopolymer>

[0648] Probe: 10mmφ cryoprobe

[0649] Sample temperature: 120℃

[0650] Pulse angle: 45°

[0651] Pulse interval: 38.5 seconds

[0652] Cumulative times: 256-512 times

[0653] Decoupling conditions: broadband decoupling method

[0654] Chemical shift: The chemical shift of the 13C signal of hexamethyldisiloxane was set to 1.98 ppm, and the chemical shifts of other 13C signals were based on this.

[0655] <Ethylene (E) / VC copolymer>

[0656] Probe: 10mmφ cryoprobe

[0657] Sample temperature: 120℃

[0658] Pulse angle: 90°

[0659] Pulse interval: 51.5 seconds

[0660] Cumulative times: 512 times

[0661] Decoupling conditions: Anti-gating decoupling method

[0662] Chemical shift: Hexamethyldisiloxane 13 The chemical shift of the C signal was set to 1.98 ppm, and the other 13 The chemical shift of the C signal is based on this.

[0663] [Comonomer calculation method]

[0664] Hereinafter, I represents the integrated intensity, and the value of the subscript of I represents the range of chemical shift. 80.0～2.0 Represents the integrated intensity of the signals detected between 80.0 ppm and 2.0 ppm.

[0665] <Ethylene (E) / tBA copolymer>

[0666] use 13 The tBA content was calculated from the signal of C-NMR spectrum using the following formula.

[0667] tBA content (mol%) = I (tBA) ×100 / (I (E) +I (tBA) )

[0668] Here, I (tBA) ,I (E) The quantities are shown in the following formulas respectively.

[0669] I (tBA) =I 79.5～79.0

[0670] I (E) =(I 180.0～136.0 +I 120.0～100.0 +I 80.0～2.0 -I (tBA) ×7) / 2

[0671] <Ethylene (E) / MA copolymer>

[0672] MA content (mol%)

[0673] =I (MA) ×100 / (I (E) +I (MA) )

[0674] Here, I (MA) ,I (E) The quantities are shown in the following formulas respectively.

[0675] I (MA) =I 51.5～50.5

[0676] I (E) =(I 180.0～136.0 +I120.0～100.0 +I 55.0～2.0 -I (MA) ×4) / 2

[0677] <Ethylene (E) / NB copolymer>

[0678] use 13 The NB content was calculated from the signal of C-NMR spectrum using the following formula.

[0679] NB content (mol%) = I (NB) ×100 / (I (E) +I (NB) )

[0680] Here, I (NB) ,I (E) The quantities are shown in the following formulas respectively.

[0681] I (NB) =I 48.3～41.3 / 4

[0682] I (E) =(I 180.0～136.0 +I 120.0～100.0 +I 50.0～2.0 -I (NB) ×7) / 2

[0683] <Ethylene (E) / VC copolymer>

[0684] use 13 The polar group-containing monomer content was calculated from the signal at 77.7 to 80.2 ppm in the C-NMR spectrum using the following formula.

[0685] VC (closed ring) amount (mol%) = I (VC) ×100 / 〔I (VC) +I (E) 〕

[0686] Here, I (VC) ,I (E) The quantities are shown in the following formulas respectively.

[0687] I (VC) =(I 78.8～80.2 +I 77.7～78.2 ) / 2

[0688] I (E) =(I 2.0～120.0 +I 135.0～200.0 -I(VC)×3) / 2

[0689] <Propylene / MU copolymer>

[0690] use 13 The MU content was calculated from the signal of C-NMR spectrum using the following formula.

[0691] MU content (mol%) = I (MU) ×100 / (I (P) +I (MU) )

[0692] Here, I (MU) ,I (P) The quantities are shown in the following formulas respectively.

[0693] I (MU) =I 50.8～50.6

[0694] I (P) =(I 180.0～136.0 +I 120.0～100.0 +I 55.0～2.0 -I (MU) ×12) / 3

[0695] [Calculation of MU Remaining Amount]

[0696] use 13 The remaining amount of MU was calculated from the signal of C-NMR spectrum using the following formula.

[0697] MU residual amount (mol%) = I (MU单体) ×100 / (I (P) +I (MU) )

[0698] Here, I (MU单体) ,I (P) The quantities are shown in the following formulas respectively.

[0699] I (MU monomer ) =I 114.3～114.1

[0700] I (P) =(I 180.0～136.0 +I 120.0～100.0 +I 55.0～2.0 -I (MU) ×12) / 3

[0701] The branched structure can be 13 C-NMR spectrum of tertiary carbon atoms. For example, for methyl branches, 13 The value I is obtained by dividing the sum of the integrated intensities of the signals of methyl carbon at 20.0 to 19.8 ppm (corresponding to v in the following structural formula) and methylene carbon at 37.6 to 37.3 ppm (corresponding to x in the following structural formula) in the C-NMR spectrum by 3. B1 , the number of methyl branches per 1,000 carbon atoms was calculated by the following formula.

[0702] Number of methyl branches (per 1000 carbon atoms) = 1 B1 ×1000 / I total

[0703] Here, I B1 ,I total The quantities are shown in the following formulas respectively.

[0704] I B1 =(I 20.0～19.8 +I 37.6～37.3 ) / 3

[0705] I total =I 180.0～136.0 +I 120.0～100.0 +I 80.0～2.0

[0706]

[0707] [Stereoregularity in propylene polymerization]

[0708] The stereoregularity of polypropylene can also be measured quantitatively. 13 C-NMR structural analysis. 13 In the C-NMR spectrum, the three peaks at 21.1ppm to 22.4ppm correspond to mm, the three peaks at 20.3ppm to 21.1ppm correspond to mr, and the three peaks at 19.4ppm to 20.3ppm correspond to rr. By calculating the integral ratio of these, the ratio of mm, mr, and rr can be found.

[0709] [Number average molecular weight and weight average molecular weight]

[0710] The number average molecular weight and weight average molecular weight are calculated by size exclusion chromatography using polystyrene as a molecular weight standard substance. The specific measurement method of GPC is as follows.

[0711] Apparatus: GPC manufactured by Agilent Technologies (PL-GPC220)

[0712] Detector: IR detector

[0713] Column: AT806MS manufactured by Showa Denko K.K. (3 connected in series)

[0714] Mobile phase solvent: ODCB

[0715] Measuring temperature: 140℃

[0716] Flow rate: 1.0mL / min

[0717] Injection volume: 0.3mL

[0718] [Preparation of sample]

[0719] The sample was dissolved in ODCB containing 0.24 mg / mL of TMP (2,3,6-trimethylphenol) at 140° C. for about 1 hour to prepare a 1 mg / mL sample solution.

[0720] The retention volume obtained in the GPC measurement is converted into a molecular weight using a pre-made standard curve based on standard polystyrene (PS). The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000. A calibration curve was prepared using standard polystyrene solutions dissolved in ODCB containing 0.24 mg / mL of TMP in a manner of 0.5 mg / mL. The calibration curve uses a cubic polynomial approximated by the least squares method. It should be noted that the viscosity formula [η] used when converting to molecular weight is [η] = K×M α Use the following values.

[0721] PS: K = 1.38 × 10 -4 , α=0.700

[0722] PP: K = 1.03 × 10 -4 , α=0.780

[0723] PE: K = 3.92 × 10 -4 , α=0.733

[0724] The catalyst activity was calculated by the following formula.

[0725] Catalyst activity (kg / mol / h) = yield of polymer obtained (kg) / {amount of ligand used (mol) × reaction time (h)}

[0726] <Example I Series: First Embodiment of the Present Invention>

[0727] (Synthesis Example I-1: Synthesis of AL-29)

[0728] (1) Synthesis of 2,3,5,6-tetrahydrobenzo[1,2-b:5,4-b']difuran

[0729] The compound of the following chemical formula was synthesized according to the description of Tetrahedron, 2005, 61, 4805-4810.

[0730]

[0731] (2) Synthesis of bis(2,3,5,6-tetrahydrobenzo[1,2-b:5,4-b']difuran-8-yl)phosphine chloride

[0732] 2,3,5,6-tetrahydrobenzo[1,2-b:5,4-b']difuran (5 g, 30.8 mmol, 1 eq) was dissolved in 400 mL of diethyl ether. The resulting solution was cooled to -78°C, n-BuLi (37 mmol, 1.2 eq) was added, and the mixture was stirred at -78°C for 30 minutes. Then, the resulting reaction solution was heated to 0°C and stirred for 4 hours to obtain a yellow suspension.

[0733] The suspension was cooled to -78°C and PCl3 (2.12 g, 15.4 mmol, 0.5 eq) was added at once. The mixture was heated to 20°C and stirred for 12 hours to obtain a yellow solution. The resulting yellow solution was evaporated to dryness to obtain 12 g of a mixture containing the target product. The obtained mixture was used directly in the subsequent synthesis without purification.

[0734] 31 P{ 1 H}NMR (162 MHz, CDCl3) δ: 49.4 (s, integral ratio about 20% intensity), -4.3 (s, integral ratio about 80%)

[0735]

[0736] (3) Synthesis of bis(2,3,5,6-tetrahydrobenzo[1,2-b:5,4-b']difuran-8-yl)phosphine

[0737] Dissolve bis(2,3,5,6-tetrahydrobenzo[1,2-b:5,4-b']difuran-8-yl)phosphine chloride (6 g, 15.4 mmol, 1 eq) in 100 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, lithium aluminum hydride (1.17 g, 30.9 mmol, 2 eq) was added, and the mixture was stirred at 20°C for 2 hours to obtain a colorless suspension. Ethyl acetate (50 mL x 4) was added to the suspension to stop the reaction, and the obtained suspension was evaporated to dryness to obtain a colorless solid. The solid was purified by silica gel chromatography (developing solvent: petroleum ether / ethyl acetate / dichloromethane = 4 / 1 / 1) under atmospheric pressure to obtain 4.5 g (12.7 mmol, yield 82% when the raw material purity is set to 100%) of the target compound.

[0738] 1 H NMR (400MHz, CDCl3) δ: 6.87 (s, 2H), 5.23 (d, J = 237Hz, 1H), 4.55 (t, J = 8.6Hz, 8H), 3.06 (t, J = 8.6Hz, 8H)

[0739] 31 P{ 1 H}NMR(162MHz, CDCl3)δ: -128.0(s)

[0740]

[0741] (4) Synthesis of AL-29

[0742] 500 mg (1.4 mmol) of the above-synthesized bis(2,3,5,6-tetrahydrobenzo[1,2-b:5,4-b']difuran-8-yl)phosphine was weighed into a Schlenk tube, and 18 mL of tetrahydrofuran was added. After the resulting solution was cooled to -78°C, 0.98 mL (1.6 mmol) of n-BuLi was slowly added dropwise. After the addition was completed, the mixture was stirred at -78°C for 1 hour and 10 minutes. The mixture was then heated to 0°C, and 265 mg (1.4 mmol) of α-(trifluoromethyl)styrene oxide dissolved in 4.7 mL of tetrahydrofuran was slowly added. The mixture was stirred at room temperature for 2 hours and 30 minutes, and then stirred at 60°C for 2 hours and 10 minutes. After that, the solvent was completely distilled off from the mixture, and 23 mL of tetrahydrofuran was added to the residue. After the generated solution was cooled to 0°C, 0.85 mL (1.7 mmol) of an ether solution of hydrogen chloride (hereinafter also referred to as "ethereal hydrochloric acid solution") was slowly added dropwise. After the obtained solution was stirred at 0°C for 30 minutes, 14 mL of degassed water was added to the solution for washing, and the organic layer was separated. 8 mL of ether was added to the aqueous layer and the organic layer was extracted. This operation was repeated 3 times. After drying the collected organic layer with sodium sulfate, the sodium sulfate was removed using a glass filter. After evaporating the filtrate to dryness, the obtained solid was purified by silica gel column chromatography (developing solvent: hexane / acetone = 5 / 1 to 3 / 1, further changed to 1 / 1) under atmospheric pressure to obtain 189 mg of a solid. Using 31 The purity of AL-29 determined by P-NMR was 97%.

[0743] 1 H NMR (400MHz, CDCl3) δ: 7.50-7.48 (m, 2H), 7.23-7.19 (m, 3H), 6.86 (s, 2H), 5.02 (brs, 1H ), 4.52-4.46 (m, 6H), 4.38-4.31 (m, 2H), 3.86 (dd, J=15.3, 3.6Hz, 1H), 3.04-2.95 (m, 9H)

[0744] 19 F NMR(376MHz, CDCl3)δ: -80.4(s)

[0745] 31 P{ 1 H}NMR(162MHz, CDCl3)δ: -64.9(s)

[0746]

[0747] (Synthesis Example I-2: Synthesis of AL-36)

[0748] 500 mg (1.4 mmol) of bis(2,3,5,6-tetrahydrobenzo[1,2-b:5,4-b']difuran-8-yl)phosphine was weighed into a Schlenk tube, and 18 mL of tetrahydrofuran was added. After the resulting solution was cooled to -78°C, 0.98 mL (1.6 mmol) of n-BuLi was slowly added dropwise. After the addition was completed, the mixture was stirred at -78°C for 2 hours. The mixture was then heated to 0°C, and 0.15 mL (1.4 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 4.7 mL of tetrahydrofuran was slowly added. The mixture was stirred at room temperature for 1 hour and 30 minutes, cooled to 0°C, and 0.85 mL (1.7 mmol) of hydrochloric acid ether solution was slowly added dropwise. The mixture was stirred at 0°C for 30 minutes, and then 14 mL of degassed water was added for washing, and the organic layer was separated. 8 mL of ether was added to the aqueous layer and the organic layer was extracted. This operation was repeated 3 times. The collected organic layer was dried over sodium sulfate and the sodium sulfate was removed using a glass filter. The filtrate was evaporated to dryness and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane / acetone = changed from 5 / 1 to 3 / 1) under atmospheric pressure to obtain 426 mg of solid. 31 The purity of AL-36 determined by P-NMR was 99% or more.

[0749] 1 H NMR (400MHz, CDCl3) δ: 6.92 (s, 2H), 5.48 (d, J = 3.7Hz, 1H), 4.56-4.46 (m, 8H), 3.15 (s, 2H), 3.05 (t, J = 8.8Hz, 8H)

[0750] 19 F NMR (376MHz, CDCl3) δ: -77.1 (d, J=22.0Hz) 31 P{ 1 H}NMR (162MHz, CDCl3) δ: -65.3 (septet, J=22.5Hz)

[0751]

[0752] (Synthesis Example I-3: Synthesis of AL-36 / NiMePy)

[0753] Weigh 85 mg (0.19 mmol) of dichlorotetra(pyridine)nickel (II) into a Schlenk tube, add 1.8 mL of toluene and 0.2 mL of tetrahydrofuran. After cooling the resulting solution to 0°C, slowly drop 80 μL (0.99 mmol) of pyridine and 0.35 mL (0.38 mmol) of methyl lithium to obtain a transition metal compound solution. On the other hand, add 0.6 mL of toluene to a Schlenk tube to which 100 mg of AL-36 (0.19 mmol) has been added to obtain an AL-36 solution. Add the above AL-36 solution to the above transition metal compound solution. Furthermore, wash the Schlenk tube to which AL-36 has been added twice with 0.2 mL of toluene, and the washing liquid is also added to the above transition metal compound solution. After stirring the mixture at 40°C for 2 hours and 20 minutes, completely distill off the solvent. Add 10 mL of toluene to the obtained residue, and filter the mixture with diatomaceous earth. The solvent of the filtrate was completely distilled off, and the residue was washed twice with 1 mL of hexane and once with 2 mL of hexane. The residue was evaporated to dryness to obtain 52 mg of a solid.

[0754] use 31 The purity of AL-36 / NiMePy determined by P-NMR was 99% or more.

[0755] AL-36 / NiMePy is a metal complex having the following structure.

[0756] 1 H NMR (400MHz, C6D5CD3) δ: 8.90 (br, 2H), 6.77 (br, 1H), 6.64 (s, 2H), 6.47 (br, 2H), 4.11 (t, J=8.7Hz, 8H), 4.00 (d, J=12.5Hz, 2H), 2.54 (t, J=8.6Hz, 8H), -0.47 (d, J=6.3Hz, 3H)

[0757] 19 F NMR(376MHz, C6D5CD3)δ: -77.1(s)

[0758] 31 P{ 1 H}NMR(162MHz, C6D5CD3)δ: 5.2(s)

[0759]

[0760] (Synthesis Example I-4: Synthesis of AL-52)

[0761] (1) Synthesis of 4-bromo-1,2,3,5,6,7-hexahydro-s-indane

[0762] 1,2,3,5,6,7-hexahydro-s-indane-4-amine (10 g, 57.7 mmol) was dissolved in 48% aqueous hydrogen bromide solution (40 mL). After the solution was cooled to 0°C, sodium nitrite (4.38 g, 63.5 mmol) was added very slowly. The reaction temperature was maintained in the range of 0°C to 5°C and the mixture was stirred for 2 hours to obtain a solution of a diazonium salt. Next, the obtained solution was added to a mixture of copper bromide (11.6 g, 80.8 mmol) and 48% aqueous hydrogen bromide solution (35 mL). The mixture was stirred at 100°C for 18 hours to obtain a black solution. From the mixture, organic matter was extracted 3 times with dichloromethane, and the collected organic layer was washed with potassium hydroxide aqueous solution (1 M), then washed with water, and dried over magnesium sulfate. The solvent was distilled off to obtain a brown solid. The obtained solid was purified by silica gel column chromatography (developing solvent: petroleum ether 100%) to obtain the target compound as a white solid (4.0 g, 17 mmol).

[0763] 1 H NMR (CDCl3, 500MHz) δ: 7.53 (d, J=2.0Hz, 1H), 3.28-3.15 (m, 8H), 2.36 (quintet, J=7.0Hz, 4H)

[0764]

[0765] (2) Synthesis of ethoxybis(1,2,3,5,6,7-hexahydro-s-benzoindane-4-yl)phosphine

[0766] A tetrahydrofuran solution (17 mL) of 4-bromo-1,2,3,5,6,7-hexahydro-s-benzodiindene (4 g, 17 mmol) was slowly added dropwise to magnesium (615 mg, 25.3 mmol) at 20°C. The mixture was stirred at 20°C for 2 hours to obtain an off-white suspension. Next, a tetrahydrofuran solution (10 mL) of ethyl dichlorophosphite (1.18 g, 8.00 mmol) was cooled to -78°C, and the off-white suspension (16.0 mL) obtained above was added dropwise thereto at -78°C. The mixture was slowly heated to 20°C and stirred for 18 hours to obtain a yellow solution.

[0767] 31 P{ 1 H}NMR (162MHz, CDCl3) δ: 112.2 (s, integration ratio 19%)

[0768]

[0769] (3) Synthesis of ethoxybis(1,2,3,5,6,7-hexahydro-s-benzoindane-4-yl)phosphine borane

[0770] Ethoxybis(1,2,3,5,6,7-hexahydro-s-indane-4-yl)phosphine (3.12 g) was dissolved in toluene (10 mL), and borane dimethyl sulfide (10 M, 3.99 mL, 39.9 mmol) was added dropwise at 20°C for 3 minutes. The resulting solution was stirred at 20°C for 6 hours to obtain a light yellow solution. The mixture was cooled to 0°C, and water (10 mL) was added dropwise while the reaction temperature was maintained in the range of 0°C to 10°C. The resulting mixture was stirred for 0.5 hours. From the mixture, the organic layer was extracted 3 times with ethyl acetate (100 mL), and the collected organic layer was washed with saturated brine. After that, it was dried over sodium sulfate, and the solvent was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = 10 / 1) to obtain a white solid (1.5 g, 3.7 mmol).

[0771] 1 H NMR (CDCl3, 400MHz) δ: 7.21 (s, 2H), 3.94 (dq, J=7.2, 7.2Hz, 2H), 2.85-2.75 (m, 16H), 1.99-1.92 (m, 8H), 1.27 (t, J=6.8Hz, 3H), 1.50-0.50 (br)

[0772] 31 P{ 1 H}NMR (CDCl3, 162MHz) δ: 108.4-108.0 (m, integration ratio 85%)

[0773]

[0774] (4) Synthesis of bis(1,2,3,5,6,7-hexahydro-s-indane-4-yl)phosphine borane

[0775] Ethoxybis(1,2,3,5,6,7-hexahydro-s-indane-4-yl)phosphine borane (1.25 g) and naphthalene (39.6 mg, 309 μmol) were dissolved in tetrahydrofuran (10 mL), and sodium (156 mg, 6.80 mmol) was added at 20°C. The mixture was stirred at 20°C for 18 hours to obtain a reddish brown solution. The reddish brown solution was cooled to 0°C, and water (236 mg, 13.1 mmol) was added dropwise thereto. The obtained white suspension was stirred for 0.5 hours. The organic layer was extracted from the mixture three times with dichloromethane (20 mL). The collected organic layer was washed with a saturated aqueous ammonium chloride solution (30 mL) and then with a saturated saline solution (20 mL). After that, it was dehydrated with sodium sulfate and the solution was distilled off to obtain a yellow solid. The obtained solid was purified by silica gel column chromatography (developing solvent: petroleum ether / dichloromethane = 1 / 1) to obtain a white solid (0.7 g, 2.0 mmol).

[0776] 1 H NMR (CDCl3, 500MHz) δ: 7.19 (s, 2H), 6.47 (dq, J=379, 7.5Hz, 1H), 2.93-2.80 (m, 16H), 2.10-1.95 (m, 8H), 1.45-0.50 (br)

[0777] 31 P{ 1 H}NMR (CDCl3, 202MHz) δ: -20.3-(-21.0)(br)

[0778]

[0779] (5) Synthesis of bis(1,2,3,5,6,7-hexahydro-s-benzoindane-4-yl)phosphine

[0780] At 20°C, bis(1,2,3,5,6,7-hexahydro-s-indane-4-yl)phosphine borane (2.5 g, 6.94 mmol) was dissolved in a dioxane solution of hydrogen chloride (10 mL) and stirred for 12 hours to obtain a white suspension. After distilling off the solvent, the obtained residue was dissolved in dichloromethane (about 100 mL), and the mixture was washed once with a saturated sodium bicarbonate aqueous solution (50 mL), and then washed twice with saturated brine (50 mL). After that, it was dehydrated with sodium sulfate and the solvent was removed to obtain a crude product as a yellow solid. The crude product was purified by silica gel column chromatography (developing solvent: dichloromethane / petroleum ether = 1 / 2) to obtain a white solid (0.9 g, 2.6 mmol).

[0781] 1H NMR (CDCl3, 400MHz) δ: 7.06 (s, 2H), 2.85 (t, J=7.4Hz, 8H), 2.73 (t, J=7.4Hz, 8H), 2.15-1.95 (m, 8H)

[0782] 31 P{ 1 H}NMR (CDCl3, 162MHz) δ: -85.0 (s)

[0783]

[0784] (6) Synthesis of AL-52

[0785] 300 mg (0.87 mmol) of the above-synthesized bis(1,2,3,5,6,7-hexahydro-s-indane-4-yl)phosphine was weighed into a Schlenk tube, and 11 mL of tetrahydrofuran was added. After the resulting solution was cooled to -78°C, 0.60 mL (0.96 mmol) of n-BuLi was slowly added dropwise. After the addition was completed, the mixture was stirred at -78°C for 1 hour and 40 minutes. The mixture was then heated to 0°C, and 164 mg (0.87 mmol) of α-(trifluoromethyl)styrene oxide dissolved in 2.8 mL of tetrahydrofuran was slowly added. The container containing α-(trifluoromethyl)styrene oxide was then washed twice with 0.6 mL of tetrahydrofuran, and the washing liquid was also added to the Schlenk tube. After the mixture was stirred at room temperature for 1 hour, the solvent was completely distilled off, and 15 mL of tetrahydrofuran was added to the residue. After the resulting solution was cooled to 0°C, 1.0 mL (1.0 mmol) of hydrochloric acid ether solution was slowly added dropwise. After the mixture was stirred at 0°C for 30 minutes, 9 mL of water was added for washing and the organic layer was separated. All subsequent operations were performed under the atmosphere. 5 mL of ether was added to the aqueous layer and the organic layer was extracted. This operation was repeated 3 times. After the collected organic layer was dried over sodium sulfate, the sodium sulfate was removed using a glass filter. After the filtrate was evaporated to dryness, the obtained solid was purified 3 times by silica gel column chromatography (developing solvent: hexane / acetone = 40 / 1 for the first time, hexane / acetone = 20 / 1 for the second and third times) to obtain 83 mg of solid. Using 31 The purity of AL-52 determined by P NMR was 94%.

[0786] 1H NMR (400MHz, CDCl3) δ: 7.35 (d, J=7.2Hz, 2H), 7.24-7.14 (m, 3H), 7.06 (s, 1H), 6.95 (s, 1H), 3.48 (dd, J=14.2, 2.6Hz, 1H), 3. 35 (d, J=14.4Hz, 1H), 3.31 (d, J=9.6Hz, 1H), 2.77 (t, J=7.6Hz, 4H), 2.73-2.58 (m, 10H), 2.39-2.32 (m, 2H), 1.98-1.76 (m, 8H)

[0787] 19 F NMR(376MHz, CDCl3)δ: -81.0(s)

[0788] 31 P{ 1 H}NMR(162MHz, CDCl3)δ: -40.1(s)

[0789]

[0790] (Synthesis Example I-5: Synthesis of AL-61)

[0791] (1) Synthesis of tert-butyl (2,3,5,6-tetrahydrobenzo [1,2-b:5,4-b'] difuran-8-yl) phosphine borane

[0792] A solution of 2,3,5,6-tetrahydrobenzo[1,2-b:5,4-b']difuran (4 g, 25 mmol) in diethyl ether (100 mL) was cooled to 0°C, and n-butyl lithium (2.5 M, 10.9 mL, 27.3 mmol) was added. After the mixture was stirred at 20°C for 3 hours, the resulting mixture was added to a solution of tert-butylphosphine dichloride (4.31 g, 27.1 mmol) in tetrahydrofuran (20 mL) cooled to -78°C. The mixed solution was stirred at 20°C for 16 hours to obtain a white suspension of tert-butyl(2,3,5,6-tetrahydrobenzo[1,2-b:5,4-b']difuran-8-yl)phosphine chloride.

[0793] 31 P{ 1 H}NMR (202MHz, CDCl3) δ: 33.6 (s, integration ratio 91%)

[0794] Borane dimethyl sulfide (10 M, 7.40 mL, 74.0 mmol) was added to the above-mentioned white turbid suspension at 0° C. The mixture was stirred at 20° C. for 16 hours to obtain a colorless solution.

[0795] 31 P{1 H}NMR(162MHz, CDCl3)δ: 114.4-114.1(m)

[0796] The colorless solution was cooled to 0°C and lithium aluminum hydride (1M, 36.9 mL, 36.9 mmol) was added. The mixture was stirred at 20°C for 16 hours to obtain a white suspension. Degassed water (1.5 mL) was slowly added to the mixture, followed by a degassed 15% aqueous sodium hydroxide solution (1.5 mL), and then a degassed water (4.5 mL) was slowly added. After stirring at room temperature for 30 minutes, the mixture was filtered and the filtrate was concentrated to obtain a white oily substance. The oily substance was purified by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = 10 / 1) to obtain the target compound as a white solid (4.42 g, 16.7 mmol).

[0797] 1 H NMR (400MHz, CDCl3) δ: 7.06 (s, 1H), 5.43 (dq, J=377, 7.0Hz, 1H), 4.67-4.54 (m, 4H), 3.12 (t, J=8.6Hz, 4H), 1.22 (d, J=15.2Hz, 9H), 1.02-0.20 (br, 3H)

[0798] 31 P{ 1 H}NMR(162MHz, CDCl3)δ: 1.3-0.9(br)

[0799]

[0800] (2) Synthesis of AL-61

[0801] 300 mg (1.14 mmol) of the synthesized tert-butyl (2,3,5,6-tetrahydrobenzo [1,2-b: 5,4-b'] difuran-8-yl) phosphine borane was weighed into a Schlenk tube, and 10 mL of tetrahydrofuran was added. After the resulting solution was cooled to -78°C, 2.45 mL (1.47 mmol) of a 0.6 M toluene solution of potassium bis (trimethylsilyl) amide was slowly added dropwise. After the addition was completed, the mixture was heated to 0°C, and 10 mL of tetrahydrofuran was added. After the mixture was stirred at 0°C for 1 hour, 0.140 mL (1.28 mmol) of 2,2-bis (trifluoromethyl) oxirane was slowly added. After the mixture was stirred at room temperature for 2 hours, it was cooled to 0°C, and 0.87 M hydrochloric acid (3.4 mmol) was slowly added dropwise. The product was extracted from the mixture with 5 mL of ether three times, and the collected organic layer was washed with 5 mL of water. Next, the organic layer was dried over sodium sulfate and filtered through absorbent cotton to remove the sodium sulfate. The filtrate was evaporated to dryness, and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane / dichloromethane = 2 / 1) in air to obtain 384 mg of a solid.

[0802] To 299 mg (0.675 mmol) of the solid obtained above, 91 mg (0.81 mmol) of 1,4-diazabicyclo[2.2.2]octane dissolved in 5 mL of toluene was added, the mixture was heated to 60°C, and then stirred for one and a half hours. The obtained solution was purified by silica gel column chromatography (developing solvent: hexane / acetone = 5 / 1) under nitrogen to obtain 234 mg of solid. The solid was purified again by silica gel column chromatography (developing solvent: hexane / acetone = 5 / 1) to obtain 118 mg of solid. 31 The purity of AL-61 determined by P{1H}NMR was 97%.

[0803] 1 H NMR (400MHz, CDCl3) δ: 7.02 (s, 1H), 4.61-4.51 (m, 5H), 3.76 (dd, J=16.0Hz, 3. 2Hz, 1H), 3.10 (t, J=8.6Hz, 4H), 2.06 (d, J=16.0Hz, 1H), 1.09 (d, J=13.7Hz, 9H)

[0804] 19 F NMR (376MHz, CDCl3) δ: -77.1 (q, J=11.7Hz), -77.5 (dq, J=11.7, 11.7Hz)

[0805] 31 P{ 1H}NMR (162MHz, CDCl3) δ: -30.2 (septet, J=13.8Hz)

[0806]

[0807] (Synthesis Example I-6: Synthesis of AL-62)

[0808] Weigh 407 mg (1.2 mmol) of bis(2,3,5,6-tetrahydrobenzo[1,2-b:5,4-b']difuran-8-yl)phosphine into a Schlenk tube, and add 15 mL of tetrahydrofuran. After cooling the resulting solution to -78°C, slowly drop 0.84 mL (1.3 mmol) of n-BuLi. After the dropwise addition is completed, stir the mixture at -78°C for 1 hour. Then, warm the mixture to 0°C, and then slowly add 145 mg (0.85 mmol) of methyl 2-(trifluoromethyl)-2-oxiranecarboxylate dissolved in 2.8 mL of tetrahydrofuran. Then, rinse the container containing methyl 2-(trifluoromethyl)-2-oxiranecarboxylate twice with 0.3 mL of tetrahydrofuran, and add the rinse solution to the Schlenk tube. After stirring the mixture at room temperature for 1 hour and 40 minutes, the mixture was cooled to 0°C, and 1.4 mL (1.4 mmol) of hydrochloric acid ether solution was slowly added dropwise. After stirring the mixture at 0°C for 2 hours, 8.4 mL of water was added to wash and the organic layer was separated. All subsequent operations were performed under atmospheric pressure. The operation of adding 5 mL of diethyl ether to the aqueous layer to extract the organic layer was performed twice, and the operation of adding 6 mL of diethyl ether to the aqueous layer to extract the organic layer was performed once. The collected organic layers were dried over sodium sulfate, and the sodium sulfate was removed using a glass filter. The filtrate was evaporated to dryness, and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane / acetone = 10 / 1 to 5 / 1, further changed to 2 / 1) to obtain 202 mg of solid. Using 31 The purity of AL-62 determined by P-NMR was 99% or more.

[0809] 1 H NMR (400MHz, CDCl3) δ: 6.89 (d, J=13.2Hz, 2H), 4.68 (d, J=0.8Hz, 1H), 4.58-4.45 (m, 8H ), 3.71 (s, 3H), 3.68 (dd, J=15.2, 2.8Hz, 1H), 3.06-3.00 (m, 8H), 2,92 (d, J=14.8Hz, 1H)

[0810] 19 F NMR (376MHz, CDCl3) δ: -79.0 (br)

[0811] 31 P{ 1H}NMR(162MHz, CDCl3)δ: -61.6-(-61.8)(m)

[0812]

[0813] (Synthesis Example I-7: Synthesis of AL-68)

[0814] (1) Synthesis of 5-bromo-2,3-dihydro-1,4-benzodioxane

[0815] 3-Bromo-1,2-benzenediol (10 g, 52.9 mmol) and 1,2-dibromoethane (19.9 g, 106 mmol) were dissolved in N,N-dimethylformamide (100 mL). Potassium carbonate (21.9 g, 159 mmol) and potassium fluoride (1.54 g, 26.5 mmol) were added to the solution, and the mixture was stirred at 135°C for 2 hours to obtain a yellow suspension. The mixture was added to water (200 mL), and the organic layer was extracted 3 times with ethyl acetate (200 mL). The collected organic layer was washed 3 times with water (300 mL), and then washed twice with saturated brine (100 mL). The organic layer was dried over anhydrous sodium sulfate and filtered, and the filtrate was concentrated. The resulting residue was purified by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = changed from 100 / 0 to 20 / 1) to obtain 11.2 g (52.2 mmol) of the target product as a yellow oily substance.

[0816] 1 H NMR (400MHz, CDCl3) δ: 7.10 (dd, J=8.0, 1.6Hz, 1H), 6.84 (dd, J=8.0, 1.2Hz, 1H), 6.73 (dd, J=8.0, 8.0Hz, 1H), 4.38-4.36 (m, 2H), 4.28-4.26 (m, 2H)

[0817]

[0818] (2) Synthesis of tert-butyl (2,3-dihydro-1,4-benzodioxane-5-yl) phosphine borane

[0819] To a tetrahydrofuran solution (50 mL) of 5-bromo-2,3-dihydro-1,4-benzodioxane (6.5 g, 30 mmol) at -78°C, n-butyl lithium (2.5 M, 14.5 mL, 36.2 mmol) was slowly added. The mixture was stirred at -78°C for 1 hour, and a tetrahydrofuran solution (10 mL) of tert-butyl dichlorophosphine (7.21 g, 45.3 mmol) was quickly added thereto at -78°C. The mixture was stirred at room temperature for 2 hours, thereby obtaining a yellow solution. The solvent was removed by distillation, and tert-butyl (2,3-dihydro-1,4-benzodioxane-5-yl) chlorophosphine was obtained as a crude product in the form of a pale yellow oily substance (15.6 g).

[0820] Lithium aluminum hydride (2.5M, 17.4mL, 43.5mmol) was slowly added to a tetrahydrofuran solution (40mL) of the above oily substance (7.5g). The mixture was then stirred at room temperature for 2 hours to obtain a yellow solution. Borane dimethyl sulfide (10M, 4.35mL, 43.5mmol) was added to the mixture at 0°C, and the mixture was then stirred at room temperature for 4 hours to obtain a yellow solution. Hydrochloric acid (1N, 10mL) was slowly added to the mixture, and the organic layer was extracted 3 times with ethyl acetate (150mL), and the collected organic layer was washed with saturated brine (100mL). The organic layer was dried over sodium sulfate, the sodium sulfate was filtered out, and the filtrate was concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = changed from 40 / 1 to 10 / 1) to obtain a white solid (1.1g, 4.6mmol).

[0821] 1 H NMR (400MHz, CDCl3) δ: 7.28-7.26 (m, 1H), 7.02 (dd, J=8.0, 1.5Hz, 1H), 6.95 (ddd, 7.5, 7.5, 2.5Hz , 1H), 5.56 (dq, J=380, 7.0Hz, 1H), 4.35-4.23 (m, 4H), 1.19 (d, J=15.0Hz, 9H), 1.03-0.33 (br, 3H)

[0822] 31 P{ 1 H}NMR(202MHz, CDCl3)δ: 2.4-2.1(m)

[0823]

[0824] (3) Synthesis of AL-68

[0825] Weigh 250 mg (1.1 mmol) of the synthesized tert-butyl (2,3-dihydro-1,4-benzodioxane-5-yl) phosphine borane into a Schlenk tube, and add 11 mL of tetrahydrofuran. Cool the resulting solution to -78°C, and slowly drop 1.9 mL (1.2 mmol) of a toluene solution of potassium bis(trimethylsilyl)amide. After the dropwise addition, stir the mixture at -78°C for 1 hour. Warm the mixture to 0°C, and slowly add 0.11 mL (1.1 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 3.5 mL of tetrahydrofuran. Rinse the container containing 2,2-bis(trifluoromethyl)oxirane twice with 0.5 mL of tetrahydrofuran, and add the washing liquid to the Schlenk tube. Stir the mixture at room temperature for 1 hour, and then completely distill off the solvent. The obtained solid was purified by silica gel column chromatography (developing solvent: hexane / dichloromethane = 5 / 1) under atmospheric pressure to obtain 323 mg of a solid.

[0826] To 323 mg of the above solid was added 5 mL of methanol, and the mixture was stirred at 60° C. for 8 hours. After stirring, the solvent was distilled off to obtain 229 mg of a solid. 31 The purity of AL-68 determined by P-NMR was 98%.

[0827] 1 H NMR (400MHz, CDCl3) δ: 6.99 (ddd, J=7.7, 7.7, 1.9Hz, 1H), 6.93 (dd, J=8.2, 1.8Hz, 1H), 6.87 (dd, J=7.8, 7. 8Hz, 1H), 4.33-4.24 (m, 5H), 3.06 (dd, J=16.0, 1.8Hz, 1H), 2.15 (d, J=16.0Hz, 1H), 1.06 (d, J=13.6Hz, 9H)

[0828] 19 F NMR (376MHz, CDCl3) δ: -76.8 (q, J=14.5Hz), -77.8 (q, J=11.3Hz)

[0829] 31 P{ 1 H}NMR(162MHz, CDCl3)δ: -25.3(s)

[0830]

[0831] (Synthesis Example I-8: Synthesis of AL-69)

[0832] (1) Synthesis of 7-bromo-2,3-dihydro-2,2-dimethylbenzofuran

[0833] The compound of the following chemical formula was synthesized according to the description of Organic Letters, 2011, 13, 4974-4976.

[0834]

[0835] (2) Synthesis of tert-butyl (2,3-dihydro-2,2-dimethylbenzofuran-7-yl) phosphine borane

[0836] A tetrahydrofuran solution (30 mL) of 7-bromo-2,3-dihydro-2,2-dimethylbenzofuran (6.5 g, 28.6 mmol) was cooled to -78°C, and n-butyl lithium (2.5 M, 12.6 mL, 31.5 mmol) was added. The mixture was stirred at -78°C for 3 hours, and a tetrahydrofuran solution (6 mL) of tert-butylphosphine dichloride (5.01 g, 31.5 mmol) was added thereto. The mixture was stirred at 20°C for 1 hour to obtain a colorless solution. The solution was concentrated to obtain tert-butyl (2,3-dihydro-2,2-dimethylbenzofuran-7-yl) phosphine chloride as a crude product of a white solid.

[0837] 31 P{ 1 H}NMR (162 MHz, CDCl3) δ: 99.0 (s, integration ratio 98%)

[0838] A tetrahydrofuran solution (30 mL) of the white solid (7.75 g, 28.6 mmol) was cooled to 0°C, and borane dimethyl sulfide (10 M, 5.73 mL, 57.3 mmol) was added. The mixture was stirred at room temperature for 16 hours to obtain tert-butyl (2,3-dihydro-2,2-dimethylbenzofuran-7-yl) chlorophosphine borane as a white suspension.

[0839] 31 P{ 1 H}NMR (162MHz, CDCl3) δ: 119.2-118.9 (m, integration ratio 78%)

[0840] The above white suspension was cooled to 0°C and lithium aluminum hydride (2.5M, 17.2mL, 43mmol) was added. The mixture was stirred at 20°C for 16 hours to obtain a colorless solution. Water (0.5mL) was slowly added thereto, followed by a 15% aqueous sodium hydroxide solution (0.5mL) and then water (1.5mL) was slowly added. After stirring at room temperature for 30 minutes, the mixture was filtered and the filtrate was concentrated to obtain a colorless oily substance. The obtained oily substance was purified by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = 50 / 1) to obtain 3.2g of the target substance as a white solid.

[0841] 1 H NMR (400MHz, CDCl3) δ: 7.46 (dd, J=10.4, 8.0Hz, 1H), 7.26 (d, J=7.4Hz, 1H), 6.91 (ddd, J=7.4Hz, 7.4Hz, 1.8Hz, 1H ), 5.44 (dq, J = 377, 6.8Hz, 1H), 3.06 (s, 2H), 1.50 (s, 3H), 1.46 (s, 3H), 1.19 (d, J = 15.2Hz, 9H), 0.97-0.20 (br, 3H)

[0842] 31 P{ 1 H}NMR(162MHz, CDCl3)δ: 4.6-4.2(m)

[0843]

[0844] (3) Synthesis of AL-69

[0845] 250 mg (1.0 mmol) of the synthesized tert-butyl (2,3-dihydro-2,2-dimethylbenzofuran-7-yl) phosphine borane was weighed into a Schlenk tube, and 13 mL of tetrahydrofuran was added. After the resulting solution was cooled to -78°C, 1.8 mL (1.1 mmol) of a toluene solution of potassium bis(trimethylsilyl)amide was slowly added dropwise. After the addition was completed, the mixture was stirred at -78°C for 1 hour. The mixture was then heated to 0°C, and 0.11 mL (1.0 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 3.3 mL of tetrahydrofuran was slowly added. The container containing 2,2-bis(trifluoromethyl)oxirane was washed twice with 0.5 mL of tetrahydrofuran, and the washing liquid was also added to the Schlenk tube. After the mixture was stirred at room temperature for 1 hour, the solvent was distilled off. The obtained solid was purified by silica gel column chromatography (developing solvent: hexane / dichloromethane=5 / 1) under atmospheric pressure to obtain 192 mg of a solid.

[0846] To 192 mg of the above solid was added 3 mL of methanol, and the mixture was stirred at 60° C. for 7 hours. After stirring, the solvent was distilled off to obtain 146 mg of a solid. 31 The purity of AL-69 determined by P-NMR was 98%.

[0847] 1 H NMR (400MHz, CDCl3) δ: 7.27-7.20 (m, 1H), 7.20-7.14 (m, 1H), 6.83 (ddd, J=7.6, 7.6, 0.8Hz, 1H), 4.56 (d, J=8.0Hz, 1H) , 3.50 (dd, J=15.8, 3.4Hz, 1H), 3.01 (s, 2H), 2.09 (d, J=16.0Hz, 1H), 1.47 (s, 3H), 1.46 (s, 3H), 1.06 (d, J=13.6Hz, 9H)

[0848] 19 F NMR(376MHz, CDCl3)δ: -77.1-(-77.3)(m)

[0849] 31 P{ 1 H}NMR (162MHz, CDCl3) δ: -15.3 (septet, J=14.2Hz)

[0850]

[0851] [Comparative Synthesis Example 1] (Synthesis of AL-2al)

[0852] AL-2al shown in the following chemical formula was synthesized with reference to pages 51 to 52 of International Publication No. 2001 / 092342. 31 P{ 1 The purity of the complex was 90% by H}-NMR. 31 P{ 1 H}-NMR showed a purity of 76% of the complex.

[0853]

[0854] The autoclave used in the following polymerization experiments was used after being thoroughly dried and purged with nitrogen.

[0855] [Example I-1]

[0856] Weigh 68.8 mg (0.25 mmol) of Ni(cod)2 into a flask and dissolve it in 25 mL of toluene. In addition, weigh 10.5 mg (0.019 mmol) of AL-29 obtained in Synthesis Example I-1 into another flask. Measure 20 mL of the toluene solution of Ni(cod)2 and add the solution to the flask containing AL-29. Heat the resulting solution of the catalyst composition in a water bath at 40°C and stir for 15 minutes to obtain a catalyst composition solution (hereinafter referred to as the catalyst solution. AL-29 concentration: about 1 mM).

[0857] 1000 mL of toluene was added to a 2.4 L autoclave, and the temperature inside the autoclave was raised to 90° C. Nitrogen gas was added so that the internal pressure of the autoclave became 0.5 MPa.

[0858] Next, ethylene was added to make the internal pressure of the autoclave 3.0 MPa. 5.0 mL of the above catalyst solution was injected into the catalyst cartridge, and high-pressure nitrogen was added to the autoclave, and this moment was regarded as the start time of the reaction. One minute after the reaction started, the ethylene pressure was released, and 10 mL of 1,2-butanediol toluene solution (0.2 M) was added to stop the reaction. The autoclave was returned to room temperature and 1000 mL of acetone was added. The precipitated solid was recovered by filtration, and the solid was washed twice with 100 mL of acetone and dried under reduced pressure. The obtained polymer was 31.6 g.

[0859] [Example I-2]

[0860] Prepare 25 mL of catalyst solution (AL-29 concentration: about 4 mM) in the same manner as Example I-1, except that Ni(cod)2 was changed to 302.4 mg (1.1 mmol), toluene was changed to 27.5 mL, AL-29 was changed to 54.3 mg (0.10 mmol), and the toluene solution of Ni(cod)2 added to AL-29 was changed to 25 mL.

[0861] Add 940 mL of toluene (hereinafter referred to as toluene-1) to a 2.4 L autoclave. Inject 2.9 mL (20 mmol) of tBA (hereinafter referred to as comonomer and its addition amount-1) into the catalyst cartridge, and add it to the autoclave with high-pressure nitrogen. Wash the catalyst cartridge with 10 mL of toluene, and add the washing liquid to the autoclave with high-pressure nitrogen. Add 1.0 mL of a toluene solution of TNOA (0.1 M) to the catalyst cartridge, and add it to the autoclave with high-pressure nitrogen. Wash the catalyst cartridge with 10 mL of toluene, and add the washing liquid to the autoclave with high-pressure nitrogen. Raise the temperature in the autoclave to 90°C, and add nitrogen so that the internal pressure of the autoclave becomes 0.5 MPa (hereinafter referred to as nitrogen pressure-1). Next, add ethylene so that the internal pressure of the autoclave becomes 3.0 MPa (hereinafter referred to as ethylene pressure-1). 5 mL of the above catalyst solution (hereinafter referred to as initial catalyst-1) was added to the catalyst cartridge, and introduced into the autoclave using high-pressure nitrogen gas. This time was regarded as the reaction start time.

[0862] 3 minutes after the start of the reaction, the catalyst cartridge was cleaned with 10 mL of toluene, and the cleaning liquid was added to the autoclave with high-pressure nitrogen (hereinafter referred to as initial cleaning and its time-1). 9 minutes after the start of the reaction, 9 mL of catalyst solution was added to the catalyst cartridge, and added to the autoclave with high-pressure nitrogen. Furthermore, 13 minutes after the start of the reaction, 9 mL of catalyst solution was added to the catalyst cartridge, and added to the autoclave with high-pressure nitrogen. 16 minutes after the start of the reaction, the catalyst cartridge was cleaned with 10 mL of toluene, and the cleaning liquid was added to the autoclave with high-pressure nitrogen (hereinafter referred to as catalyst addition-1). 52 minutes after the start of the reaction (hereinafter referred to as reaction time-1), 10 mL of 1,2-butanediol toluene solution (0.2 M) was added with high-pressure nitrogen to stop the reaction, and the ethylene pressure was released.

[0863] Purification method: The autoclave was returned to room temperature, and 1000 mL of acetone was added. The precipitated solid was recovered by filtration, washed twice with 1000 mL of acetone, and dried under reduced pressure. The obtained polymer was 28.7 g.

[0864] [Example I-3]

[0865] Prepare 6 mL of catalyst solution (AL-29 concentration: about 4 mM) in the same manner as Example I-1, except that Ni(cod)2 was changed to 88.2 mg (0.32 mmol), toluene was changed to 8 mL, AL-29 was changed to 13.2 mg (0.024 mmol), and the toluene solution of Ni(cod)2 added to AL-29 was changed to 6 mL.

[0866] Add 90 mL of toluene (hereinafter referred to as toluene-2) to a 0.2 L autoclave. Add 0.75 mL (5.2 mmol) of tBA (hereinafter referred to as comonomer and its addition amount-2) and 0.6 mL of a toluene solution of TNOA (0.1 M) (hereinafter referred to as TNOA addition amount-2) from the reagent inlet. Raise the temperature in the autoclave to 90°C, add nitrogen gas so that the internal pressure of the autoclave becomes 0.5 MPa (hereinafter referred to as nitrogen pressure-2). Next, add ethylene so that the internal pressure of the autoclave becomes 3.0 MPa (hereinafter referred to as ethylene pressure-2). Inject 3 mL of the above catalyst solution (hereinafter referred to as initial catalyst-2) into the catalyst cartridge, add high-pressure nitrogen to the autoclave, and this moment is regarded as the start time of the reaction. 4 minutes after the start of the reaction, wash the catalyst cartridge with 3 mL of toluene, and add the washing liquid to the autoclave with high-pressure nitrogen (hereinafter referred to as initial washing and its time-2). 30 minutes after the reaction started, 0.1 mL of tBA (0.7 mmol) was added to the catalyst cartridge, and 1 mL of toluene was added very slowly, and the solution was added to the autoclave with high-pressure nitrogen. 31 minutes after the reaction started, the catalyst cartridge was cleaned with 3 mL of toluene, and the cleaning solution was added to the autoclave with high-pressure nitrogen. 60 minutes after the reaction started (hereinafter referred to as reaction time-2), 3 mL of 1,2-butanediol toluene solution (0.2 M) (hereinafter referred to as reaction terminator) was added with high-pressure nitrogen to stop the reaction, and the ethylene pressure was released.

[0867] Purification method: The autoclave was returned to room temperature, and 100 mL of acetone was added. The precipitated solid was recovered by filtration, and the solid was washed twice with 100 mL of acetone and dried under reduced pressure. The polymer obtained was 0.70 g.

[0868] [Example I-4]

[0869] Prepare 22 mL of catalyst solution (AL-29 concentration: about 1 mM) in the same manner as Example I-1, except that Ni(cod)2 was changed to 69.2 mg (0.25 mmol), AL-29 was changed to 11.8 mg (0.022 mmol), and the toluene solution of Ni(cod)2 added to AL-29 was changed to 22 mL.

[0870] Using the catalyst solution prepared above, a polymerization operation was carried out in the same manner as in Example I-3 except that the catalyst was added as follows and the polymerization conditions were changed as follows, thereby obtaining 0.46 g of a polymer.

[0871] Toluene-2: 88mL

[0872] Comonomer and its added amount-2: Toluene solution of norbornene (0.318 g / g, 3.89 g, 13 mmol), and no additional comonomer was added.

[0873] Amount of TNOA added-2: Not added

[0874] Nitrogen pressure-2: 0.2MPa

[0875] Ethylene pressure-2: 0.8MPa (internal pressure 1.0MPa)

[0876] Initial catalyst-2: 1 mL of the catalyst solution was injected, followed by very slow addition of 2 mL of toluene, which was then added into the autoclave using high-pressure nitrogen.

[0877] Initial cleaning and its time-2: None

[0878] Catalyst addition: 10 minutes after the reaction started, 1 mL of catalyst solution was added to the catalyst cartridge and added to the autoclave with high-pressure nitrogen. Furthermore, 15 minutes after the reaction started, the cleaning solution obtained by cleaning the catalyst cartridge with 3 mL of toluene was added to the autoclave with high-pressure nitrogen.

[0879] Reaction time -2: 30 minutes

[0880] [Example I-5]

[0881] Prepare 22 mL of catalyst solution (AL-29 concentration: about 1 mM) in the same manner as Example I-1, except that Ni(cod)2 was changed to 68.7 mg (0.25 mmol), AL-29 was changed to 12.0 mg (0.022 mmol), and the toluene solution of Ni(cod)2 added to AL-29 was changed to 22 mL.

[0882] Using the catalyst solution prepared above, a polymerization operation was carried out in the same manner as in Example I-3 except that the catalyst was added as follows and the polymerization conditions were changed as follows, thereby obtaining 0.80 g of a polymer.

[0883] Toluene-2: 88mL

[0884] Comonomer and amount thereof added-2: vinylene carbonate (1.3 mL, 21 mmol), and no additional comonomer was added thereafter.

[0885] Amount of TNOA added-2: 0.1 mL (0.010 mmol)

[0886] Nitrogen pressure-2: unpressurized

[0887] Ethylene pressure-2: 2.5MPa

[0888] Initial cleaning and time-2: 2 minutes after the reaction starts, 3 mL of toluene

[0889] Catalyst addition: 7 minutes and 18 minutes after the start of the reaction, 2 mL and 3 mL of catalyst solution were injected into the catalyst cartridge, respectively, and added to the autoclave with high-pressure nitrogen. 11 minutes and 20 minutes after the start of the reaction, the catalyst cartridge was cleaned with 3 mL of toluene, respectively, and the cleaning solution was added to the autoclave with high-pressure nitrogen.

[0890] Reaction time -2: 35 minutes

[0891] Purification method: After precipitating the polymer with 100 mL of acetone, 100 mL of acetone and 1 mL of a 10 wt% hydrochloric acid aqueous solution were added to the polymer, and the mixture was stored in a refrigerator overnight. The polymer was then washed twice with 100 mL of acetone.

[0892] [Example I-6]

[0893] Ni(cod)2 was changed to 68.9 mg (0.25 mmol), AL-29 was replaced with 11.6 mg (0.022 mmol) of AL-36 obtained in Synthesis Example I-2, and the toluene solution of Ni(cod)2 added to AL-36 was changed to 22 mL. The same procedure as in Example I-1 was followed to prepare 22 mL of a catalyst solution (AL-36 concentration: about 1 mM).

[0894] Using the catalyst solution prepared above, a polymerization operation was carried out in the same manner as in Example I-3 except that the catalyst was added as follows and the polymerization conditions were changed as follows, thereby obtaining 1.52 g of a polymer.

[0895] Toluene-2: 93mL

[0896] Comonomer and amount thereof added-2: tBA (0.3 mL, 2.1 mmol), and no additional comonomer was added thereafter.

[0897] Amount of TNOA added-2: 0.1 mL (0.010 mmol)

[0898] Initial catalyst-2: 0.5 mL of the catalyst solution was injected, followed by very slowly adding 3 mL of toluene, which was then added into the autoclave using high-pressure nitrogen.

[0899] Initial cleaning and its time-2: None

[0900] Addition of catalyst: 5 minutes after the start of the reaction, 0.5 mL of the catalyst solution was injected into the catalyst cartridge, and 3 mL of toluene was further added very slowly, and then added to the autoclave with high-pressure nitrogen.

[0901] [Example I-7]

[0902] The same method as in Example 1-6 was followed except that Ni(cod)2 was changed to 11.2 mg (0.04 mmol), toluene was changed to 4 mL, AL-36 was changed to 10.6 mg (0.02 mmol), and the toluene solution of Ni(cod)2 added to AL-36 was changed to 2 mL to prepare 2 mL of a solution (AL-36 concentration: about 10 mM). Then, 18 mL of toluene was added to the solution to prepare 20 mL of a catalyst solution (AL-36 concentration: about 1 mM).

[0903] Using the catalyst solution prepared above, a polymerization operation was carried out in the same manner as in Example I-3 except that the catalyst was added as follows and the polymerization conditions were changed as follows, thereby obtaining 1.80 g of a polymer.

[0904] Toluene-2: 93mL

[0905] Comonomer and amount thereof added-2: tBA (0.3 mL, 2.1 mmol), and no additional comonomer was added thereafter.

[0906] Amount of TNOA added-2: 0.1 mL (0.010 mmol)

[0907] Initial catalyst-2: 1 mL of the catalyst solution was injected, followed by very slow addition of 2 mL of toluene, which was then added into the autoclave using high-pressure nitrogen.

[0908] Initial cleaning and its time-2: None

[0909] Catalyst addition: 6 minutes and 17 minutes after the start of the reaction, 2 mL of catalyst solution was injected into the catalyst cartridge, and added to the autoclave with high-pressure nitrogen. 32 minutes after the start of the reaction, the catalyst cartridge was cleaned with 3 mL of toluene, and the cleaning solution was added to the autoclave with high-pressure nitrogen.

[0910] [Example I-8]

[0911] 4 mL of a solution (AL-36 concentration: about 5 mM) was prepared in the same manner as in Example 1-6, except that Ni(cod)2 was replaced with 10.2 mg (0.04 mmol) of Ni(acac)2, toluene was changed to 8 mL, AL-36 was changed to 10.6 mg (0.02 mmol), and the toluene solution of the metal compound added to AL-36 was changed to 4 mL. Then, 16 mL of toluene was added to the solution to prepare 20 mL of a catalyst solution (AL-36 concentration: about 1 mM).

[0912] Using the catalyst solution prepared above, a polymerization operation was carried out in the same manner as in Example I-3 except that the catalyst was added as follows and the polymerization conditions were changed as follows, thereby obtaining 2.10 g of a polymer.

[0913] Toluene-2: 93mL

[0914] Comonomer and amount thereof added-2: tBA (0.3 mL, 2.1 mmol), and no additional comonomer was added thereafter.

[0915] Amount of TNOA added-2: 0.2 mL (0.020 mmol)

[0916] Initial catalyst-2: 1 mL of the catalyst solution was injected, followed by very slow addition of 2 mL of toluene, which was then added into the autoclave using high-pressure nitrogen.

[0917] Initial cleaning and its time-2: None

[0918] Catalyst addition: 6 minutes after the start of the reaction and 19 minutes after the start of the reaction, 3 mL and 2 mL of the catalyst solution were injected into the catalyst cartridge, respectively, and added to the autoclave using high-pressure nitrogen. 22 minutes after the start of the reaction, the catalyst cartridge was cleaned with 3 mL of toluene, and the cleaning solution was added to the autoclave using high-pressure nitrogen.

[0919] [Example I-9]

[0920] 6 mL of catalyst solution (AL-36 concentration: about 5 mM) was prepared in the same manner as in Example 1-6, except that Ni(cod)2 was replaced with 10.2 mg (0.04 mmol) of Ni(acac)2, toluene was changed to 8 mL, AL-36 was changed to 16.1 mg (0.03 mmol), and the toluene solution of the metal compound added to AL-36 was changed to 6 mL.

[0921] A polymerization operation was carried out in the same manner as in Example I-2, except that the catalyst solution prepared above was used and the polymerization conditions were changed as follows, to obtain 6.62 g of a polymer.

[0922] Toluene-1: 950mL

[0923] Initial catalyst-1: 4 mL of the catalyst solution was injected, followed by very slow addition of 8 mL of toluene, which was then added into the autoclave using high-pressure nitrogen.

[0924] Initial cleaning and its time-1: 5 minutes after the start of the reaction, the catalyst cartridge was cleaned with 10 mL of toluene.

[0925] Catalyst addition-1: No catalyst was added.

[0926] Reaction time -1: 60 minutes

[0927] [Example I-10]

[0928] 16.5 mg (0.024 mmol) of AL-36 / NiMePy obtained in Synthesis Example I-3 was weighed, and 12 mL of toluene was added to prepare a metal complex solution (hereinafter referred to as catalyst solution) (AL-36 concentration: about 2 mM).

[0929] A polymerization operation was carried out in the same manner as in Example I-2, except that the catalyst solution prepared above was used and the polymerization conditions were changed as follows, to obtain 12.3 g of a polymer.

[0930] Toluene-1: 950mL

[0931] Comonomer and its addition amount-1: tBA (2.9 mL, 20 mmol) was injected into the catalyst cartridge, and then 9 mL of toluene was added very slowly, and the solution was introduced into the autoclave with high-pressure nitrogen. The catalyst cartridge was not cleaned.

[0932] Amount of TNOA added-1: 1.0 mL (0.10 mmol) of TNOA was injected into the catalyst cartridge, and then 10 mL of toluene was added very slowly, and the solution was introduced into the autoclave using high-pressure nitrogen gas.

[0933] Initial catalyst-1: 2 mL of catalyst solution was injected, followed by very slow addition of 10 mL of toluene, which was then added into the autoclave using high-pressure nitrogen.

[0934] Initial cleaning and its time-1: 2 minutes after the start of the reaction, the catalyst cartridge was cleaned with 10 mL of toluene.

[0935] Catalyst addition-1: 17 minutes after the reaction started, 3 mL of the catalyst solution was injected into the catalyst cartridge and added to the autoclave using high-pressure nitrogen. 19 minutes after the reaction started, the catalyst cartridge was cleaned with 10 mL of toluene and the cleaning solution was added to the autoclave using high-pressure nitrogen.

[0936] Reaction time -1: 60 minutes

[0937] [Example I-11]

[0938] Ni(cod)2 was changed to 69.3 mg (0.25 mmol), toluene was changed to 10 mL, AL-36 was changed to 10.5 mg (0.02 mmol), and the toluene solution of Ni(cod)2 added to AL-36 was changed to 8 mL. Otherwise, the same procedure as in Example I-6 was followed to prepare 8 mL of a catalyst solution (AL-36 concentration: approximately 2.5 mM).

[0939] A polymerization operation was carried out in the same manner as in Example I-3, except that the catalyst solution prepared above was used and the polymerization conditions were changed as follows, to obtain 1.16 g of a polymer.

[0940] Toluene-2: 93mL

[0941] Comonomer and amount thereof added-2: tBA (1.2 mL, 8.3 mmol), and no additional comonomer was added thereafter.

[0942] Amount of TNOA added-2: 0.25 mL (0.025 mmol)

[0943] Initial catalyst-2: 2 mL of catalyst solution

[0944] Initial cleaning and time-2: 3 minutes after the start of the reaction, the catalyst cartridge was cleaned with 3 mL of toluene.

[0945] Purification method: After precipitating the polymer with 100 mL of acetone, 100 mL of acetone and 1 mL of a 10 wt % aqueous hydrochloric acid solution were added to the polymer and stored in a refrigerator overnight. The polymer was then washed twice with 100 mL of acetone.

[0946] [Example I-12]

[0947] Ni(cod)2 was changed to 99.5 mg (0.36 mmol), toluene was changed to 9 mL, AL-36 was changed to 14.9 mg (0.028 mmol), and the toluene solution of Ni(cod)2 added to AL-36 was changed to 7 mL. Otherwise, the same procedure as in Example I-6 was followed to prepare 7 mL of a catalyst solution (AL-36 concentration: approximately 4 mM).

[0948] A polymerization operation was carried out in the same manner as in Example I-3, except that the catalyst solution prepared above was used and the polymerization conditions were changed as follows, to obtain 0.54 g of a polymer.

[0949] Toluene-2: 93mL

[0950] Comonomer and its added amount-2: MA (0.3 mL, 3.3 mmol), and no additional comonomer was added thereafter.

[0951] Amount of TNOA added-2: 1.0 mL (0.10 mmol)

[0952] Initial catalyst-2: 2.5 mL of catalyst solution

[0953] Initial cleaning and time-2: 2 minutes after the start of the reaction, the catalyst cartridge was cleaned with 3 mL of toluene.

[0954] Reaction stopper: 1.0 mL of a toluene solution of deuterated acetic acid (2 M) was added to replace the toluene solution of 1,2-butanediol.

[0955] [Example I-13]

[0956] Ni(cod)2 was changed to 69.0 mg (0.25 mmol), AL-36 was changed to 12.0 mg (0.022 mmol), and the toluene solution of Ni(cod)2 added to AL-36 was changed to 22 mL. The same procedure as in Example I-6 was followed to prepare 22 mL of a catalyst solution (AL-36 concentration: approximately 1 mM).

[0957] Using the catalyst solution prepared above, a polymerization operation was carried out in the same manner as in Example I-3 except that the catalyst was added as follows and the polymerization conditions were changed as follows, thereby obtaining 1.57 g of a polymer.

[0958] Toluene-2: 88mL

[0959] Comonomer and its added amount-2: Toluene solution of norbornene (about 4.6 mL, 0.318 g / g, 4.23 g, 14 mmol), and no additional comonomer was added.

[0960] Amount of TNOA added-2: Not added

[0961] Nitrogen pressure-2: 0.2MPa

[0962] Ethylene pressure-2: 0.8MPa (internal pressure 1.0MPa)

[0963] Initial catalyst-2: 1 mL of the catalyst solution was injected, followed by very slow addition of 2 mL of toluene, which was then added into the autoclave using high-pressure nitrogen.

[0964] Initial cleaning and its time-2: None

[0965] Catalyst addition: 6 minutes, 8 minutes, and 14 minutes after the start of the reaction, 2 mL of the catalyst solution was injected into the catalyst cartridge, and added to the autoclave with high-pressure nitrogen. Furthermore, 20 minutes after the start of the reaction, 3 mL of the catalyst solution was injected into the catalyst cartridge, and added to the autoclave with high-pressure nitrogen. 15 minutes and 22 minutes after the start of the reaction, the catalyst cartridge was cleaned with 3 mL of toluene, and the cleaning solution was added to the autoclave with high-pressure nitrogen.

[0966] Reaction time -2: 37 minutes

[0967] [Example I-14]

[0968] 22 mL of a catalyst solution (AL-36 concentration: about 1 mM) was prepared in the same manner as in Example I-6 except that AL-36 was changed to 11.7 mg (0.022 mmol) and the toluene solution of Ni(cod)2 added to AL-36 was changed to 22 mL.

[0969] A polymerization operation was carried out in the same manner as in Example I-3, except that the catalyst solution prepared above was used and the polymerization conditions were changed as follows, to obtain 1.16 g of a polymer.

[0970] Toluene-2: 94mL

[0971] Comonomer and amount thereof added-2: vinylene carbonate (1.3 mL, 21 mmol), and no additional comonomer was added thereafter.

[0972] Amount of TNOA added-2: 0.1 mL (0.010 mmol)

[0973] Nitrogen pressure-2: 0MPa

[0974] Ethylene pressure-2: 2.5MPa

[0975] Initial catalyst-2: 1 mL of catalyst solution

[0976] Catalyst addition: 11 minutes after the reaction started, 1 mL of catalyst solution was injected into the catalyst cartridge and added to the autoclave with high-pressure nitrogen. 14 minutes after the reaction started, the catalyst cartridge was cleaned with 3 mL of toluene and the cleaning solution was added to the autoclave with high-pressure nitrogen.

[0977] Reaction time -2: 30 minutes

[0978] [Example I-15]

[0979] Ni(cod)2 was changed to 66.2 mg (0.24 mmol), toluene was changed to 24 mL, AL-29 was replaced with 10.8 mg (0.020 mmol) of AL-52 obtained in Synthesis Example I-4, and the toluene solution of Ni(cod)2 added to AL-52 was changed to 20 mL. Otherwise, the same procedure as in Example I-1 was followed to prepare 20 mL of a catalyst solution (AL-52 concentration: about 1 mM).

[0980] 1000 mL of toluene was added to a 2.4 L autoclave, and the temperature in the autoclave was raised to 90°C. Nitrogen was added to make the internal pressure of the autoclave 0.5 MPa. Next, ethylene was added to make the internal pressure of the autoclave 3.0 MPa. 1.0 mL of the above catalyst solution was injected into the catalyst cartridge, and then 10 mL of toluene was added very slowly and allowed to stand. The solution was added to the autoclave with high-pressure nitrogen, and this moment was taken as the reaction start time. 4 minutes after the reaction started, the catalyst cartridge was cleaned with 10 mL of toluene, and the cleaning liquid was added to the autoclave with high-pressure nitrogen. 5 minutes after the reaction started, 10 mL of a toluene solution of 1,2-butanediol (0.2 M) was added to stop the reaction, and the pressure of ethylene was released. The autoclave was returned to room temperature, and 1000 mL of acetone was added. The precipitated solid was recovered by filtration, and the solid was cleaned twice with 1000 mL of acetone and dried under reduced pressure. The obtained polymer was 14.6 g.

[0981] [Example I-16]

[0982] 4 mL of catalyst solution (AL-61 concentration: about 10 mM) was prepared in the same manner as in Example I-1 except that Ni(cod)2 was replaced with 15.4 mg (0.060 mmol) of Ni(acac)2, toluene was replaced with 6 mL, AL-29 was replaced with 17.0 mg (0.040 mmol) of AL-61 obtained in Synthesis Example I-5, and the toluene solution of Ni(acac)2 added to AL-61 was changed to 4 mL.

[0983] Using the catalyst solution prepared above, a polymerization operation was carried out in the same manner as in Example I-3 except that the catalyst was added as follows and the polymerization conditions were changed as follows, thereby obtaining 2.78 g of a polymer.

[0984] Toluene-2: 94mL

[0985] Comonomer and its added amount-2: MA (0.3 mL, 3.3 mmol), and no additional comonomer was added thereafter.

[0986] Amount of TNOA added-2: 1.0 mL (0.10 mmol)

[0987] Nitrogen pressure-2: 0.5MPa

[0988] Ethylene pressure-2: 2.5MPa

[0989] Initial catalyst-2: 1 mL of catalyst solution

[0990] Additional addition of catalyst: 9 minutes after the start of the reaction, 1 mL of the catalyst solution was injected into the catalyst cartridge and added to the autoclave using high-pressure nitrogen.

[0991] Initial cleaning and time-2: 15 minutes after the start of the reaction, the catalyst cartridge was cleaned with 3 mL of toluene.

[0992] Reaction time: 36 minutes

[0993] Reaction stop agent: 0.5 mL of a toluene solution of deuterated acetic acid (2 M) was added instead of the toluene solution of 1,2-butanediol.

[0994] [Example I-17]

[0995] 4 mL of catalyst solution (AL-62 concentration: about 10 mM) was prepared in the same manner as in Example I-1 except that Ni(cod)2 was replaced with 15.8 mg (0.060 mmol) of Ni(acac)2, toluene was changed to 6 mL, AL-29 was replaced with 20.9 mg (0.040 mmol) of AL-62 obtained in Synthesis Example I-6, and the toluene solution of Ni(acac)2 added to AL-62 was changed to 4 mL.

[0996] A polymerization operation was carried out in the same manner as in Example I-3, except that the catalyst solution prepared above was used and the polymerization conditions were changed as follows, to obtain 0.38 g of a polymer.

[0997] Toluene-2: 92mL

[0998] Comonomer and amount thereof added-2: MA (0.9 mL, 10 mmol), and no additional comonomer was added thereafter.

[0999] Amount of TNOA added-2: 1.5 mL (0.15 mmol)

[1000] Nitrogen pressure-2: 0.5MPa

[1001] Ethylene pressure-2: 2.5MPa

[1002] Initial cleaning and time-2: 2 minutes after the start of the reaction, the catalyst cartridge was cleaned with 3 mL of toluene.

[1003] Reaction stopper: Add 1.5 mL of a toluene solution of deuterated acetic acid (2 M) instead of the toluene solution of 1,2-butanediol.

[1004] [Example I-18]

[1005] 4 mL of catalyst solution (AL-68 concentration: about 10 mM) was prepared in the same manner as in Example I-1 except that Ni(acac)2 was replaced with 15.4 mg (0.060 mmol) of Ni(cod)2, toluene was replaced with 6 mL, AL-68 obtained in Synthesis Example I-7 was replaced with 16.7 mg (0.040 mmol) of AL-29, and the toluene solution of Ni(acac)2 added to AL-68 was changed to 4 mL.

[1006] A polymerization operation was carried out in the same manner as in Example I-3, except that the catalyst solution prepared above was used and the polymerization conditions were changed as follows, to obtain 0.98 g of a polymer.

[1007] Toluene-2: 93mL

[1008] Comonomer and its added amount-2: MA (0.3 mL, 3.3 mmol), and no additional comonomer was added thereafter.

[1009] Amount of TNOA added-2: 1.0 mL (0.10 mmol)

[1010] Nitrogen pressure-2: 0.5MPa

[1011] Ethylene pressure-2: 2.5MPa

[1012] Initial catalyst-2: 1 mL of catalyst solution

[1013] Initial cleaning and time-2: 2 minutes after the start of the reaction, the catalyst cartridge was cleaned with 3 mL of toluene.

[1014] Reaction stopper: 1.0 mL of a toluene solution of deuterated acetic acid (2 M) was added to replace the toluene solution of 1,2-butanediol.

[1015] [Example I-19]

[1016] 7 mL of catalyst solution (AL-69 concentration: about 10 mM) was prepared in the same manner as in Example I-1 except that Ni(cod)2 was replaced with 22.8 mg (0.090 mmol) of Ni(acac)2, toluene was replaced with 9 mL, AL-29 was replaced with 29.1 mg (0.070 mmol) of AL-69 obtained in Synthesis Example I-8, and the toluene solution of Ni(acac)2 added to AL-69 was changed to 7 mL.

[1017] A polymerization operation was carried out in the same manner as in Example I-3, except that the catalyst solution prepared above was used and the polymerization conditions were changed as follows, to obtain 2.36 g of a polymer.

[1018] Toluene-2: 93mL

[1019] Comonomer and its added amount-2: MA (0.3 mL, 3.3 mmol), and no additional comonomer was added thereafter.

[1020] Amount of TNOA added-2: 1.5 mL (0.15 mmol)

[1021] Nitrogen pressure-2: 0.5MPa

[1022] Ethylene pressure-2: 2.5MPa

[1023] Initial cleaning and time-2: 2 minutes after the start of the reaction, the catalyst cartridge was cleaned with 3 mL of toluene.

[1024] Reaction time: 32 minutes

[1025] [Example 1-20]

[1026] Ni(cod)2 was changed to 16.7 mg (0.060 mmol), toluene was changed to 6 mL, AL-29 was replaced with 17.2 mg (0.040 mmol) of AL-61 obtained in Synthesis Example I-5, and the toluene solution of Ni(cod)2 added to AL-61 was changed to 4 mL. Otherwise, the same procedure as in Example I-1 was followed to prepare 4 mL of a catalyst solution (AL-61 concentration: approximately 10 mM).

[1027] Add 50 mL of toluene (hereinafter referred to as toluene-3) to a 0.2L autoclave, and raise the temperature in the autoclave to 50°C. Next, add 25 g of propylene. Inject 2 mL of the above catalyst solution (hereinafter referred to as initial catalyst-3) into the catalyst cartridge, add high-pressure nitrogen to the autoclave, and use this time as the reaction start time. 2 minutes after the start of the reaction, wash the catalyst cartridge with 3 mL of toluene, and add the washing liquid to the autoclave with high-pressure nitrogen (initial washing and its time-3). 60 minutes after the start of the reaction, add 3 mL of 1,2-butanediol toluene solution (0.2M) to stop the reaction, and release the pressure of propylene. Concentrate the recovered toluene solution to obtain a yellow oily polymer. Dissolve the obtained oily polymer in 10 mL of heptane, and add 100 mg of ISOLUTE (registered trademark) SCX-2 (manufactured by Biotage). The obtained mixture is stirred at 80°C for one hour, SCX-2 is removed by filtration, and concentrated with an evaporator to obtain a colorless and transparent polymer. The polymer was vacuum dried at 80°C for 3 hours or more to obtain 4.97 g of a polymer.

[1028] [Example I-21]

[1029] Ni(cod)2 was changed to 16.7 mg (0.060 mmol), toluene was changed to 6 mL, AL-29 was replaced with 16.3 mg (0.040 mmol) of AL-68 obtained in Synthesis Example I-7, and the toluene solution of Ni(cod)2 added to AL-68 was changed to 4 mL. Otherwise, the same procedure as in Example I-1 was followed to prepare 4 mL of a catalyst solution (AL-68 concentration: about 10 mM).

[1030] A polymerization operation was carried out in the same manner as in Example I-20, except that the catalyst was added as follows using the catalyst solution prepared above, to obtain 3.23 g of a polymer.

[1031] Catalyst addition: 12 minutes after the reaction started, 1.2 mL of catalyst solution was injected into the catalyst cartridge and added to the autoclave using high-pressure nitrogen. 14 minutes after the reaction started, the catalyst cartridge was cleaned with 3 mL of toluene and the cleaning solution was added to the autoclave using high-pressure nitrogen.

[1032] [Example I-22]

[1033] Ni(cod)2 was changed to 25.0 mg (0.090 mmol), toluene was changed to 9 mL, AL-29 was replaced with 28.7 mg (0.070 mmol) of AL-68 obtained in Synthesis Example I-7, and the toluene solution of Ni(cod)2 added to AL-68 was changed to 7 mL. Otherwise, the same procedure as in Example I-1 was followed to prepare 7 mL of a catalyst solution (AL-68 concentration: about 10 mM).

[1034] Add 43 mL of toluene to a 0.2L autoclave. Add 1.1 mL (4.9 mmol) of MU and 0.6 mL of a toluene solution (0.1 M) of Al(OiPr)3 from the reagent inlet. Add 25 g of propylene and raise the temperature in the autoclave to 50°C. Inject 3 mL of the above catalyst solution into the catalyst cartridge and add it to the autoclave with high-pressure nitrogen. This moment is taken as the start of the reaction. 2 minutes after the start of the reaction, wash the catalyst cartridge with 3 mL of toluene, and add the washing liquid to the autoclave with high-pressure nitrogen. 20 minutes after the start of the reaction, inject 3 mL of the catalyst solution into the catalyst cartridge and add it to the autoclave with high-pressure nitrogen. 22 minutes after the start of the reaction, wash the catalyst cartridge with 3 mL of toluene, and add the washing liquid to the autoclave with high-pressure nitrogen. 60 minutes after the start of the reaction, add 3 mL of a toluene solution (0.2 M) of 1,2-butanediol to stop the reaction and release the pressure on propylene. Concentrate the recovered toluene solution to obtain a yellow oily liquid. 10 mL of heptane was added to the oily liquid, and 100 mg of ISOLUTE (registered trademark) SCX-2 (manufactured by Biotage) was added. The obtained mixture was stirred at 80°C for 1 hour, SCX-2 was removed by filtration, and concentrated by an evaporator to obtain a colorless transparent liquid. The obtained liquid was heated to 120°C and vacuum dried for 15 minutes to obtain a polymer. Then, the obtained polymer was heated to 150°C and vacuum dried for 50 minutes to obtain 3.45 g of a polymer (wherein the residual amount of MU was 2.4 mol%).

[1035] [Example I-23]

[1036] Ni(cod)2 was changed to 16.7 mg (0.060 mmol), toluene was changed to 6 mL, AL-29 was replaced with 16.8 mg (0.040 mmol) of AL-69 obtained in Synthesis Example I-8, and the toluene solution of Ni(cod)2 added to AL-69 was changed to 4 mL. Otherwise, the same procedure as in Example I-1 was followed to prepare 4 mL of a catalyst solution (AL-69 concentration: about 10 mM).

[1037] Using the catalyst solution prepared above, a polymerization operation was carried out in the same manner as in Example I-20 except that the catalyst was added as follows and the polymerization conditions were changed as follows, thereby obtaining 3.74 g of a polymer.

[1038] Initial catalyst-3: 1mL

[1039] Initial cleaning and its time-3: 3 minutes after the reaction started, the catalyst cartridge was cleaned with 3 mL of toluene, and the cleaning liquid was added into the autoclave with high-pressure nitrogen.

[1040] Catalyst addition: 7 minutes after the reaction started, 1.5 mL of catalyst solution was injected into the catalyst cartridge and added to the autoclave using high-pressure nitrogen. 8 minutes after the reaction started, the catalyst cartridge was cleaned with 3 mL of toluene and the cleaning solution was added to the autoclave using high-pressure nitrogen.

[1041] [Comparative Example 1]

[1042] 92.6 mg (0.18 mmol) of tri(pentafluorophenyl)borane was weighed into a flask, and 6 mL of toluene was added to dissolve it. 13.0 mg (0.03 mmol) of AL-2a1 was weighed into another flask, and 5 mL of a toluene solution of tri(pentafluorophenyl)borane was added thereto. The solution was stirred at room temperature for 30 minutes to prepare a catalyst solution (6 mM).

[1043] 92 mL of toluene was added to a 0.2 L autoclave, and the temperature in the autoclave was raised to 90°C. Nitrogen was added to make the internal pressure of the autoclave 0.5 MPa. Next, ethylene was added to make the internal pressure of the autoclave 3.0 MPa. 0.5 mL of the above catalyst solution and 2.5 mL of toluene were added to the catalyst cartridge, and 3.3 MPa of nitrogen was added to the autoclave, and this time was regarded as the reaction start time. 5 minutes after the start of the reaction, 1.0 mL and 2.5 mL of the catalyst solution were added after 12 minutes, respectively. 16 minutes after the start of the reaction, the catalyst cartridge was washed with 3 mL of toluene, and the washing liquid was added to the autoclave. 60 minutes after the start of the reaction, a toluene solution (0.2 M) of 1,2-butanediol was added to stop the reaction, and ethylene was released from the pressure. The autoclave was returned to room temperature, and acetone (100 mL) was added. The precipitated solid was recovered by filtration, and the solid was washed with acetone (100 mL × 2), and dried under reduced pressure. The amount of polymer obtained was 0.57 g.

[1044] [Comparative Example 2]

[1045] A catalyst solution (10 mM) was prepared in the same manner as in Comparative Example 1 except that tri(pentafluorophenyl)borane was changed to 383.5 mg (0.75 mmol), toluene was changed to 15 mL, AL-2al was changed to 25.9 mg (0.06 mmol), and the toluene solution of tri(pentafluorophenyl)borane was changed to 6 mL.

[1046] To a 0.2 L autoclave, 91 mL of toluene and 0.3 mL (2.1 mmol) of tBA were added, and 100 μL of a toluene solution of TNOA (0.1 M) was added, and the temperature inside the autoclave was raised to 90°C.

[1047] Nitrogen was added to make the internal pressure of the autoclave 0.5 MPa. Next, ethylene was added to make the internal pressure of the autoclave 3.0 MPa. 2.5 mL of the above catalyst solution was added to the catalyst cartridge, and 3.3 MPa of nitrogen was added to the autoclave, and this moment was regarded as the start time of the reaction. 3 minutes after the start of the reaction, 2.5 mL of the catalyst solution was added. 6 minutes after the start of the reaction, the catalyst cartridge was cleaned with 3 mL of toluene, and the cleaning liquid was added to the autoclave. 60 minutes after the start of the reaction, a toluene solution (0.2 M) of 1,2-butanediol was added to stop the reaction, and the pressure of ethylene was released. The autoclave was returned to room temperature, and acetone (100 mL) was added. The precipitated solid was recovered by filtration, and the solid was cleaned with acetone (100 mL×2), and dried under reduced pressure. The obtained polymer was 0.016 g.

[1048] [Comparative Example 3]

[1049] 384.0 mg (0.75 mmol) of tri(pentafluorophenyl)borane was weighed into a flask, and 15 mL of toluene was added to dissolve it. 26.0 mg (0.06 mmol) of AL-2a1 was weighed into another flask, and 6 mL of a toluene solution of tri(pentafluorophenyl)borane was added thereto. The solution was stirred at room temperature for 30 minutes to prepare a catalyst solution (10 mM).

[1050] 50 mL of toluene and 25 g of propylene were added to a 0.2 L autoclave, and the temperature in the autoclave was raised to 50°C. 2.5 mL of the above catalyst solution was injected into the catalyst cartridge, and high-pressure nitrogen was added to the autoclave, and this time was regarded as the reaction start time. 4 minutes after the reaction started, the catalyst cartridge was cleaned with 3 mL of toluene, and the cleaning liquid was added to the autoclave with high-pressure nitrogen. 8 minutes after the reaction started, 2.5 mL of the above catalyst solution was injected into the catalyst cartridge, and high-pressure nitrogen was added to the autoclave. 10 minutes after the reaction started, the catalyst cartridge was cleaned with 3 mL of toluene, and the cleaning liquid was added to the autoclave with high-pressure nitrogen. 60 minutes after the reaction started, 3 mL of 1,2-butanediol toluene solution (0.2 M) was added to stop the reaction, and the pressure of propylene was released. The autoclave was returned to room temperature, and toluene was distilled off to obtain oily polypropylene. The obtained polypropylene was purified by silica gel column chromatography (developing solvent: hexane 100%) under the atmosphere. The obtained oily substance was dried under reduced pressure to obtain 0.021 g of polypropylene.

[1051] The polymerization conditions of Examples I-1 to I-19 are summarized in Table 1, and the results obtained are summarized in Table 2. The polymerization conditions of Examples I-20 to I-23 are summarized in Table 3, and the results obtained are summarized in Table 4. The polymerization conditions of Comparative Examples 1 to 3 are summarized in Table 5, and the results obtained are summarized in Table 6 or 7. It should be noted that "nm" in the table means not measured (a sample amount sufficient for measurement was not obtained).

[1052] [Table 1]

[1053] Table 1

[1054]

[1055] [Table 2]

[1056] Table 2

[1057]

[1058] [Table 3]

[1059] Table 3

[1060]

[1061] [Table 4]

[1062] Table 4

[1063]

[1064] [Table 5]

[1065] Table 5

[1066]

[1067] [Table 6]

[1068] Table 6

[1069]

[1070] [Table 7]

[1071] Table 7

[1072]

[1073] By comparing the examples and comparative examples of the first embodiment of the present invention, it can be seen that the novel compound that can be used as a ligand according to the first embodiment of the present invention, the metal complex using the novel compound, the catalyst composition for olefin polymerization and the catalyst for olefin polymerization, as well as the method for producing an olefin-based polymer using the catalyst, have improved catalytic properties such as activity and molecular weight, and can be used for the polymerization or copolymerization of olefins, especially for copolymerizing at least one monomer selected from the group consisting of polar group-containing monomers and cyclic olefins with non-cyclic olefins.

[1074] <Example II series: Second embodiment of the present invention>

[1075] (Synthesis Example II-1: Synthesis of AL-39)

[1076] (1) Synthesis of 2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxolane)

[1077] The compound of the following chemical formula was synthesized according to the description of Bioorg. Med. Chem. Lett. 2014, 24, 2379-2382.

[1078]

[1079] (2) Synthesis of bis(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxolane)-4-yl)phosphine chloride

[1080] Dissolve 2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxolane) (5 g, 22.5 mmol, 1 eq) in 50 mL of tetrahydrofuran. Cool the resulting solution to 0°C, slowly add n-BuLi (24.8 mmol, 1.1 eq), and stir the mixture at 20°C for 2.5 hours to obtain a yellow solution. Cool the solution to -78°C, and add PCl3 (1.39 g, 10.1 mmol, 0.45 eq) all at once. Warm the mixture to 20°C and stir for 1.5 hours to obtain a yellow suspension. Dry the suspension to obtain 5.72 g of a yellow, viscous mixture containing the target. The obtained mixture is used directly in the subsequent synthesis without purification.

[1081] 31 P{ 1 H}NMR (162MHz, CDCl3) δ: 46.3 (integral ratio 100%)

[1082]

[1083] (3) Synthesis of bis(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxolane)-4-yl)phosphine

[1084] Dissolve bis(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxolane)-4-yl)phosphine chloride (5.72 g, 11.2 mmol, 1 eq) in 50 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, lithium aluminum hydride (0.64 g, 16.9 mmol, 1.5 eq) was added, and the mixture was stirred at 20°C for 12 hours to obtain a colorless suspension. The resulting suspension was cooled to 0°C, 0.6 mL of water, 0.6 mL of 10% sodium hydroxide aqueous solution, and 1.8 mL of water were added in sequence, and the resulting mixture was stirred at room temperature for 30 minutes to stop the reaction. The mixture was filtered, and the filtrate was evaporated to dryness to obtain a colorless solid. Next, 30 mL of water was added to the obtained solid, and the product was extracted 3 times with 30 mL of dichloromethane. The collected organic layer was dried over sodium sulfate, the solid was filtered out, and the filtrate was concentrated to obtain a yellow crude product. The crude product was purified by silica gel chromatography (developing solvent: petroleum ether / ethyl acetate = 20 / 1) under atmospheric pressure and washed with 10 mL of hexane to obtain 3.1 g (6.5 mmol, 58%) of the target compound as a colorless solid.

[1085] 1 H NMR (400MHz, CDCl3) δ: 6.26 (s, 2H), 5.15 (d, J=235Hz, 1H), 1.57 (s, 24H)

[1086] 31 P{ 1 H}NMR(162MHz, CDCl3)δ: -126.8(s)

[1087]

[1088] (4) Synthesis of AL-39

[1089] 300 mg (0.63 mmol) of bis(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxolane)-4-yl)phosphine was weighed into a Schlenk tube, and 8 mL of tetrahydrofuran was added. After the resulting solution was cooled to 0°C, 0.44 mL (0.69 mmol) of n-BuLi was slowly added dropwise. After the addition was completed, the mixture was stirred at room temperature for 1 hour and 10 minutes. Thereafter, the mixture was cooled to 0°C, and 119 mg (0.63 mmol) of α-(trifluoromethyl)styrene oxide dissolved in 2.1 mL of tetrahydrofuran was slowly added. After the mixture was stirred at room temperature for 3 hours, it was cooled to 0°C, and 0.76 mL (0.76 mmol) of an ether solution of hydrogen chloride (hereinafter also referred to as "hydrochloric acid ether solution") was slowly added dropwise. After the mixture was stirred at 0°C for 1 hour, the solvent was distilled off. The obtained solid was purified by silica gel column chromatography (developing solvent: hexane / tetrahydrofuran / triethylamine = changed from 100 / 5 / 1 to 100 / 10 / 1) under air. After purification, it was recrystallized with 1 mL of tetrahydrofuran and 10 mL of hexane to obtain 157 mg of a solid. 31 The purity of AL-39 determined by P NMR was 99% or more.

[1090] 1 H NMR (400MHz, CDCl3) δ: 7.56 (d, J=7.4Hz, 2H), 7.34-7.31 (m, 3H), 6.27 (s, 1H), 6.24 (s, 1H), 4.66 (s, 1H), 4.02 (dd, J=15.4, 4.7Hz, 1H), 2.85 (d, J=15.6Hz, 1H), 1.59 (s, 6H), 1.58 (s, 6H), 1.51 (s, 6H), 1.44 (s, 6H)

[1091] 19 F NMR(376MHz, CDCl3)δ: -80.7(br)

[1092] 31 P{ 1 H}NMR (162MHz, CDCl3) δ: -61.2 (q, J=5.2Hz)

[1093]

[1094] (Synthesis Example II-2: Synthesis of AL-40)

[1095] 400 mg (0.84 mmol) of bis(2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxolane)-4-yl)phosphine was weighed into a Schlenk tube, and 11 mL of tetrahydrofuran was added. After the resulting solution was cooled to -78°C, 0.58 mL (0.92 mmol) of n-BuLi was slowly added dropwise. After the addition was completed, the mixture was stirred at -78°C for 1 hour. The mixture was then heated to 0°C, and 92 μL (0.84 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 2.8 mL of tetrahydrofuran was slowly added. After the mixture was stirred at room temperature for 1 hour, the solvent was distilled off. 14 mL of tetrahydrofuran was added to the residue, which was then cooled to 0°C, and 1.0 mL (1.0 mmol) of hydrochloric acid ether solution was slowly added dropwise. After the mixture was stirred at 0°C for 1 hour, 8 mL of water was added under the atmosphere for washing and the organic layer was separated. 4 mL of ether was added to the aqueous layer and the organic layer was extracted. This operation was repeated 3 times. After the collected organic layer was dried over sodium sulfate, the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane / acetone=10 / 1) under the atmosphere to obtain 242 mg of solid.

[1096] use 31 The purity of AL-40 determined by P NMR was 99% or more.

[1097] 1 H NMR (400MHz, CDCl3) δ: 6.30 (s, 2H), 4.76 (d, J=3.4Hz, 1H), 3.25 (brs, 2H), 1.58 (s, 12H), 1.55 (s, 12H)

[1098] 19 F NMR (376MHz, CDCl3) δ: -77.0 (d, J=22.0Hz) 31 P{ 1 H}NMR (162MHz, CDCl3) δ: -62.1 (septet, J=22.9Hz)

[1099]

[1100] (Synthesis Example II-3: Synthesis of AL-58)

[1101] (1) Synthesis of tert-butyl (2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxolane)-4-yl)phosphine borane

[1102] A tetrahydrofuran solution (20 mL) of 2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxolane) (2 g, 9 mmol, 1 eq) was cooled to 0°C, n-BuLi (2.5 M, 4.0 mL, 1.1 eq) was added, and the mixture was stirred at 20°C for 2 hours. The resulting mixture was added to a tetrahydrofuran solution (10 mL) of tert-butylphosphine dichloride (1.72 g, 10.8 mmol, 1.2 eq) cooled to -78°C. The mixture was stirred at 20°C for 12 hours to obtain a yellow suspension. The suspension was brought to 0°C, and borane dimethyl sulfide (10 M, 2.7 mL, 3 eq) was added. The resulting mixture was stirred at 20°C for 12 hours to obtain a light yellow solution. The solution was brought to 0°C, and lithium aluminum hydride (2.5 M, 10.8 mL, 27.0 mmol) was added. The obtained mixture was stirred at 20°C for 12 hours to obtain a yellow solution. The reaction mixture was injected into 100 mL of water, stirred thoroughly, and the organic layer was extracted with dichloromethane (50 mL×2). The collected organic layer was washed with 50 mL of saturated brine, the organic layer was dried over sodium sulfate, and the sodium sulfate was filtered out. The filtrate was concentrated under reduced pressure to obtain a crude product. The synthesis of the crude product was repeated several times to obtain 3.73 g of a crude product. The crude product was crushed and washed with 15 mL of petroleum ether at 20°C for 30 minutes to obtain 3.26 g (10.1 mmol) of the target product as a white solid.

[1103] 1 H NMR (400MHz, CDCl3) δ: 6.42 (s, 1H), 5.32 (dq, J = 375, 7.2Hz, 1H), 1.65 (s, 6H), 1.64 (s, 6H), 1.25 (d, J = 15.5Hz, 9H)

[1104] 31 P NMR (162MHz, CDCl3) δ: 3.6 (br).

[1105]

[1106] (2) Synthesis of AL-58

[1107] Mix 69 mg (0.20 mmol) of tetrabutylammonium hydrogen sulfate and 10.0 g of 5% sodium hypochlorite aqueous solution (13.0 mmol) and cool to 0°C. Add 1.09 g (6.49 mmol) of methyl 2-trifluoromethylacrylate to the mixture and stir at 0°C for 3 hours. Extract the product three times with 5 mL of ether from the mixture, and wash the collected organic layer with water. Extract the product twice with 3 mL of ether from the washing water. Add 5 mL of ether and 5 mL of water to the emulsified water layer and cool at -15°C overnight. Combine all the above organic layers, dry with sodium sulfate, and filter. Concentrate the filtrate at room temperature under reduced pressure of 74-17 mmHg. Add 8 mL of ether, add sodium sulfate to dry, filter, and concentrate the filtrate under slightly reduced pressure to obtain 391 mg of colorless liquid epoxide.

[1108] 300 mg (0.925 mmol) of tert-butyl (2,2,6,6-tetramethylbenzo [1,2-d: 5,4-d'] bis ([1,3] dioxolane) -4-yl) phosphine borane synthesized in the above (1) was weighed into a Schlenk tube, and 8 mL of tetrahydrofuran was added. After the resulting solution was cooled to -78°C, 1.88 mL (1.13 mmol) of a 0.6 M toluene solution of potassium bis (trimethylsilyl) amide was slowly added dropwise. After the addition was completed, the mixture was heated to 0°C, and a mixture of 155 mg of the previously synthesized colorless liquid epoxide and 1.6 mL of THF was slowly added. After the mixture was stirred at room temperature for 3 hours, it was cooled to 0°C, and then 0.87 M hydrochloric acid (3.5 mmol) was slowly added dropwise. The product was extracted from the mixture with 5 mL of ether three times, and the collected organic layer was washed with 5 mL of water. After the organic layer was dried over sodium sulfate, the sodium sulfate was removed by filtration using absorbent cotton. The filtrate was evaporated to dryness, and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane / dichloromethane = changed from 1 / 2 to 1 / 3) under atmospheric pressure to obtain 216 mg of a white solid.

[1109] 201 mg (0.407 mmol) of the solid obtained above and 55 mg (0.49 mmol) of 1,4-diazabicyclo[2.2.2]octane were dissolved in 3.5 mL of toluene. The obtained solution was heated to 60°C and then stirred for one and a half hours. After stirring, the solution was purified by silica gel column chromatography (developing solvent: hexane / acetone = 3 / 1) under nitrogen to obtain 180 mg of solid. 1 The ratio of diastereoisomers determined by H NMR was 1:0.3.

[1110] 1H NMR (400MHz, CDCl3) δ: 6.33 (s, 1H), 3.92 (s, 3H), 3.76 (dd, J=14.8, 4.4Hz, 1H), 3.4 4 (s, 1H), 2.05 (d, J = 14.6Hz, 1H), 1.66 (s, 6H), 1.59 (s, 6H), 1.09 (d, J = 13.2Hz, 9H)

[1111] 19 F NMR (376MHz, CDCl3) δ: -79.1 (br)

[1112] 31 P{ 1 H}NMR (162MHz, CDCl3) δ: -18.2 (q, J=5.5Hz)

[1113] Diastereomers

[1114] 1 H NMR (400MHz, CDCl3) δ: 6.35 (s, 1H), 4.07 (br, 1H), 3.73 (s, 3H), 3.43 (dd, J=14.8, 4.0H z, 1H), 2.00 (dd, J=14.8, 1.4Hz, 1H), 1.65 (s, 6H), 1.62 (s, 6H), 1.11 (d, J=13.7Hz, 9H)

[1115] 19 F NMR(376MHz, CDCl3)δ: -78.8(s)

[1116] 31 P{ 1 H}NMR(162MHz, CDCl3)δ: -21.7(s)

[1117]

[1118] (Synthesis Example II-4: Synthesis of AL-59)

[1119] 296 mg (0.913 mmol) of tert-butyl (2,2,6,6-tetramethylbenzo [1,2-d:5,4-d'] bis ([1,3] dioxolane) -4-yl) phosphine borane synthesized in the same manner as in (1) of Synthesis Example II-3 was weighed into a Schlenk tube, and 10 mL of tetrahydrofuran was added. After the resulting solution was cooled to -78°C, 2.0 mL (1.2 mmol) of a 0.6 M toluene solution of potassium bis (trimethylsilyl) amide was slowly added dropwise. After the addition was completed, the mixture was heated to 0°C and stirred for 1 hour. 0.133 mL (1.22 mmol) of 2,2-bis (trifluoromethyl) oxirane was slowly added to the mixture. The mixture was heated to room temperature, stirred for 2 hours, cooled to 0°C, and 4 mL (3.48 mmol) of 0.87 M hydrochloric acid was slowly added dropwise. From this mixture, the product was extracted 3 times with 5 mL of ether, and the collected organic layer was washed with 5 mL of water. After the collected organic layer was dried with sodium sulfate, sodium sulfate was removed by filtering using absorbent cotton. After the filtrate was evaporated to dryness, the obtained solid was purified by silica gel column chromatography (developing solvent: hexane / dichloromethane=2 / 1) under atmosphere to obtain 283 mg of white solid.

[1120] To 200 mg (0.397 mmol) of the solid obtained above was added 54 mg (0.48 mmol) of 1,4-diazabicyclo[2.2.2]octane dissolved in 3.5 mL of toluene, and the mixture was heated to 60°C and stirred for 1.5 hours. After stirring, the obtained solution was purified by silica gel column chromatography (developing solvent: hexane / acetone = 5 / 1) under nitrogen to obtain 234 mg of a solid. 31 P{ 1 The purity of AL-59 determined by H NMR was 100%.

[1121] 1 H NMR (400MHz, CDCl3) δ: 6.38 (s, 1H), 4.26 (d, J=8.7Hz, 1H), 3.63 (dd, J=16.0, 3.2 Hz, 1H), 2.03 (d, J = 16.0Hz, 1H), 1.65 (s, 6H), 1.61 (s, 6H), 1.13 (d, J = 14.2Hz, 9H)

[1122] 19 F NMR (376MHz, CDCl3) δ: -76.7 (dq, J=10.9, 10.9Hz), -77.7 (dq, J=10.9, 10.9Hz)

[1123] 31 P{ 1 H}NMR(162MHz, CDCl3)δ: -30.2(m)

[1124]

[1125] (Synthesis Example II-5: Synthesis of AL-63)

[1126] (1) Synthesis of 1,2,4,5-Tetrahydroxybenzene

[1127] Sodium dithionite (37.28 g, 214.14 mmol, 46.60 mL, 2 eq) and hydrochloric acid (12 M, 49.07 mL, 5.5 eq) were added to a solution formed by adding 200 mL of water to 2,5-dihydroxy-1,4-benzoquinone (15 g, 107.7 mmol, 1 eq). The resulting solution was stirred at 20°C for 30 minutes to obtain a white suspension. The suspension was filtered, and 200 mL of ethyl acetate was added to the filtrate twice to obtain a brown solution. The obtained organic layer was washed twice with 200 mL of water, sodium sulfate was added, and dried. The solid was then filtered out, and the filtrate was concentrated to obtain 14 g of a brown solid residue. The obtained compound was used directly in the subsequent synthesis without purification.

[1128] 1 H NMR (500 MHz, dimethyl sulfoxide-d6) δ: 7.93 (brs, 4H), 6.20 (s, 2H)

[1129]

[1130] (2) Synthesis of dispiro[cyclopentane-1,2'-benzo[1,2-d:4,5-d']bis([1,3]dioxolane)-6',1"-cyclopentane]

[1131] 1,2,4,5-Tetrahydroxybenzene (8g, 56mmol, 1eq) was dissolved in 80mL of dichloromethane. Cyclopentanone (18.94g, 225.2mmol, 19.9mL, 4eq) and dichlorodimethylsilane (14.53g, 112.6mmol, 13.6mL, 2eq) were added to the resulting solution, and the mixture was stirred at 20°C for 12 hours to obtain a brown solution. The resulting solution was concentrated, and 10mL of heptane was added to the obtained crude product and stirred for 3 minutes. The solution generated after stirring was filtered, 1.5mL of acetone was added to the filtrate, the mixture was refluxed, and then cooled to -10°C for recrystallization to obtain a black solid crude product. The solid was purified by silica gel column chromatography (developing solvent: petroleum ether / dichloromethane = 10 / 1) to obtain a white solid (5g, 18mmol).

[1132] 1H NMR (400MHz, CDCl3) δ: 6.34 (s, 2H), 2.09-2.05 (m, 8H), 1.83-1.79 (m, 8H)

[1133]

[1134] (3) Synthesis of bis(dispiro[cyclopentane-1,2'-benzo[1,2-d:4,5-d']bis([1,3]dioxolane)-6',1"-cyclopentane]-4'-yl)phosphine

[1135] Dispiro[cyclopentane-1,2'-benzo[1,2-d:4,5-d']bis([1,3]dioxolane)-6',1"-cyclopentane] (1 g, 3.7 mmol, 1 eq) was dissolved in 15 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, n-BuLi (2.5 M, 1.60 mL, 4.0 mmol, 1.1 eq) was slowly added, and the mixture was stirred at 20°C for 2.5 hours to obtain a yellow solution. The resulting solution was cooled to -78°C, and PCl3 (225 mg, 1.64 mmol, 143 μL, 0.45 eq) was added. The mixture was warmed to 20°C and then stirred for 1.5 hours to obtain a yellow suspension. The resulting yellow suspension was evaporated to dryness to obtain 1.12 g of a yellow and viscous compound.

[1136] The obtained yellow and viscous compound was dissolved in 15 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, lithium aluminum hydride (2.5M, 1.1 mL, 2.8 mmol) was slowly added, and the mixture was stirred at 20°C for 12 hours to obtain a brown suspension. The suspension was cooled to 0°C, 0.6 mL of water, 0.6 mL of 10% sodium hydroxide aqueous solution, and 1.8 mL of water were added in sequence, and the resulting mixture was stirred at room temperature for 30 minutes. The mixture was filtered, and the filtrate was evaporated to dryness to obtain a white solid. Then, 30 mL of water was added to the white solid, and the generated organic matter was extracted with dichloromethane (30 mL×3). The collected organic layer was dried over sodium sulfate, the solid was filtered out, and the filtrate was concentrated to obtain a crude product in the form of a yellow solid. The crude product was purified by silica gel chromatography (developing solvent: petroleum ether / ethyl acetate = 20 / 1), washed with 10 mL of hexane, and 0.16 g (0.28 mmol) of the target compound was obtained as a white solid.

[1137] 1 H NMR (400MHz, CDCl3) δ: 6.28 (s, 2H), 5.19 (d, J=234Hz, 1H), 1.99 (br, 16H), 1.76 (br, 16H)

[1138] 31 P{ 1 H}NMR(162MHz, CDCl3)δ: -125.2(s)

[1139]

[1140] (4) Synthesis of AL-63

[1141] 300 mg (0.52 mmol) of bis(dispiro[cyclopentane-1,2'-benzo[1,2-d:4,5-d']bis([1,3]dioxolane)-6',1"-cyclopentane]-4'-yl)phosphine synthesized in the above (3) was weighed into a Schlenk tube, and 6.8 mL of tetrahydrofuran was added. The resulting solution was cooled to -78°C, and 0.38 mL (0.57 mmol) of n-BuLi was slowly added dropwise. After the addition was completed, the mixture was stirred at -78°C for 1 hour and 20 minutes. The mixture was then heated to 0°C, and 57 μL (0.52 mmol) of 2,2-bis(trifluoromethyl)ethylene oxide dissolved in 1.3 mL of tetrahydrofuran was slowly added. The container containing 2,2-bis(trifluoromethyl)ethylene oxide was filled with 0.2 m L of tetrahydrofuran was used to wash twice, and the washing liquid was also added to the Schlenk tube. After stirring the mixture at room temperature for 2 hours and 40 minutes, the solvent was distilled off. 8 mL of tetrahydrofuran was added to the residue, and then cooled to 0°C, and then 0.62 mL (0.62 mmol) of hydrochloric acid ether solution was slowly added dropwise. After stirring the mixture at 0°C for 15 minutes, 5 mL of water was added under the atmosphere for washing, and the organic layer was separated. All subsequent operations were carried out under the atmosphere. 3 mL of ether was added to the aqueous layer, and the organic layer was extracted, and this operation was repeated 3 times. After drying the collected organic layers with sodium sulfate, the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane / acetone = 10 / 1) to obtain 120 mg of solid. Using 31 The purity of AL-63 determined by P NMR was 97%.

[1142] 1 H NMR (400MHz, CDCl3) δ: 6.32 (s, 2H), 4.67 (s, 1H), 3.25 (s, 2H), 2.01-1.92 (m, 16H), 1.77-1.73 (m, 16H)

[1143] 19 F NMR (376MHz, CDCl3) δ: -76.9 (d, J=22.2Hz)

[1144] 31 P{ 1H}NMR (162MHz, CDCl3) δ: -62.2 (septet, J=22.0Hz)

[1145]

[1146] (Synthesis Example II-6: Synthesis of AL-64)

[1147] (1) Synthesis of 2,3,7,8-tetrahydrobenzo[1,2-b:4,5-b']bis([1,4]dioxin

[1148] 1,2,4,5-Tetrahydroxybenzene (8 g, 56 mmol, 1 eq) and 1,2-dibromoethane (42.30 g, 225.2 mmol, 17.0 mL, 4 eq) were dissolved in 500 mL of dimethylformamide. Potassium carbonate (31.12 g, 225.2 mmol, 4 eq) was added to the resulting solution, and the mixture was stirred at 90°C for 12 hours to obtain a brown suspension. 1 After H-NMR confirmed the completion of the reaction, 500 mL of water was added to the reaction solution, and the solution was filtered to obtain a crude product. The crude product was dissolved in 200 mL of methanol, and 450 mL of toluene was added to dry solid to obtain 19 g of a gray compound.

[1149] 1 H NMR (400MHz, CDCl3) δ: 6.42 (s, 2H), 4.20 (s, 8H)

[1150]

[1151] (2) Synthesis of bis(2,3,7,8-tetrahydrobenzo[1,2-b:4,5-b']bis([1,4]dioxin-5-yl)phosphine

[1152] 2,3,7,8-Tetrahydrobenzo[1,2-b:4,5-b']bis([1,4]dioxin (4.4 g, 23 mmol) was dissolved in 100 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, n-BuLi (2.5 M, 9.5 mL, 23.8 mmol) was added, and the mixture was stirred at 0°C for 1 hour to obtain a yellow suspension. The resulting suspension was added to a toluene solution (10 mL) of (diethylamino)phosphine dichloride (1.58 g, 9.08 mmol) cooled to 0°C. The mixture was stirred at 0°C for 1 hour to obtain a yellow suspension. A dioxane solution of hydrogen chloride (4 M, 20 mL) was added to the suspension at 0°C, and the mixture was stirred at 20°C for 1 hour to obtain a yellow suspension. The resulting yellow suspension was evaporated to dryness to obtain 4.11 g of a yellow solid.

[1153] The yellow solid was dissolved in 80 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, lithium aluminum hydride (2.5 M, 7.3 mL, 18.3 mmol) was slowly added, and the mixture was stirred at 20°C for 12 hours to obtain a brown suspension. The suspension was cooled to 0°C again, 0.7 mL of water, 0.7 mL of 10% sodium hydroxide aqueous solution, and 2.1 mL of water were added in sequence, and the resulting mixture was stirred at room temperature for 30 minutes. The mixture was filtered, and the filtrate was evaporated to dryness to obtain a white solid. Then, 80 mL of water was added to the white solid, and the organic matter was extracted with dichloromethane (40 mL×3). The collected organic layer was dried over sodium sulfate, the solid was filtered out, and the filtrate was concentrated to obtain a crude product in the form of a yellow solid. The crude product was purified by silica gel chromatography (developing solvent: petroleum ether / ethyl acetate = changed from 10 / 1 to 5 / 1), crushed and washed with 10 mL of hexane, and 1.03 g (2.46 mmol) of the target compound was obtained as a white solid.

[1154] 1 H NMR (500MHz, CDCl3) δ: 6.36 (s, 2H), 5.40 (d, J=243Hz, 1H), 4.14 (s, 16H)

[1155] 31 P{ 1 H}NMR(202MHz, CDCl3)δ: -132.3(s)

[1156]

[1157] (3) Synthesis of AL-64

[1158] 250 mg (0.60 mmol) of bis(2,3,7,8-tetrahydrobenzo[1,2-b:4,5-b']bis([1,4]dioxin)-5-yl)phosphine synthesized in (2) above was weighed into a Schlenk tube, and 8 mL of tetrahydrofuran was added. The resulting solution was cooled to -78°C, and 0.43 mL (0.66 mmol) of n-BuLi was slowly added dropwise. After the addition was completed, the mixture was stirred at -78°C for 45 minutes. The mixture was then heated to 0°C, and 65 μL (0.60 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 2.0 mL of tetrahydrofuran was slowly added. The container containing 2,2-bis(trifluoromethyl)oxirane was rinsed twice with 0.2 mL of tetrahydrofuran, and the rinse solution was also added to the Schlenk tube. The obtained mixture was stirred at room temperature for 1 hour and 40 minutes, cooled to 0°C, and 0.72 mL (0.72 mmol) of hydrochloric acid ether solution was slowly added dropwise. After stirring the mixture at 0°C for 40 minutes, 5.7 mL of water was added under the atmosphere for washing, and the organic layer was separated. All subsequent operations were performed under the atmosphere. 3 mL of ether was added to the aqueous layer and the organic layer was extracted, and this operation was repeated 3 times. After drying the collected organic layer with sodium sulfate, the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane / acetone = 10 / 1 to 5 / 1, then changed to 4 / 1, and further changed to 2 / 1) to obtain 131 mg of solid. Using 31 The purity of AL-64 determined by P-NMR was 98%.

[1159] 1 H NMR (400MHz, CDCl3) δ: 6.41 (s, 2H), 5.09 (d, J=5.2Hz, 1H) 4.15-4.08 (m, 16H), 3.21 (s, 2H)

[1160] 19 F NMR (376MHz, CDCl3) δ: -77.3 (d, J=22.2Hz)

[1161] 31 P{ 1 H}NMR (162MHz, CDCl3) δ: -59.5 (septet, J=21.1Hz)

[1162]

[1163] (Synthesis Example II-7: Synthesis of AL-66)

[1164] (1) Synthesis of benzo[1,2-d:4,5-d']bis([1,3]dioxolane)

[1165] Potassium carbonate (62.2 g, 450 mmol) and dibromomethane (31.6 mL, 78.3 g, 450 mmol) were added to a dimethylformamide solution (50 mL) of 1,2,4,5-tetrahydroxybenzene (8 g, 56 mmol) below 25°C, and the resulting mixture was stirred at 100°C for 16 hours to obtain a red suspension. The suspension was added to water (150 mL), and the organic layer was extracted with ethyl acetate (150 mL×3). The collected organic layer was washed with 150 mL of saturated brine and dried over sodium sulfate. The sodium sulfate was filtered out, and the filtrate was concentrated to obtain a crude product. The crude product was purified by silica gel chromatography (developing solvent: petroleum ether / ethyl acetate = 10 / 1) to obtain 0.8 g (4.8 mmol) of the target product as a yellow solid.

[1166] 1 H NMR (400MHz, CDCl3) δ: 6.50 (s, 2H), 5.88 (s, 4H)

[1167]

[1168] (2) Synthesis of bis(benzo[1,2-d:4,5-d']bis([1,3]dioxolane)-4-yl)-N,N-diethylaminophosphine

[1169] Dissolve benzo[1,2-d:4,5-d']bis([1,3]dioxolane) (2g, 12mmol, 1eq) in 20mL of tetrahydrofuran. Cool the resulting solution to 0°C, slowly add n-BuLi (2.5M, 5.3mL, 13.3mmol, 1.1eq), slowly warm the mixture to 20°C, and stir for 2 hours to obtain a yellow solution. Cool the resulting solution to 0°C, and add (diethylamino)phosphine dichloride (942mg, 5.41mmol, 0.45eq) dissolved in 10mL of tetrahydrofuran. Stir the mixture at 0°C for 1 hour to obtain a yellow solution. Dry the solution to obtain 2.61g of crude product as a yellow solid. The obtained solid is used directly in the subsequent synthesis without purification.

[1170] 31 P{ 1 H}NMR (162 MHz, CDCl3) δ: 21.6 (s, integration ratio 100%)

[1171]

[1172] (3) Synthesis of bis(benzo[1,2-d:4,5-d']bis([1,3]dioxolane)-4-yl)phosphine chloride

[1173] The crude product (2.61 g) obtained in (2) above was dissolved in 40 mL of toluene. The resulting solution was cooled to 0°C, a solution of hydrogen chloride in dioxane (4 M, 20 mL) was added, and the mixture was stirred at 20°C for 1 hour to obtain a yellow solution. The resulting solution was used directly in the next synthesis without purification.

[1174] 31 P{ 1 H}NMR (162 MHz, CDCl3) δ: 41.9 (s, integration ratio 44%)

[1175]

[1176] (4) Synthesis of bis(benzo[1,2-d:4,5-d']bis([1,3]dioxolane)-4-yl)phosphine

[1177] The solvent of the yellow solution obtained in (3) above was changed to 30 mL of tetrahydrofuran. The resulting solution was cooled to 0°C, lithium aluminum hydride (2.5 M, 3.6 mL, 9.0 mmol) was added, and the mixture was slowly stirred at 20°C for 12 hours to obtain a yellow solution. The yellow solution was cooled to 0°C, 0.4 mL of water, 0.4 mL of 10% sodium hydroxide aqueous solution, and 1.2 mL of water were added in sequence, and the resulting mixture was stirred at 20°C for 30 minutes. The mixture was filtered, and the filtrate was evaporated to dryness to obtain a yellow solid. The obtained solid was purified by silica gel chromatography (developing solvent: petroleum ether / dichloromethane = changed from 5 / 1 to 1 / 1, and further to 0 / 1) to obtain 0.22 g of the target compound as a white solid.

[1178] 1 H NMR (400MHz, CDCl3) δ: 6.47 (s, 2H), 5.89 (s, 8H), 5.26 (d, J=235Hz, 1H)

[1179] 31 P{ 1 H}NMR(162MHz, CDCl3)δ: -126.0(s)

[1180]

[1181] (5) Synthesis of AL-66

[1182] 200 mg (0.55 mmol) of bis(benzo[1,2-d:4,5-d']bis([1,3]dioxolane)-4-yl)phosphine synthesized in (4) above was weighed into a Schlenk tube, and 7.3 mL of tetrahydrofuran was added. The resulting solution was cooled to -78°C, and 1.0 mL (0.61 mmol) of a toluene solution of potassium bis(trimethylsilyl)amide was slowly added dropwise. After the addition was completed, the mixture was stirred at -78°C for 45 minutes. The mixture was then heated to 0°C, and 60 μL (0.55 mmol) of 2,2-bis(trifluoromethyl)oxirane dissolved in 1.8 mL of tetrahydrofuran was slowly added. The container containing 2,2-bis(trifluoromethyl)oxirane was rinsed twice with 0.3 mL of tetrahydrofuran, and the rinse solution was also added to the Schlenk tube. The mixture was stirred at room temperature for 1 hour and 30 minutes, and the solvent was distilled off. After adding 9.7 mL of tetrahydrofuran to the residue, cool to 0°C, and slowly dropwise add 0.66 mL (0.66 mmol) of hydrochloric acid ether solution. After stirring the obtained mixture at 0°C for 1 hour, add 5.2 mL of water under air for washing, and separate the organic layer. All subsequent operations were performed under air. Add 2.6 mL of ether to the aqueous layer and extract the organic layer, and repeat this operation 3 times. After drying the collected organic layer with sodium sulfate, remove the sodium sulfate by filtration. The filtrate was evaporated to dryness, and the obtained solid was purified by silica gel column chromatography (developing solvent: hexane / acetone = changed from 10 / 1 to 5 / 1) to obtain 136 mg of solid. Using 31 The purity of AL-66 determined by P-NMR was 99% or more.

[1183] 1 H NMR (400MHz, CDCl3) δ: 6.50 (s, 2H), 5.86 (d, J = 1.2Hz, 4H), 5.84 (d, J = 1.6Hz, 4H), 4.10 (d, J = 2.8Hz, 1H), 3.24 (d, J = 1.6Hz, 2H)

[1184] 19 F NMR (376MHz, CDCl3) δ: -77.1 (d, J=22.2Hz)

[1185] 31 P{ 1 H}NMR (162MHz, CDCl3) δ: -64.7 (septet, J=20.6Hz)

[1186]

[1187] (Synthesis Example II-8: Synthesis of AL-40 / NiArPy)

[1188] 393 mg (1.4 mmol) of Ni(cod)2 was weighed into a Schlenk tube, and 6 mL of toluene was added. 0.21 mL (1.4 mmol) of tetramethylethylenediamine and 0.16 mL (1.4 mmol) of 4-bromofluorobenzene were added to the solution, and the mixture was stirred at room temperature for 3 hours. After stirring, the supernatant was separated and the residue was washed with 2 mL of hexane, and the operation was repeated 3 times. After washing, the solvent was distilled off to obtain a solid 1.

[1189] Then, 92 mg (0.14 mmol) of AL-40 was weighed into a Schlenk tube, and 5.3 mL of tetrahydrofuran was added thereto. The solution was cooled to 0°C, and 79 μL (0.15 mmol) of a tetrahydrofuran solution of sodium hexamethyldisilazane was slowly added thereto. After the mixture was stirred at room temperature for 1 hour, the solvent was completely distilled off. 1.9 mL of tetrahydrofuran was added to the obtained residue to obtain a sodium solution of AL-40.

[1190] Weigh 70 mg (0.20 mmol) of the solid 1 into a Schlenk tube, add 1.0 mL of tetrahydrofuran, and obtain a transition metal compound solution. Add the sodium solution of AL-40 to the transition metal compound solution at room temperature. Wash the Schlenk tube to which the sodium solution of AL-40 has been added twice with 0.2 mL of tetrahydrofuran, and add the washing liquid to the transition metal compound solution. Stir the mixture at room temperature for 2 hours and 30 minutes, and then filter it with diatomaceous earth. After filtering, distill the solvent from the filtrate, and wash the residue 8 times with 2 mL of hexane. The residue is completely dried to obtain 98 mg of solid 2.

[1191] Then, 271 mg of the solid was weighed into a Schlenk tube, and 3.2 mL of tetrahydrofuran was added thereto. 13 μL (0.16 mmol) of pyridine was added to the resulting solution, and after stirring at room temperature for 1 hour, diatomaceous earth filtration was performed. After filtration, the solv...

Claims

1. A compound represented by the following general formula (A), In formula (A), X 1 represents an oxygen atom or a sulfur atom, E 1 represents a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom, Z represents a hydrogen atom, a leaving group, or a cation having a valence of 1 or more and 4 or less, m is an integer greater than or equal to 1 and less than or equal to the valence number of Z, n is 0, 1, 2, 3 or 4. When n is 0, E 1 With X 1 , R 5 and R 6 The bonded carbon atoms are directly bonded, R 1 represents a hydrocarbon group represented by the following general formula (B) or (C), R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, which is different from the hydrocarbon group represented by the following general formula (B) or (C) and which may contain at least one heteroatom, l is 1 or 2. When l is 2, R 2 does not exist, R 3 , R 4 , R 5 and R 6 Each independently represents an atom or group selected from the group consisting of the following (i) to (iv), (i) Hydrogen atom (ii) Halogen atoms (iii) a hydrocarbon group having 1 to 30 carbon atoms and optionally containing at least one heteroatom (iv)OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group, wherein R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, y represents 0, 1 or 2, R 3 , R 4 , R 5 and R 6 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom, In formula (B) and formula (C), *Indicates the same as E 1 The connection key, R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A), R 7 , R 8 , R 9 and R 10 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom, A 1 , A 2 , A 3 and A 4 Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)-, wherein each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom, in, In formula (B), A 1 , A 2 , A 3 and A 4 At least two of them are -C(R)2-, in formula (C), A 3 and A 4 At least one of them is -C(R)2- and R 12 and R 13 At least one of them is an atom or group selected from the group consisting of (i) and (iii), or A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 are atoms or groups selected from the group consisting of (i) and (iii), W 1 and W 2 Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8 and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R 10 does not exist, h and i are each independently an integer of 1 to 6, 1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R 7 , R 8 , R 9 and R 10 They may be the same or different.

2. A metal complex represented by the following general formula (D), In formula (D), X 1 represents an oxygen atom or a sulfur atom, E 1 represents a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom, n is 0, 1, 2, 3 or 4. When n is 0, E 1 With X 1 , R 5 and R 6 The bonded carbon atoms are directly bonded, R 1 represents a hydrocarbon group represented by the following general formula (B) or (C), R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, which is different from the hydrocarbon group represented by the following general formula (B) or (C) and which may contain at least one heteroatom, l is 1 or 2. When l is 2, R 2 does not exist, R 3 , R 4 , R 5 and R 6 Each independently represents an atom or group selected from the group consisting of the following (i) to (iv), (i) Hydrogen atom (ii) Halogen atoms (iii) a hydrocarbon group having 1 to 30 carbon atoms and optionally containing at least one heteroatom (iv)OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group, wherein R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, y represents 0, 1 or 2, R 3 , R 4 , R 5 and R 6 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom, M 1 represents a nickel atom or a palladium atom, L 1 and L 2 Each independently represents the coordination in M 1 The ligand, L 1 and L 2 Optionally bonded to each other to form a 1 The ring, In formula (B) and formula (C), *Indicates the same as E 1 The connection key, R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A), R 7 , R 8 , R 9 and R 10 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom, A 1 , A 2 , A 3 and A 4 Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)-, wherein each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom, in, In formula (B), A 1 , A 2 , A 3 and A 4 At least two of them are -C(R)2-, in formula (C), A 3 and A 4 At least one of them is -C(R)2- and R 12 and R 13 At least one of them is an atom or group selected from the group consisting of (i) and (iii), or A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 are atoms or groups selected from the group consisting of (i) and (iii), W 1 and W 2 Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8 and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R 10 does not exist, h and i are each independently an integer of 1 to 6, 1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R 7 , R 8 , R 9 and R 10 They may be the same or different.

3. A catalyst composition for olefin polymerization, comprising the compound represented by the general formula (A) according to claim 1 and a transition metal compound represented by the following general formula (E) or (F), In formula (E) and formula (F), M 1 represents a nickel atom or a palladium atom, L 1 and L 2 Each independently represents the coordination in M 1 The ligand, L 1 and L 2 Optionally bonded to each other to form a 1 The ring, M 2 and M 3 each independently represents a nickel atom or a palladium atom, L 3 , L 4 , L 5 , L 6 , L 9 and L 10 Each independently represents the coordination in M 1 、M 2 or M 3 The ligand, L 7 and L 8 Each independently represents the coordination in M 2 and M 3 The ligand, q is 0, 1, or 2, L 3 and L 4 Optionally bonded to each other to form a 1 The ring, L 5 and L 6 Optionally bonded to each other to form a 2 The ring, L 9 and L 10 Optionally bonded to each other to form a 3 Ring.

4. The compound according to claim 1, characterized in that The R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv).

5. The metal complex according to claim 2, characterized in that The R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv).

6. The catalyst composition for olefin polymerization according to claim 3, characterized in that The R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv).

7. The compound according to claim 1, characterized in that The R 5 is an atom or group selected from the group consisting of (i) and (iii), wherein R 6 is selected from (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in the group, where R a , R b , y as defined in claim 1.

8. The metal complex according to claim 2, characterized in that The R 5 is an atom or group selected from the group consisting of (i) and (iii), wherein R 6 is selected from (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in the group, where R a , R b , y as defined in claim 2.

9. The catalyst composition for olefin polymerization according to claim 3, characterized in that The R 5 is an atom or group selected from the group consisting of (i) and (iii), wherein R 6 is selected from (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in the group, where R a , R b , y as defined in claim 1.

10. The compound according to any one of claims 1, 4 and 7, characterized in that The R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv).

11. The metal complex according to any one of claims 2, 5 and 8, characterized in that The R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv).

12. The catalyst composition for olefin polymerization according to any one of claims 3, 6 and 9, characterized in that The R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv). 13 . An olefin polymerization catalyst comprising the olefin polymerization catalyst composition according to claim 3 .

14. A catalyst for olefin polymerization, comprising the metal complex according to claim 2.

15. A method for producing an olefin polymer, characterized in that: Olefins are polymerized or copolymerized in the presence of the olefin polymerization catalyst according to claim 13 or 14.

16. The method for producing an olefin-based polymer according to claim 15, wherein: The acyclic olefin is copolymerized with at least one monomer selected from the group consisting of a polar group-containing monomer and a cyclic olefin.

17. A compound represented by the following general formula (A), In formula (A), X 1 represents an oxygen atom or a sulfur atom, E 1 represents a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom, Z represents a hydrogen atom, a leaving group, or a cation having a valence of 1 or more and 4 or less, m is an integer greater than or equal to 1 and less than or equal to the valence number of Z, n is 0, 1, 2, 3 or 4. When n is 0, E 1 With X 1 , R 5 and R 6 The bonded carbon atoms are directly bonded, R 1 represents a hydrocarbon group represented by the following general formula (B) or (C), R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, which is different from the hydrocarbon group represented by the following general formula (B) or (C) and which may contain at least one heteroatom, l is 1 or 2. When l is 2, R 2 does not exist, R 3 , R 4 , R 5 and R 6 Each independently represents an atom or group selected from the group consisting of the following (i) to (iv), (i) Hydrogen atom (ii) Halogen atoms (iii) a hydrocarbon group having 1 to 30 carbon atoms and optionally containing at least one heteroatom (iv)OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group, wherein R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, y represents 0, 1 or 2, R 3 , R 4 , R 5 and R 6 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom, In formula (B) and formula (C), *Indicates the same as E 1 The connection key, R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A), R 7 , R 8 , R 9 and R 10 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom, A 1 , A 2 , A 3 and A 4 Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)-, wherein each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom, in, In formula (B), A 1 , A 2 , A 3 and A 4 At least three of them are groups other than -C(R)2-, In formula (C), A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 At least one of the above is an atom or group selected from the group consisting of (ii) and (iv), wherein (iv) in formula (C) does not include an epoxy-containing group, W 1 and W 2 Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8 and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R 10 does not exist, h and i are each independently an integer of 1 to 6, 1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R 7 , R 8 , R 9 and R 10 They may be the same or different.

18. A metal complex represented by the following general formula (D): In formula (D), X 1 represents an oxygen atom or a sulfur atom, E 1 represents a nitrogen atom, a phosphorus atom, an arsenic atom or an antimony atom, n is 0, 1, 2, 3 or 4. When n is 0, E 1 With X 1 , R 5 and R 6 The bonded carbon atoms are directly bonded, R 1 represents a hydrocarbon group represented by the following general formula (B) or (C), R 2 represents a hydrocarbon group having 1 to 20 carbon atoms, which is different from the hydrocarbon group represented by the following general formula (B) or (C) and which may contain at least one heteroatom, l is 1 or 2. When l is 2, R 2 does not exist, R 3 , R 4 , R 5 and R 6 Each independently represents an atom or group selected from the group consisting of the following (i) to (iv), (i) Hydrogen atom (ii) Halogen atoms (iii) a hydrocarbon group having 1 to 30 carbon atoms and optionally containing at least one heteroatom (iv)OR b 、C(O)OR b 、C(O)OM'、C(O)N(R a )2. C(O)R b 、OC(O)R b , SR b 、S(O)2R b 、S(O)R b 、OS(O)2R b ,SF5,P(O)(OR b ) 2-y (R a ) y 、CN、N(H)R a 、N(R b )2、Si(OR a ) 3-x (R a ) x 、OSi(OR a ) 3-x (R a ) x , NO2, S(O)2OM', P(O)(OM')2, P(O)(OR b )2M' or an epoxy-containing group, wherein R a Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R b Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, M' represents an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or phosphonium, x represents 0, 1, 2 or 3, y represents 0, 1 or 2, R 3 , R 4 , R 5 and R 6 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring or a heterocyclic ring containing at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom, M 1 represents a nickel atom or a palladium atom, L 1 and L 2 Each independently represents the coordination in M 1 The ligand, L 1 and L 2 Optionally bonded to each other to form a 1 The ring, In formula (B) and formula (C), *Indicates the same as E 1 The connection key, R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Each independently represents an atom or group selected from the group consisting of (i) to (iv) defined in the above formula (A), R 7 , R 8 , R 9 and R 10 Adjacent substituents are optionally linked to each other to form a 5- to 8-membered alicyclic ring, aromatic ring or heterocyclic ring containing at least one heteroatom selected from oxygen atom, nitrogen atom or sulfur atom, A 1 , A 2 , A 3 and A 4 Each independently represents an oxygen atom, a sulfur atom, -C(R)2-, -S(O)-, -S(O)2-, -N(R)-, -P(R)- or -P(O)(R)-, wherein each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom, in, In formula (B), A 1 , A 2 , A 3 and A 4 At least three of them are groups other than -C(R)2-, In formula (C), A 3 and A 4 are all groups other than -C(R)2- and R 12 and R 13 At least one of the above is an atom or group selected from the group consisting of (ii) and (iv), wherein (iv) in formula (C) does not include an epoxy-containing group, W 1 and W 2 Each independently represents a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -P(O)- or -S(O)2-. When it is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R 8 and R 10 Not present, when it is an oxygen atom or -S(O)2-, R 7 and R 8 and R 9 and R 10 does not exist, h and i are each independently an integer of 1 to 6, 1 , W 2 , R 7 , R 8 , R 9 and R 10 When there are multiple W 1 , W 2 , R 7 , R 8 , R 9 and R 10 They may be the same or different.

19. A catalyst composition for olefin polymerization, comprising the compound represented by the general formula (A) according to claim 17 and a transition metal compound represented by the following general formula (E) or (F), In formula (E) and formula (F), M 1 represents a nickel atom or a palladium atom, L 1 and L 2 Each independently represents the coordination in M 1 The ligand, L 1 and L 2 Optionally bonded to each other to form a 1 The ring, M 2 and M 3 each independently represents a nickel atom or a palladium atom, L 3 , L 4 , L 5 , L 6 , L 9 and L 10 Each independently represents the coordination in M 1 、M 2 or M 3 The ligand, L 7 and L 8 Each independently represents the coordination in M 2 and M 3 The ligand, q is 0, 1, or 2, L 3 and L 4 Optionally bonded to each other to form a 1 The ring, L 5 and L 6 Optionally bonded to each other to form a 2 The ring, L 9 and L 10 Optionally bonded to each other to form a 3 Ring.

20. The compound according to claim 17, characterized in that The R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv).

21. The metal complex according to claim 18, characterized in that The R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv).

22. The catalyst composition for olefin polymerization according to claim 19, characterized in that The R 5 and R 6 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv).

23. The compound according to claim 17, characterized in that The R 5 is an atom or group selected from the group consisting of (i) and (iii), wherein R 6 is selected from (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in the group, where R a , R b , y as defined in claim 17.

24. The metal complex according to claim 18, characterized in that The R 5 is an atom or group selected from the group consisting of (i) and (iii), wherein R 6 is selected from (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in the group, where R a , R b , y as defined in claim 18.

25. The catalyst composition for olefin polymerization according to claim 19, characterized in that The R 5 is an atom or group selected from the group consisting of (i) and (iii), wherein R 6 is selected from (i), (iii), C(O)OR b 、C(O)N(R a )2. C(O)R b 、S(O)2R b and P(O)(OR b ) 2-y (R a ) y The atoms or groups in the group, where R a , R b , y as defined in claim 17.

26. The compound according to any one of claims 17, 20 and 23, characterized in that The R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv).

27. The metal complex according to any one of claims 18, 21 and 24, characterized in that The R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv).

28. The catalyst composition for olefin polymerization according to any one of claims 19, 22 and 25, characterized in that The R 3 and R 4 At least one of them is an atom or group selected from the group consisting of (i), (iii) and (iv).

29. An olefin polymerization catalyst comprising the olefin polymerization catalyst composition according to claim 19.

30. A catalyst for olefin polymerization, comprising the metal complex according to claim 18.

31. A method for producing an olefin polymer, characterized in that: Olefins are polymerized or copolymerized in the presence of the olefin polymerization catalyst according to claim 29 or 30.

32. The method for producing an olefin-based polymer according to claim 31, wherein The acyclic olefin is copolymerized with at least one monomer selected from the group consisting of a polar group-containing monomer and a cyclic olefin.

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