Metal complexes with sulfilimine-type ligands and their use as polymerization catalysts - Patents.com

Abstract

Metal complexes of general formula (I): Cyc LMZ p (I) wherein M is a metal selected from the group consisting of titanium, zirconium, and hafnium; Cyc is a cyclic ligand selected from cyclopentadienyl, indenyl, and fluorenyl, which may bear one or more substituents; Z is an anionic ligand; and L is a group represented by the general formula (II): JPEG2024515258000022.jpg33170 sulfilimine-containing ligands, where Sub1 and Sub2 are, independently of each other, aromatic residues that may be unsubstituted or may contain at least one substituent. Methods for the use of the compounds for the polymerization of monomers and for producing polymers using the metal complexes are also provided.

Description

[Technical field]

[0001] The present disclosure relates to metal complexes comprising Group 4 metals and having sulfilimine-type containing ligands, the use of the metal complexes for the polymerization of olefins, and methods for making polymers using the metal complexes. [Background technology]

[0002] Polyolefins are polymers produced from simple alkenes, such as α-olefins or polyenes. They can be distinguished into thermoplastic polyolefins, such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), very low density polyethylene (ULDPE), medium density polyethylene (MDPE), polypropylene (PP), polymethylpentene (PMP), and polybutene-1 (PB-1); and polyolefin elastomers (POE), such as high density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), polyisobutylene (PIB), poly-α-olefin-ethylene-propylene rubber (EPM), and ethylene propylene diene monomer rubber (EPDM rubber). These polymers are generally produced using a polymerization catalyst. Many such catalysts are known. Half metallocene catalysts having amide group-containing ligands and their use in the polymerization of olefins to produce high molecular weight polymers have been described, for example, in U.S. Patent No. 6,114,481 and WO 2005 / 090418. However, there remains a need for alternative or improved polymerization catalysts. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Patent No. 6,114,481 [Patent Document 2] International Publication No. 2005 / 090418 Summary of the Invention [Problem to be solved by the invention]

[0004] It has now also been found that half metallocene metal complexes comprising a Group 4 metal and a sulfilimine-type ligand can be used in the polymerization of olefins to produce polyolefins, in particular olefins of high molecular weight, preferably of at least 200,000 g / mol molecular weight (Mw). [Means for solving the problem]

[0005] In one embodiment, a metal complex of general formula (I): Cyc LMZ p (I) (In the formula, M is a metal selected from the group consisting of titanium, zirconium, and hafnium; Cyc is a cyclic ligand bonded to the metal M and is selected from unsubstituted and substituted cyclopentadienyl, indenyl, and fluorenyl; Z is independently selected from neutral or anionic ligands bound to the metal M, where the neutral ligands are selected from conjugated dienes having 4 to 40 carbon atoms which may be optionally substituted one or more times with a substituent selected from the group consisting of hydrocarbyl, silyl, halocarbyl, and combinations thereof, and the anionic ligands are selected from -H, -F, -Cl, -Br, -I, pseudohalogens, -C 1~12 -Alkyl, -OC 1~12 -Alkyl, -C(=O)C 1~12 -Alkyl, -acetylacetonate, C 1~12 Alkyl biscarboxylates, -phenyl, -O-phenyl, -Si(C 1~12 -alkyl) 3 , -Ge(C 1~12 -alkyl) 3 , -N(C 1~12 -alkyl) 2 , -P(C 1~12 )-Alkyl) 2 , -SC 1~12 -alkyl anionic forms, and combinations thereof; preferably -C 1~12-Alkyl, benzyl, -Si(CH 3 ) 3 , -CH 2 -Si(CH 3 ) 3 , -phenyl, O-phenyl, -C 1~12 Alkyl, -OC 1~12 -Alkyl, -N(C 1~12 -alkyl) 2 , -F, -Cl, -Br, -I, -pseudohalogens, and -Si(C 1~12 -alkyl) 3 -phenyl and -O-phenyl substituted with 1, 2, 3, 4 or 5 substituents independently selected from the group consisting of The index p is either 1 or 2, preferably 2; L is bonded to the metal M by the nitrogen atom of the sulfur-nitrogen double bond, general formula (II): [ka] where Sub1 and Sub2 are, independently of each other, aromatic residues which may be unsubstituted or which may contain at least one substituent. is provided.

[0006] In another aspect, there is provided a method for preparing a polymer, comprising the steps of: (a) providing a monomer composition comprising ethylene; and (b) contacting at least a portion of the monomer composition with a catalyst composition comprising a metal complex to produce a polymer comprising units derived from ethylene.

[0007] In a further aspect, there is provided the use of a composition comprising a metal complex as a polymerization catalyst for producing a polymer comprising units derived from ethylene. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] For a complete understanding of the present disclosure and its advantages, reference is made to the following detailed description.

[0009] It should be understood that the various aspects and embodiments of the detailed description disclosed herein are intended to illustrate specific ways of making and using the disclosure, and do not limit the scope of the disclosure when considered in conjunction with the claims and the detailed description. It will also be understood that features from various aspects and embodiments of the disclosure may be combined with features from various aspects and embodiments of the disclosure.

[0010] In the following description, the terms "containing," "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional element, step or procedure, whether or not it is specifically disclosed.

[0011] In the following description, several standards may be used. Unless otherwise indicated, the standards are used in the version that came into force on March 1, 2020. If there is no version in force as of that date, for example because a standard has expired, the version in force on the date closest to March 1, 2020 is referenced.

[0012] In the following description, amounts of components of compositions or polymers may be indicated by "weight percent," "wt.%," or "% by weight." The terms "weight percent," "wt.%," or "% by weight" are used interchangeably and are based on the total weight of the composition or polymer, respectively, which total weight is 100% unless otherwise indicated.

[0013] The term "phr" means parts per hundred rubber, i.e., the weight percentage based on the total amount of rubber, which is set to 100%.

[0014] Ranges specified in this disclosure are intended to include and disclose all values ​​between the endpoints of the range, as well as the endpoints, unless otherwise specified.

[0015] The term "substituted" is used to describe an organic compound in which at least one hydrogen atom has been replaced with a chemical entity other than hydrogen. This chemical entity is referred to interchangeably herein as a "substituent," "residue," or "radical." For example, the term "methyl group substituted with fluorine" or "fluorine-substituted methyl group" refers to a fluorinated methyl group and includes the group -CF 3 , -CHF 2 and -CH 2 The term "unsubstituted" is intended to refer to an organic compound or residue in which none of the hydrogen atoms have been replaced. For example, the term "unsubstituted methyl group" refers to methyl, i.e., -CH 3 Refers to...

[0016] Metal complexes Ligand Cyc The ligands designated "Cyc" are selected from cyclopentadienyl, indenyl and fluorenyl ligands. Cyc-ligands may be unsubstituted or they may be substituted, meaning that they contain one or more substituents.

[0017] Preferably, the substituents are, independently of one another, C 1~12 -Alkyl, C 6 ~C 12 aryl, and trialkylsilanes. 1 ~C 12 Examples of alkyl include, but are not limited to, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -C 4 H 9 (including isomers), -C6 H 13 (including isomers), or -C 10 H 21 (including isomers). 6 ~C 12 Examples of aryl include, but are not limited to, phenyl, biphenyl (including isomers), and phenyl containing one or more alkyl substituents having 1 to 6 carbon atoms.

[0018] In a preferred embodiment of the present disclosure, the ligand Cyc is selected from cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl and pentamethylcyclopentadienyl.

[0019] metal M The metal M of the metal complex of the present disclosure is a group 4 metal. For the purposes of this disclosure, the term "group 4 metal" refers to the conventional IUPAC nomenclature. Preferably, the metal M is selected from the group consisting of titanium, zirconium, and hafnium. In a particularly preferred embodiment of the present invention, the metal M is titanium. The oxidation state of the metal M may vary depending on whether the ligand Z is an anionic or neutral ligand, but the metal M is in such an oxidation state that the overall charge of the metal complex is neutral.

[0020] Ligand Z In a preferred embodiment, the ligand Z is anionic. Preferably, the ligand Z is -H, -F, -Cl, -Br, -I, -pseudohalogen, -C 1~12 -Alkyl, -OC 1~12 -Alkyl, -C(=O)C 1~12 -Alkyl, -acetylacetonate, C 1~12 Alkyl biscarboxylates, -phenyl, -O-phenyl; -Si(C 1~12 -alkyl) 3 , -Ge(C 1~12 -alkyl) 3 , -N(C 1~12 -alkyl) 2, -P(C 1~12 )-Alkyl) 2 , -SC 1~12 -alkyl, and combinations thereof; preferably -C 1~12 -alkyl, where these ligands are in their anionic form. Pseudohalogens are polyatomic analogs of halogens that are similar in chemical properties to true halogens and can be substituted for halogens in some types of chemical compounds. Suitable examples include, but are not limited to, -CN, -OCN, -SCN or -N 3 Examples include:

[0021] Preferably, the ligand Z is -CH 3 , -benzyl, -Si(CH 3 ) 3 , -CH 2 -Si(CH 3 ) 3 , -phenyl, -OC 1~12 -Alkyl, -N(C 1~12 -alkyl) 2 , -F, and -Si(C 1~12 -alkyl) 3 -phenyl substituted with 1, 2, 3, 4 or 5 substituents selected independently from the group consisting of, for example, methoxyphenyl, dimethoxyphenyl, N,N-dimethylaminophenyl, bis(N,N-dimethylamino)phenyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, perfluorophenyl, trimethylsilylphenyl, bis(trimethylsilyl)phenyl, tris(trimethylsilyl)phenyl; preferably, Z is -CH 3 It is.

[0022] In another embodiment of the present disclosure, the ligand Z is a neutral ligand and is selected from conjugated dienes. The diene ligand may be bonded to the metal M in either the s-trans configuration (π-bonded) or the s-cis configuration (either π-bonded or σ-bonded). Preferably, the conjugated diene contains 4 to 40 carbon atoms and may be optionally substituted one or more times with substituents independently selected from the group consisting of hydrocarbyl, silyl, halocarbyl, or combinations thereof. Examples of suitable neutral ligands include, but are not limited to, butadiene, isoprene, 1,3-pentadiene, 1,4-diphenyl-1,3-butadiene; 2,3-diphenyl-1,3-butadiene; 3-methyl-1,3-pentadiene; 1,4-dibenzyl-1,3-butadiene; 2,4-hexadiene; 2,4,5,7-tetramethyl-3,5-octadiene; 2,2,7,7-tetramethyl-3,5-octadiene; 1,4-ditolyl-1,3-butadiene; 1,4-bis(trimethylsilyl)-1,3-butadiene; and 2,3-dimethylbutadiene.

[0023] In a particularly preferred embodiment of the present disclosure, the index p is 2, such that the metal complex comprises two ligands Z, preferably both ligands Z being identical. In a particularly preferred embodiment of the present disclosure, each of the two ligands Z is a methyl anion.

[0024] In a preferred embodiment of the metal complex according to the present disclosure, the index p is 1 and the complex corresponds to the following general formula (IA) or (IB), or the index p is 2 and the metal complex according to the present disclosure corresponds to the following general formula (IC): [ka] wherein R6, R7, R8, R9 and R10 are each independently -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -C4 H 9 (including isomers), -C 6 H 13 (including isomers), -C 10 H 21 (including isomers), -phenyl, -biphenyl (including isomers), -Si(CH 3 ) 3 and mixtures thereof; preferably, -CH 3 In the compounds of general formula (IB), the ligand Z is bidentate. The bidentate ligand Z can be monoanionic (e.g. acetylacetonate) or dianionic (e.g. biscarboxylate such as oxalate). Preferably, Z in formulae (IA) and (IC) is -CH 3 , -benzyl, -Si(CH 3 ) 3 , -CH 2 -Si(CH 3 ) 3 , -phenyl; -OC 1~12 -Alkyl, -N(C 1~12 -alkyl) 2 , -F, and -Si(C 1~12 -alkyl) 3 and more preferably, Z is -CH 3 It is.

[0025] Preferably, the metal complexes of the present disclosure correspond to formula (IC):

[0026] Ligand L The ligand L is a sulfilimine type ligand and has the following formula (II): [ka] The sulfilimine type ligand is bonded via its N-atom to the metal M of the metal complex. The dotted line in formula (II) indicates that the metal M and the rest of the metal complex are not shown in formula (II).

[0027] The substituents Sub1 and Sub2 of the sulfilimine-type ligand L may be the same or different. Preferably, each of the substituents Sub1 and Sub2 of the ligand L comprises an aryl residue. Preferably, the aryl residue is directly bonded to the sulfur atom of the ligand. However, it is also possible that the aryl residue is -C 1~6 -Alkylene-, -OC 1~6 -Alkylene-, -C 1~6 -Alkylene-O- or -O-; for example -CH 2 Preferably, the aryl residue is selected from phenyl, -O-phenyl, pyridinyl, preferably phenyl, where the aryl residue is C 1 ~C 4 It may contain one or more substituents selected from alkyl and halogen, preferably F. Preferred embodiments of Sub1 and Sub2, independently of each other, include phenyl, methylphenyl, dimethylphenyl, ethylphenyl, isopropylphenyl, diisopropylphenyl, 2-pyridinyl, fluorophenyl and difluorophenyl.

[0028] In a preferred embodiment of the metal complex according to the present disclosure, the ligand L has the following general formula (III): [ka] wherein R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are each independently -H, -F, -Cl, -Br, -I, -C 1~12 -Alkyl, -C 1~12 -fluoroalkyl, -Si(C 1~12 -alkyl) 3 , -phenyl, -NH 2 , -NH(C1~12 -alkyl), -N(C 1~12 -alkyl) 2 , -C(=O)-NH 2 , -C(=O)-NH(C 1~12 -alkyl), -C(=O)-N(C 1~12 -alkyl) 2 , -OH, -OC 1~12 -Alkyl, -OC 1~12 -Fluoroalkyl, -SC 1~12 -Alkyl, -C(=O)C 1~12 -alkyl, and combinations thereof; preferably -H, -F, -Cl, -Br, -I or -C 1~12 -alkyl. Similar to formula (II), the dotted line in formula (III) indicates that the metal atom M and the remainder of the metal complex are not shown in formula (III).

[0029] In another preferred embodiment of the present disclosure, R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are each independently selected from -H, -F, -Cl, -Br, -I, -C 1~12 -Alkyl, for example -CH 3 , -CF 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -C 4 H 9 (including its isomers), -C 6 H 13 (including its isomers), -C 10 H 21 (including its isomers); phenyl or biphenyl (including its isomers), or -Si(C 1~12 -alkyl) 3 , for example, -Si(CH 3 ) 3and mixtures thereof. In one embodiment, at least two or three of R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are selected from H. In one embodiment, R1 and R2 are selected from H or CH 3 R1' and R2' represent H or F, and R3, R4, R5, R3', R4', R5' preferably represent H.

[0030] In a preferred embodiment of the present disclosure, - R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' represent H, methyl, ethyl, n-propyl, isopropyl, F, trifluoromethyl and combinations thereof, where at least two of R1, R2, R3, R4 and R5 represent H and at least two of R1', R2', R3', R4' and R5' represent H; - R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' represent H, methyl, ethyl, n-propyl, isopropyl, F, trifluoromethyl and combinations thereof, where at least three of R1, R2, R3, R4 and R5 represent H and at least three of R1', R2', R3', R4' and R5' represent H; R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' represent H, methyl, ethyl, n-propyl, isopropyl, F, trifluoromethyl, and combinations thereof, where either R1, R2, R3, R4, and R5 all represent H, or R1', R2', R3', R4', and R5' all represent H.

[0031] In another preferred embodiment of the present disclosure, - R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' represent H; R1 and R2 are CH 3 wherein R3, R4, R5, R1', R2', R3', R4', and R5' represent H; or R1 and R2 are CH 3wherein R1' and R2' represent F, and R3, R4, R5, R3', R4', and R5' represent H.

[0032] Specific examples of ligands L include, but are not limited to, S,S-diphenylsulfilimine, S-2,6-dimethylphenyl-S-phenylsulfilimine and S-2,6-dimethylphenyl-S-2,6-difluorophenylsulfilimine, S-2,6-diisopropyl-S-phenylsulfilimine, S-2,6-dimethylphenyl-S-2,6-dimethylphenylsulfilimine, S-2,6-dimethyl-S-2-pyridinyl.

[0033] In a preferred embodiment of the metal complex according to the present disclosure, the index p is 1 and the metal complex corresponds to the following general formula (ID) or the index p is 2 and the metal complex corresponds to the following general formula (IE). [ka] In the formula, The metal M is selected from the group consisting of titanium, zirconium, and hafnium; preferably titanium; Ligand Z is CH 3 , benzyl, Si(CH 3 ) 3 , C.H. 2 -Si(CH 3 ) 3 , Phenyl, O.C. 1~12 -Alkyl, N(C 1~12 -alkyl) 2 , F, and Si(C 1~12 -alkyl) 3 Phenyl substituted with 1, 2, 3, 4 or 5 substituents selected independently from the group consisting of, for example, methoxyphenyl, dimethoxyphenyl, N,N-dimethylaminophenyl, bis(N,N-dimethylamino)phenyl, fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, perfluorophenyl, trimethylsilylphenyl, bis(trimethylsilyl)phenyl, tris(trimethylsilyl)phenyl; preferably CH3 selected from the group consisting of; R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are each independently H, F, Cl, Br, I, CH 3 , C.H. 2 CH 3 , C.H. 2 CH 2 CH 3 , CH(CH 3 ) 2 , C 4 H 9 (including its isomers), C 6 H 13 (including its isomers), C 10 H 21 (including its isomers), phenyl, biphenyl (including its isomers), Si(CH 3 ) 3 , and mixtures thereof; preferably H, CH 3 or F; R6, R7, R8, R9, and R10 are each independently H, CH 3 , C.H. 2 CH 3 , C.H. 2 CH 2 CH 3 , CH(CH 3 ) 2 , C 4 H 9 (including its isomers), C 6 H 13 (including its isomers), C 10 H 21 (including its isomers), phenyl, biphenyl (including its isomers), Si(CH 3 ) 3 and mixtures thereof; preferably CH 3 is selected from the group consisting of:

[0034] In a preferred embodiment of the present disclosure, the index p is 2 and the metal complex corresponds to the general formula (IE) - M represents titanium; - Z represents a methyl anion; R1, R2, R1' and R2' are -H, -CH3 or -F, and R3, R4, R5, R3', R4', and R5' represent -H; R6, R7, R8, R9 and R10 are -CH 3 Represents.

[0035] In another preferred embodiment of the present disclosure, the index p is 2 and the metal complex corresponds to the general formula (IE), - M represents titanium; - Z is -CH 3 represents; - R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' represent H; R6, R7, R8, R9, and R10 are -CH 3 Represents.

[0036] In another preferred embodiment of the present disclosure, the index p is 2 and the metal complex corresponds to the general formula (IE), - M represents titanium; - Z is -CH 3 represents; R1 and R2 are -CH 3 R3, R4, R5, R1', R2' R3', R4', and R5' represent -H; R6, R7, R8, R9, and R10 are -CH 3 Represents.

[0037] In another preferred embodiment of the present disclosure, the index p is 2 and the metal complex corresponds to the general formula (IE), - M represents titanium; - Z is -CH 3 represents; R1 and R2 are -CH 3 wherein R1' and R2' represent -F, and R3, R4, R5, R3', R4', and R5' represent -H; R6, R7, R8, R9, and R10 are -CH 3 Represents.

[0038] Methods for preparing metal complexes Another aspect of the present disclosure is a process for the preparation of a metal complex of general formula (I) above, comprising: (a) General formula (IV): Cyc MZ p (IV) (In the formula, M is a Group 4 metal as defined above; Cyc is a cyclic ligand as defined above; Z is a ligand as defined above, preferably -CH 3 where the index p is an integer 2 or 3, preferably 3. providing a reagent of (b) General formula (V) [ka] (In the formula, Sub1 and Sub2 are defined as above; Q is H + , Li + , Na + , and K + ; preferably H + (selected from the group consisting of providing a sulfilimine-type ligand precursor represented by the formula: and (c) contacting the reagent of general formula (IV) prepared in step (a) with a sulfilimine-type ligand precursor represented by general formula (V), thereby obtaining a compound of general formula (I) and a by-product QZ.

[0039] In a preferred embodiment of the method according to the present disclosure, the sulfilimine type ligand precursor of general formula (V) can be the sulfilimine described above, in which case Q is H + In another preferred embodiment of the method according to the present disclosure, the sulfilimine-type ligand precursor can be a metal salt of the above sulfilimine, where the sulfilimine is typically deprotonated and Q represents a metal atom; preferred metal atoms include, but are not limited to, Li + , Na + , and K+ In yet another preferred embodiment of the method according to the present disclosure, the sulfilimine-type ligand precursor can be an acid adduct of the above sulfilimine, in which case Q is H + In these embodiments, the sulfilimine is typically further protonated with an acid, thereby giving it a positive charge and forming an adduct with the corresponding acid anion. Examples of suitable acid anions include, but are not limited to, F - , Cl - , Br - , I - , ClO 4 - , S.O. 4 2- , HSO 4 - , P.O. 4 3- , H.P.O. 4 2- , H 2 PO 4 - , CO 3 2- , HCO 3 - , aromatic or aliphatic carboxylates, BF4 - , (substituted) tetraphenylborates, fluorinated tetraarylborates, -C 1~12 -alkylsulfonates and -arylsulfonates.

[0040] Preferably, the sulfilimine type ligand precursor is selected from the sulfilimines defined above, their metal salts, and their acid adducts; preferably, sulfilimine. Preferably, the sulfilimine type ligand precursor is selected from the sulfilimines defined above and their acid adducts, preferably, sulfilimine. 4 , H 2 SO 4 , HSO 4 - , H 3 PO 4 , H 2 PO 4 - , H.P.O. 4 2- , H2 CO 3 , HCO 3 - , aromatic or aliphatic carboxylic acid, HBF 4 , (substituted) tetraphenylboronic acids, fluorinated tetraarylboronic acids, -C 1~12 -alkylsulfonic acids and -arylsulfonic acids. Preferably, the sulfilimine type ligand precursor is a sulfilimine and step (c) comprises adding at least one equivalent of a base to the reagent of formula (IV).

[0041] Preferably, the base is selected from the group consisting of amines, phosphanes, carboxylates, fluorides, hydroxides, cyanides, amides, organolithium compounds, and alkali metals.

[0042] In a preferred embodiment of the method according to the present disclosure, step (c) is carried out in a solvent, which may be any of aromatic and aliphatic hydrocarbons, halogenated hydrocarbons, amides of aliphatic carboxylic acids and primary or secondary amines, DMSO, nitromethane, acetone, acetonitrile, benzonitrile, ethers, polyethers, cyclic ethers, aromatic and aliphatic ethers, esters, pyridine, -C 1~12 - alkylpyridines, cyclic and primary or secondary amines, and mixtures thereof; preferably aromatic hydrocarbons.

[0043] In another aspect of the present disclosure, there is provided a compound of general formula (I) as above, obtainable by the method according to the present disclosure as above.

[0044] Process for Producing Ethylene-Containing Polymers Ethylene-containing polymers can be produced by using the metal complexes according to the present disclosure, which can be used alone or in combination with other polymerization catalysts, or optionally in combination with scavengers and activators or combinations thereof.

[0045] Thus, in another aspect of the present disclosure, there is provided a method for the preparation of a polymer, comprising: (a) providing a monomer composition; (b) polymerizing the monomer composition in the presence of a composition comprising a metal complex of the present disclosure to produce a polymer.

[0046] The method may further include, optionally, providing at least one scavenger and / or, optionally, providing at least one activator. The activator and scavenger may be components of the catalyst composition comprising the metal complex of the present disclosure, or they may be provided separately, for example, as separate feed streams.

[0047] Polymers having broad or narrow molecular weight distribution (Mw / Mn) can be produced. In one embodiment, polymers having a molecular weight distribution (Mw / Mn) of 1.80-30 or 2-10 can be produced.

[0048] Polymers with high or low Mooney viscosities can be produced. In one embodiment, the polymer produced by the present method has a Mooney viscosity ML1+4 of at least 40 at 125° C. and a Mooney viscosity ML1+8 of 100 or less at 150° C. In one embodiment of the present disclosure, the polymer has a Mooney viscosity ML1+4 of about 40 to about 100 at 125° C. In another embodiment of the present disclosure, the polymer has a Mooney viscosity ML1+8 of about 50 to about 100 at 150° C.

[0049] High or low weight average molecular weight (Mw) polymers can be produced by the methods of the present disclosure, hi one embodiment, the polymer has an (Mw) of at least greater than 200,000 g / mol, for example, from about 200,000 g / mol to about 600,000 g / mol.

[0050] Polymers with high or low number average molecular weight (Mn) can be produced, hi one embodiment, the polymers produced by the method according to the present disclosure have an Mn of 40,000 g / mol to 250,000 g / mol.

[0051] Branched or linear polymers may be produced using the method according to the present disclosure. The branching level of the branched polymer may be high, medium or low. The polymer branching level may be characterized by the parameter Δδ. Δδ, expressed in degrees, is the difference between the phase angle δ at a frequency of 0.1 rad / sec and the phase angle δ at a frequency of 100 rad / sec, as measured by Dynamic Mechanical Spectroscopy (DMS) at 125° C. and 10% strain. This quantity Δδ is a measure of the amount of long chain branching structure present in the polymer and is introduced in HC Booij, Kautschuk+Gummi Kunststoffe, Vol. 44, No. 2, pages 128-130, which is incorporated herein by reference. In one embodiment of the present disclosure, polymers with Δδ between 2 and 50 may be produced.

[0052] The polymers produced by the method according to the present disclosure may be monomodal, or they may be bimodal or multimodal. The polymers may have a molecular weight distribution characterized by two peaks or one peak and one shoulder in the case of bimodal polymers, or three or more peaks or two shoulders in the case of multimodal polymers, in a diagram obtained by gel permeation chromatography (GPC). Reactor blends may also be produced, which means that the polymers are produced in at least two different reaction vessels and combined by mixing, typically wet mixing, i.e., by mixing the reaction mixture. Block or graft polymers may also be produced.

[0053] Ethylene-containing polymers: The polymers that can be produced by using the metal complexes according to the present disclosure contain units derived from ethylene, and the monomer composition provided in the method according to the present disclosure contains at least ethylene. Preferably, the polymers produced by the method according to the present disclosure are ethylene-copolymers, more preferably ethylene / α-olefin copolymers.

[0054] Ethylene / α-olefin polymers: In one embodiment of the present disclosure, the polymer produced using the metal complex according to the present disclosure is an ethylene / α-olefin polymer. The ethylene / α-olefin polymer is a copolymer of ethylene and another α-olefin and, optionally, one or more additional comonomers. Ethylene / α-olefin polymers can be produced that contain at least 20% by weight (based on the total weight of the polymer) of units derived from ethylene and may contain up to 80 weight percent (wt%) of units derived from ethylene. In one embodiment, the ethylene-α-olefin copolymer of the present disclosure contains 40-70% by weight, preferably 44-65% by weight, of units derived from ethylene. The weight percentage is based on the total weight of the copolymer.

[0055] In addition to units derived from ethylene, polymers according to the present disclosure may contain units derived from one or more other α-olefins.

[0056] Alpha-Olefins: An α-olefin is an olefin that has a single aliphatic carbon-carbon double bond. The double bond is located at the terminal (α-position) of the olefin. α-olefins can be aromatic or aliphatic, linear, branched, or cyclic. Typically, α-olefins have from 3 to 20 carbon atoms.

[0057] As the α-olefin, there is mentioned the formula: 2 C=X-CH 3 where X represents an aliphatic alkylene residue having 1 to 17 carbon atoms, which may be linear or branched. Preferably, the branches, independently of one another, contain 1 to 3 carbon atoms.

[0058] In a preferred embodiment, the α-olefin is a compound represented by the formula: 2 C=CH-(CH 2 ) n -CH 3 where n=1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, and 17.

[0059] Preferred examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene.

[0060] One or more α-olefins may be used in combination. Preferably, the polymer contains at least 5 wt. % or at least 10 wt. % of units derived from one or more α-olefins. Polymers containing up to 57 wt. % and more preferably up to 55 wt. % of units derived from one or more α-olefins (weight percentages (wt. %) based on the total weight of the polymer) may be produced. Preferably, ethylene-α-olefin copolymers contain 17-57 wt. % of total units derived from one or more α-olefins. Preferably, the polymer contains propylene.

[0061] Non-conjugated dienes: Ethylene / α-olefin polymers can be produced that, in addition to ethylene and an α-olefin, further contain units derived from one or more non-conjugated dienes as comonomers.

[0062] A non-conjugated diene is a polyene containing at least two carbon-carbon double bonds, which are non-conjugated and may be in a chain, a ring, a ring system or a combination thereof. The carbon-carbon double bonds are separated by at least two carbon atoms. The polyene may have endocyclic and / or exocyclic double bonds and may have no substituents, the same or different substituents. Preferably, the non-conjugated diene is aliphatic, more preferably aliphatic and alicyclic. Suitable non-conjugated dienes include, for example, aromatic polyenes, aliphatic polyenes and alicyclic polyenes, preferably polyenes having 6 to 30 carbon atoms (C 6 ~C 30 -polyenes, more preferably C 6 ~C 30Specific examples of non-conjugated dienes include, but are not limited to, 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 1,6-octadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4- Octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 1,6-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1, 4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene , 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 1,5,9-decatriene, 6-methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene, and mixtures thereof. Preferred non-conjugated dienes include alicyclic polyenes. The alicyclic dienes have at least one cyclic unit. In a preferred embodiment, the non-conjugated diene is selected from polyenes having at least one endocyclic double bond and optionally at least one exocyclic double bond. Preferred examples include dicyclopentadiene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene (ENB), with ENB being particularly preferred. In one embodiment, the copolymer of the present disclosure contains only ENB as the non-conjugated diene.

[0063] Further examples of non-conjugated dienes include dipolymerizable dienes. Dipolymerizable dienes include α-ω dienes, preferably linear α-ω dienes, vinyl-substituted monocyclic and bicyclic non-conjugated dienes, which may be aliphatic or aromatic. Dipolymerizable dienes may cause or contribute to the formation of polymer branches. Examples of aliphatic dipolymerizable dienes include, but are not limited to, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclo-hexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenyl-cyclohexane, 1-isopropenyl-4-vinylcyclohexane and 1-isopropenyl-3-vinylcyclopentane, dicyclopentadiene (DCPD) and 1,4-cyclohexadiene. Non-conjugated vinylnorbornene and C 8 ~C 12 Alpha-omega linear dienes (e.g., 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene) are preferred. The dipolymerizable dienes may be further substituted with at least one group containing a heteroatom of Groups 13-17, such as O, S, N, P, Cl, F, I, Br, or combinations thereof.

[0064] Examples of aromatic non-conjugated polyenes include vinylbenzene (including its isomers) and vinyl-isopropenylbenzene (including its isomers).

[0065] In a preferred embodiment of the present disclosure, the dipolymerizable diene is selected from dicyclopentadiene (DCPD), 5-vinyl-2-norbornene (VNB), 1,7-octadiene, and 1,9-decadiene, with 5-vinyl-2-norbornene (VNB) being most preferred.

[0066] In an exemplary embodiment of the present disclosure, ethylene / α-olefin copolymers containing at least 3 wt.% and up to and including 15 wt.% units derived from one or more non-conjugated dienes may be produced.

[0067] In another embodiment of the present disclosure, a polymer containing a non-conjugated diene selected from 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), 1,7-octadiene or 1,9-decadiene, dicyclopentadiene (DCPD) or a combination thereof is produced. Preferably, the copolymer of the present disclosure contains 0.05% to 5% by weight, more preferably 0.10% to 3% by weight or 0.15% to 1.2% by weight of units derived from VNB (all weight percentages based on the total weight of the ethylene-α-olefin-copolymer). In another embodiment, ethylene / α-olefin copolymers containing units derived from 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene may be produced, for example, the ethylene / α-olefin copolymers produced may contain 2-15 wt. % of units derived from ENB and 0.05-4 wt. % of units derived from VNB.

[0068] Ethylene / α-olefin copolymers, which may or may not contain units derived from other comonomers, may be produced by the process according to the present disclosure. The sum of units derived from ethylene, α-olefin and, optionally, non-conjugated dienes may be greater than 90% by weight, greater than 99% by weight (including 100% by weight), based on the total weight of the ethylene / α-olefin polymer.

[0069] Chain transfer agent: The polymerization may include the use of one or more chain transfer agents to control the molecular weight of the polymer. A preferred chain transfer agent is hydrogen (H 2 Other chain transfer agents include, but are not limited to, ethane, diethyl zinc, and combinations thereof.

[0070] Activator: One or more activators, also referred to interchangeably herein as "cocatalysts", may be used in the polymerization. Cocatalysts are also referred to in the art as "activators". The presence of a cocatalyst typically increases the rate at which the catalyst polymerizes olefins. The cocatalyst may also affect the molecular weight, branching, comonomer content, or other properties of the polymer. The cocatalyst is typically introduced into the reactor separately from the catalyst or together with the catalyst, i.e., the metal complex.

[0071] Exemplary cocatalysts include, but are not limited to, boron-containing activators. In a preferred embodiment, the activator (b) is selected from a borane (C1) or a borate (C2 or C3).

[0072] Suitable boron activators (C1) are represented by the general formula BQ 1 Q 2 Q 3 It can be represented by:

[0073] Suitable borate activators represented by (C2) have the general formula G(BQ 1 Q 2 Q 3 Q 4 )

[0074] Suitable borate activators represented by (C3) are of the general formula (JH)(BQ 1 Q 2 Q 3 Q 4 ) In the activator represented by (C1), B is boron and Q 1 ~Q 3 is a substituted or unsubstituted aryl group, preferably a phenyl group. Suitable substituents include, but are not limited to, halogen, preferably fluoride, and C 1 ~C 40 Hydrocarbyl, preferably C 1 ~C 20 Specific examples of the activator represented by (C1) include tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, and phenyl-bis(pentafluorophenyl)borane.

[0075] In the activator represented by (C2), G is an inorganic or organic cation, B is boron, and Q 1 ~Q 3 is the same as in (C1), and Q 4 The aryl group may be a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl. Substituents include, but are not limited to, halogen, preferably fluoride, and C 1 ~C 40 Hydrocarbyl, preferably C 1 ~C 20 Alkyl or aromatic. Borate group (BQ 1 Q 2 Q 3 Q 4Specific examples of G include, but are not limited to, tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(2,3,4-trifluorophenyl)borate, phenyltris(pentafluoro-phenyl)borate, and tetrakis(3,5-bistrifluoromethylphenyl)borate. Specific examples of G include ferrocenium cation, alkyl-substituted ferrocenium cation, and silver cation. Specific examples of organic cation G include triphenylmethyl cation. G is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation.

[0076] In the activator represented by (C3), J represents a neutral Lewis base, (JH) represents a Bronsted acid, B is boron, and Q 1 ~Q 4 and borate groups (BQ 1 Q 2 Q 3 Q 4) are the same as in (C2). Specific examples of Bronsted acids (JH) include trialkyl-substituted ammonium, N,N-dialkylanilinium, dialkylammonium, and triarylphosphonium. Specific examples of activators represented by (C3) include, but are not limited to, triethylammonium tetrakis(pentafluoro-phenyl)-borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium-tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-bistrifluoromethyl-phenyl)borate, N,N-dimethyl-anilinium tetrakis(pentafluoro-phenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethionyl ... Examples of suitable tetrakis(pentafluorophenyl)borate include N,N-dimethylanilinium-tetrakis(3,5-bistrifluoromethyl-phenyl)borate, diisopropyl-ammonium tetrakis(pentafluorophenyl)borate, dicyclohexyl-ammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, and tri(dimethylphenyl)-phosphonium-tetrakis(pentafluorophenyl)borate.

[0077] Other examples of cocatalysts include aluminum alkyls, including but not limited to trialkylaluminum, trimethylaluminum, triethylaluminum, tri-isobutylaluminum, or tri-n-octylaluminum. Other examples include alkylaluminum halides, including but not limited to diethylaluminum chloride, dimethylaluminum chloride, ethylaluminum sesquichloride. Further examples include but are not limited to alumoxanes, including methylalumoxane (MAO), tetraisobutylalumoxane (TIBAO), and hexaisobutylalumoxane (HIBAO).

[0078] Scavenger: Impurities can adversely affect catalysts by reducing their activity. Compounds that react with such impurities and convert them into compounds that are harmless to catalytic activity are called scavengers by those skilled in the art of polymerization. Scavenger can be used in the method according to the present disclosure. Examples of scavengers include, but are not limited to, alkylaluminum compounds such as trimethylaluminum, triethylaluminum, tri-isobutylaluminum, and trioctylaluminum. Scavenger can also act as a cocatalyst. In this case, the scavenger is generally applied in excess of that required to fully activate the catalyst.

[0079] In one embodiment of the process according to the present invention, the molar ratio of activator provided in step (c) of the process to the metal complex according to the present disclosure is from 10:1 to 1:1, preferably 2:1, preferably 1:2.

[0080] The scavenger, preferably an aluminum-containing scavenger, may be used in combination with a sterically hindered hydrocarbon or heterohydrocarbon, preferably a sterically hindered phenol containing a group 15 or 16 heteroatom (preferably O, N, P and S atoms, more preferably O and N heteroatoms). Specific examples of sterically hindered hydrocarbons include, but are not limited to, tert-butanol, iso-propanol, triphenylcarbinol, 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 2,6-di-tert-butylaniline, 4-methyl-2,6-di-tert-butylaniline, 4-ethyl-2,6-di-tert-butylaniline, diisopropylamine, di-tert-butylamine, diphenylamine, etc. A preferred sterically hindered compound is 4-methyl-2,6-tert-butylphenol.

[0081] In the method of producing a polymer according to the present disclosure, a monomer composition is contacted with at least one metal complex according to the present disclosure. The contacting can be carried out in the gas phase. The contacting can also be carried out in the presence of one or more solvents, for example in a solution or slurry. The polymerization can be carried out in a solution or slurry under sufficient pressure and temperature so that a gas phase is not formed. Preferably, the polymerization is carried out as a solution or slurry polymerization. Preferred solvents include one or more hydrocarbon solvents. Suitable solvents include C 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 150, 1000, 15 ... 5~12 Hydrocarbons are included.

[0082] The process may be carried out at reaction temperatures and pressures as are known in the art for the polymerization of such polymers. In a preferred embodiment of the present disclosure, the metal complexes according to the present disclosure have catalytic polymerization activity at temperatures as high as 130° C. and pressures of at least 8.3 bar.

[0083] In another aspect of the disclosure, there is provided a polymer obtainable by the process according to the invention as described above. In one embodiment, the polymer is an ethylene propylene rubber (EPM) or an ethylene propylene diene monomer rubber (EPDM).

[0084] Other Aspects of the Disclosure Another aspect of the present disclosure relates to the use of a metal complex according to the present disclosure as a polymerization catalyst for polymerizing a monomer composition as defined above.

[0085] In another aspect of the present disclosure, a supported catalyst is provided, comprising a metal complex according to the present disclosure on a support material. The supported catalyst may optionally further contain a scavenger or an activator or a combination of a scavenger and an activator. The support material may be a solid material with a high surface area, to which at least one metal complex according to the present disclosure is fixed. Typically, the activity of a heterogeneous catalyst occurs at the surface atoms. As a result, great efforts are made to maximize the surface area of ​​the catalyst. One suitable method for increasing the surface area includes distributing the catalyst over the support material. The support material may be inert or may participate in the catalytic reaction. Preferably, the support material is silica, magnesium halide, e.g., MgF 2 , MgCl 2 , MgBr 2 , MgI 2 , zeolites, alumina, polystyrene, polypropylene, polyethylene, polyamide, polyester and combinations thereof. EXAMPLES

[0086] The following examples further illustrate the present disclosure, without intending to limit the disclosure to these examples.

[0087] General Operating Steps: All experiments for the preparation of half-metallocene compounds were carried out under an atmosphere of argon or nitrogen using standard Schlenk line or dry box techniques. Solvents were degassed by sparging with nitrogen and dried by passing through a column of an appropriate drying agent.

[0088] The deuterated solvent was CaH 2 The NMR samples were prepared under nitrogen in 5 mm 507-PP tubes from SP Wilmad-LabGlass equipped with J. Young PTFE valves. 1 H, 19 F and 13 C-{ 1H} spectra were recorded at ambient temperature and the residual protic solvent ( 1 H) or solvent ( 13 C) Resonances are internally referenced and reported relative to tetramethylsilane (d=0 ppm). Chemical shifts are given in δ (ppm) and coupling constants are given in Hz. NMR spectra were recorded on a Bruker Avance 400 spectrometer.

[0089] The composition of the copolymer was determined using Fourier transform infrared spectroscopy (FT-IR) according to methods known in the art. FT-IR measurements show the composition of various monomers in weight percent relative to the total composition. The composition was determined using mid-range FT-IR spectroscopy.

[0090] Catalyst synthesis: Different half-metallocene metal complex catalysts (compounds 1-3, "cpds 1-3") were prepared with different sulfilimine-type ligands as follows:

[0091] (Pentamethylcyclopentadienyl)[S,S-diphenylsulfide]titaniumamine dimethyl (Cpd 1) [ka] S,S-diphenylsulfilimine (30.0 mg, 149.0 μmol) and Cp * TiMe 3 (34.0 mg, 149.0 μmol) was added to C 6 D 6 (1 mL) 1 H NMR was performed and complete conversion to the desired product was observed. 1 H NMR (300 MHz, C 6 D 6 )δ 7.90-7.77(m,4H, meta-ArH), 7.08-6.94(m,4H, ortho-ArH), 6.93-6.83(m,2H, para-ArH), 1.97(s,15H, CpCH 3 ), 0.69(s,6H,TiCH3 ). For the polymerization reaction, a solution of 5.0 mg (25 μmol) of the ligand in 1 ml of toluene was added to CpTiMe in 1 ml of toluene. 3 (5.7 mg, 25 μmol) was added to a solution of 100 mL of toluene and diluted to a total volume of 25 mL and used in a batch reactor.

[0092] (Pentamethylcyclopentadienyl)[S-2,6-dimethylphenyl-S-phenylsulfide]titaniumamine dimethyl (Cpd 2) [ka] S-2,6-dimethylphenyl-S-phenylsulfilimine (10.0 mg, 43.6 μmol) and Cp * TiMe 3 (10.0 mg, 43.6 μmol) was added to C 6 D 6 (1 mL) 1 H NMR was performed and complete conversion to the desired product was observed. 1 H NMR (300 MHz, C 6 D 6 )δ 7.82-7.74(m,2H, meta-ArH), 7.04(tt,J=6.9, 0.9Hz, 2H, ortho-ArH), 6.98-6.90(m,1H, para-A rH), 6.89-6.80(m,1H, para-ArMe2H), 6.70(dq,J=7.5, 0.7Hz, 2H, meta-ArMe2H), 2.54(s,6H, CH 3 ), 1.97(s,15H,CpCH 3 ), 0.67(d,J=0.8Hz, 3H, TiCH 3 ), 0.54(d,J=0.8Hz, 3H, TiCH 3 ). For the polymerization reaction, a solution of 5.7 mg (25 μmol) of the ligand in 1 ml of toluene was added to CpTiMe 3(5.7 mg, 25 μmol) was added to a solution of 100 mL of toluene and diluted to a total volume of 25 mL and used in a batch reactor.

[0093] (Pentamethylcyclopentadienyl)[S-2,6-dimethylphenyl-S-2,6-difluorophenylsulfide]titaniumamine dimethyl (Cpd 3) [ka] S-2,6-dimethylphenyl-S-2,6-difluorophenylsulfilimine (6.6 mg, 25 μmol) and Cp * TiMe 3 (5.7 mg, 25 μmol) was added to C 6 D 6 Dissolve in 1 H and 19 F NMR was performed and complete conversion to the desired product was observed. 1 H NMR (300 MHz, C 6 D 6 ):δ 6.89-6.82(m,1H, para-ArMe2H), 6.74(dtd,J=7.2, 1.2, 0.6Hz, 2H, meta-ArMe2H), 6.4 6-6.35(m,1H, para-ArF2H), 6.30-6.20(m,2H, meta-ArF2H), 2.83(d,J=0.8Hz, 6H, ArCH 3 ), 1.97(s,15H,CpCH 3 ), 0.54(d,J=0.6Hz, 3H, TiCH 3 ), 0.51(q,J=0.6Hz, 3H, TiCH 3 ). 19 F NMR (282 MHz, C 6 D 6 ):δ-110.93. For the polymerization reaction, a solution of 6.6 mg (25 mmol) of the ligand in 1 ml of toluene was added to CpTiMe in 1 ml of toluene. 3(5.7 mg, 25 μmol) was added to a solution of the half-metallocene complex. The resulting solution containing the half-metallocene complex was diluted with toluene to a total volume of 25 mL and used in a batch reactor.

[0094] Laboratory-scale quantities of sulfilimine-type ligands bearing substituted aryl moieties were prepared by reacting diaryl sulfide precursors with mesitylsulfonylhydroxylamine and treating with anion exchange resin (AMBERLITE IRA-402 ion exchange resin in the OH form, ethanol as eluent). Mesitylsulfonylhydroxylamine is prone to self-decomposition and must be handled with great care, so it was prepared in situ (prepared from O-mesitylsulfonylhydroxylamine in dimethylformamide in the presence of triethylamine at 0°C). Diaryl sulfide precursors were prepared as reported by Cheng et al. (Journal of Organic Chemistry 2012,77,10369) and Clayden et al. (Angew.Chem.Int.Ed.2009,48,6270).

[0095] The unsubstituted diarylsulfilimine ligand was synthesized by the reaction of CaH 2 (1g) was prepared by stirring S,S-diphenylsulfilimine monohydride (500 mg, 2.28 mmol) in toluene (30 mL). S,S-diphenylsulfilimine monohydride is commercially available, for example, from Sigma-Aldrich. The reaction mixture was filtered and the residue was washed with toluene (3×5 mL) and dried under reduced pressure.

[0096] polymerization: Polymer composition: Fourier transform infrared spectroscopy (FT-IR) can be used to determine the composition of the copolymer according to ASTM D3900 (revised 2017) for the C2 / C3 ratio and D6047 (revised 2017) for the diene content of pressed polymer films.

[0097] Phase angle measurement: Polymer branching can be determined by phase angle measurements in a Montech MDR 3000 moving die rheometer using the parameter Δδ. Δδ (expressed in degrees) is the difference between the phase angle δ measured at a frequency of 0.1 rad / s and the phase angle δ measured at a frequency of 100 rad / s, as determined by dynamic mechanical analysis (DMA) at 125° C. Δδ is a measure of the presence of long chain branching in the polymer structure and is introduced by HC Booij, in Kautschuk+Gummi Kunststoffe, Vol. 44, No. 2, pages 128-130, 1991, which is incorporated herein by reference. The lower the value of Δδ, the more long chain branching is present in the polymer.

[0098] Molecular weight: Molecular weights (Mw, Mn, Mz) and molecular weight distributions (MWD) can be determined by gel permeation size-exclusion chromatography (GPC) using a Polymer Char GPC-IR from Polymer Characterization SA (Valencia, Spain). The size-exclusion chromatograph is equipped with an online viscometer (Polymer Char V-400 viscometer), an online infrared detector (IR5 MCT), with three AGILENT PL OLEXIS columns (7.5 x 300 mm) and a Polymer Char autosampler. Universal calibration of the system is performed using polyethylene (PE) standards.

[0099] Polymer samples are weighed into the vials of a Polymer Char autosampler (with a concentration range of 0.3-1.3 mg / ml). In the autosampler, the vials are automatically filled with the solvent (1,2,4-trichlorobenzene stabilized with 1 g / l di-tertbutyl-paracresol (DBPC)). The samples are placed in a high temperature oven (160°C) for 4 hours. After this dissolution time, the samples are automatically filtered by an in-line filter before being injected into the column. The chromatographic system is operated at 160°C. The flow rate of the 1,2,4-trichlorobenzene eluent is 1.0 mL / min.

[0100] Mooney Viscosity: The Mooney viscosity of the copolymer samples can be measured using biaxially strained PP (20 μm thick) films provided by Perfon BV (Goor, The Netherlands) in accordance with ISO 289, revised 2015. The measurement conditions are typically ML(1+4) at 125° C.

[0101] Example 1 (EPM Polymer): Batch copolymerization was carried out in a 2-liter batch autoclave equipped with dual impellers and baffles. The reaction temperature was controlled by a LAUDA Thermostat. The feed streams (solvent and monomers) were purified by contacting with various adsorption media to remove catalyst killing impurities such as water, oxygen and polar compounds, as known to those skilled in the art. During polymerization, ethylene and propylene monomers were continuously fed to the gas cap of the reactor. The reactor pressure was kept constant by a back pressure valve.

[0102] In an inert atmosphere of nitrogen, the reactor was charged with pentamethylheptane (PMH) (950 mL), triisobutylaluminum (TiBA), and 2,6-di-tert-butyl-4-methylphenol (BHT). The reactor was heated to the desired temperature with stirring at 1350 rpm. The reactor was pressurized and adjusted under the determined ratio of ethylene and propylene. After 10 min, the catalyst components and, if applicable, the borate cocatalyst were added into the reactor (0.02-0.14 μmol depending on the catalyst productivity), followed by rinsing the catalyst vessel with PMH (50 mL). After 10 min of polymerization, the monomer flow was stopped and the solution was carefully placed into a 2 L Erlenmeyer flask containing a solution of IRGANOX-1076 in isopropanol and dried overnight at 100 °C under reduced pressure. The polymer was analyzed for molecular weight (SEC-IR) and composition (FT-IR).

[0103] Examples 1a-1d were carried out using Cpd 1 as the catalyst.

[0104] Examples 1e-1h were carried out using Cpd 2 as the catalyst.

[0105] Examples 1i-1l were carried out using Cpd 3 as the catalyst.

[0106] EPM polymers with high weight average molecular weight (Mw) were obtained. The results and polymerization details are summarized in Table 1.

[0107] [Table 1]

[0108] Example 2 (EPDM polymer): General steps: The procedure for EPM polymerization in Example 1 was followed, except that the reactor was charged with pentamethylheptane (PMH) (950 mL), triisobutylaluminum (TiBA), 2,6-di-tert-butyl-4-methylphenol (BHT), 5-ethylidene-2-norbornene (ENB), and 5-vinyl-2-norbornene (VNB) in an inert atmosphere. Additionally, hydrogen (0.35 NL / h) was fed to the pressurized reactor.

[0109] Example 2.1 was carried out using Cpd 1.

[0110] Example 2.2 was carried out using Cpd 2.

[0111] Example 2.3 was carried out using Cpd 3.

[0112] EPDM polymers with high weight average molecular weight (Mw), greater than 200,000 g / mol, were obtained. The results and polymerization details are summarized in Table 2.

[0113] [Table 2]

Claims

1. General formula (I): Cyc L M Z ｐ (I) (In the formula, M is a metal selected from the group consisting of titanium, zirconium, and hafnium; Cyc is a cyclic ligand selected from cyclopentadienyl, indenyl, and fluorenyl, and may bear one or more substituents; Z is independently selected from neutral or anionic ligands bound to said metal M, wherein said neutral ligands are selected from conjugated dienes having from 4 to 40 carbon atoms, optionally substituted one or more times with a substituent selected from the group consisting of hydrocarbyl, silyl, halocarbyl, and combinations thereof, and said anionic ligands are selected from -H, -F, -Cl, -Br, I, -pseudohalogen, -C １～１２ -alkyl, -O-C １～１２ -Alkyl, -C(=O)C １～１２ -Alkyl, -acetylacetonate, C １～１２ Alkyl biscarboxylates, -phenyl, -O-phenyl, -Si(C １～１２ -alkyl) ３ , -Ge(C １～１２ -alkyl) ３ , -N(C １～１２ -alkyl) ２ , -P(C １～１２ )-alkyl) ２ , -S-C １～１２ - the anionic form of alkyl, and combinations thereof; preferably -C １～１２ -Alkyl, -benzyl, -Si(CH ３ ) ３ , -CH ２ -Si(CH ３ ) ３ , -phenyl, O-phenyl; １～１２ Alkyl, —O—C １～１２ -Alkyl, -N(C １～１２ -alkyl) ２ , -F, -Cl, -Br, -I, -pseudohalogen, and -Si(C １～１２ -alkyl) ３ a ligand selected from the group consisting of -phenyl and -O-phenyl substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of The index p is either 1 or 2, preferably 2; and L is a group represented by the general formula (II): 【Chemistry 1】 wherein Sub1 and Sub2 are aromatic residues which are, independently of each other, unsubstituted or may have at least one substituent. Metal complexes of.

2. The ligand L is represented by the following general formula (III): 【Chemistry 2】 wherein R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are each independently H, F, Cl, Br, I, -C １～１２ -alkyl, -C １～１２ -fluoroalkyl, -Si(C １～１２ -alkyl) ３ , -phenyl, -NH ２ , -NH(C １～１２ -alkyl), -N(C １～１２ -alkyl) ２ , -C(=O)-NH ２ , -C(=O)-NH(C １～１２ -alkyl), -C(=O)-N(C １～１２ -alkyl) ２ , —OH, —O—C １～１２ -alkyl, -O-C １～１２ -fluoroalkyl, -S-C １～１２ -alkyl, and -C(=O)C １～１２ 2. The metal complex of claim 1, wherein the metal complex is selected from the group consisting of: -alkyl.

3. The ligand L is represented by the following general formula (III): 【Chemistry 3】 wherein R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are each independently -H, -F, -Cl, -Br, -I, -CF ３ , -CH ３ , -CH ２ CH ３ , -CH ２ CH ２ CH ３ , -CH(CH ３ ) ２ , -C ４ H ９ (including its isomers), -C ６ H １３ (including its isomers), -C １０ H ２１ (including its isomers); phenyl, and -Si(CH ３ ) ３ 2. The metal complex of claim 1, wherein at least two or at least three of R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' are selected from -H.

4. The ligand L is represented by the following general formula (III): 【Chemistry 4】 where: R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' represent residues selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, trifluoromethyl and combinations thereof, where at least two of R1, R2, R3, R4 and R5 represent H and at least two of R1', R2', R3', R4' and R5' represent hydrogen; R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' represent residues selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, trifluoromethyl and combinations thereof, where at least three of R1, R2, R3, R4 and R5 represent hydrogen and at least three of R1', R2', R3', R4' and R5' represent hydrogen; 2. A metal complex according to claim 1, wherein R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' represent residues selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, trifluoromethyl and combinations thereof, wherein either R1, R2, R3, R4 and R5 all represent hydrogen or R1', R2', R3', R4' and R5' all represent hydrogen.

5. The index p is 1 and the complex corresponds to the following general formula (IA) or (IB), or the index p is 2 and the metal complex corresponds to the following general formula (IC): 【Chemistry 5】 where R6, R7, R8, R9, and R10 are -H, -CH ３ , -CH ２ CH ３ , -CH ２ CH ２ CH ３ , -CH(CH ３ ) ２ , -C ４ H ９ (including its isomers), -C ６ H １３ (including its isomers), -C １０ H ２１ (including its isomers), -phenyl, -biphenyl (including its isomers), -Si(CH ３ ) ３ 2. The metal complex of claim 1, wherein each of said metal complexes is independently selected from the group consisting of:

6. The index p is 1 and the complex is represented by the following general formula (ID), or the index p is 2 and the complex is represented by the following general formula (IE): 【Chemistry 6】 in which in each case: The ligand Z is -CH ３ , -benzyl, -Si(CH ３ ) ３ , -CH ２ -Si(CH ３ ) ３ , -phenyl, -O-phenyl; １～１２ -Alkyl, -N(C １～１２ -alkyl) ２ , F, Cl, and -Si(C １～１２ -alkyl) ３ -phenyl and -O-phenyl substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of: R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are each independently H, F, Cl, Br, I, -C １～１２ -alkyl, -C １～１２ -fluoroalkyl, -Si(C １～１２ -alkyl) ３ , -phenyl, -NH ２ , -NH(C １～１２ -alkyl), -N(C １～１２ -alkyl) ２ , -C(=O)-NH ２ , -C(=O)-NH(C １～１２ -alkyl), -C(=O)-N(C １～１２ -alkyl) ２ , —OH, —O—C １～１２ -alkyl, -O-C １～１２ -fluoroalkyl, -S-C １～１２ -Alkyl and -C(=O)C １～１２ - alkyl; R6, R7, R8, R9, and R10 are -H, -CH ３ , -CH ２ CH ３ , -CH ２ CH ２ CH ３ , -CH(CH ３ ) ２ , -C ４ H ９ (including its isomers), -C ６ H １３ (including its isomers), -C １０ H ２１ (including its isomers), -phenyl, -biphenyl (including its isomers), and -Si(CH ３ ) ３ 2. The metal complex of claim 1, wherein each of said metal complexes is independently selected from the group consisting of:

7. The index p is 2, and the metal complex is represented by the following general formula (IE): 【Chemistry 7】 where each Z is independently -CH ３ , -benzyl, -Si(CH ３ ) ３ , -CH ２ -Si(CH ３ ) ３ , -phenyl, -O-phenyl; １～１２ -Alkyl, -N(C １～１２ -alkyl) ２ , -F, -Cl, and -Si(C １～１２ -alkyl) ３ -phenyl and -O-phenyl substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of: R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are each independently H, F, Cl, Br, I, -C １～１２ -alkyl, -C １～１２ -fluoroalkyl, -Si(C １～１２ -alkyl) ３ , -phenyl, -NH ２ , -NH(C １～１２ -alkyl), -N(C １～１２ -alkyl) ２ , -C(=O)-NH ２ , -C(=O)-NH(C １～１２ -alkyl), -C(=O)-N(C １～１２ -alkyl) ２ , —OH, —O—C １～１２ -alkyl, -O-C １～１２ -fluoroalkyl, -S-C １～１２ -Alkyl and -C(=O)C １～１２ -alkyl, R6, R7, R8, R9, and R10 are each independently -H and -CH ３ 2. The metal complex according to claim 1, wherein the metal complex is selected from the group consisting of

8. The index p is 2, and the metal complex is represented by the following general formula (IE): 【Chemistry 8】 where each Z is independently -CH ３ , -benzyl, -Si(CH ３ ) ３ , -CH ２ -Si(CH ３ ) ３ , -phenyl, -O-phenyl; １～１２ -Alkyl, -N(C １～１２ -alkyl) ２ , -F, -Cl, and -Si(C １～１２ -alkyl) ３ -phenyl and -O-phenyl substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of: R6, R7, R8, R9, and R10 are each independently -H and -CH ３ A metal complex selected from R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are each independently -H, -F, -Cl, -Br, -I, -CF ３ , -CH ３ , -CH ２ CH ３ , -CH ２ CH ２ CH ３ , -CH(CH ３ ) ２ , -C ４ H ９ (including its isomers), -C ６ H １３ (including its isomers), -C １０ H ２１ (including its isomers); phenyl, and -Si(CH ３ ) ３ 2. The metal complex of claim 1, wherein at least two or at least three of R1, R2, R3, R4, R5, R1', R2', R3', R4', and R5' are selected from -H.

9. The index p is 2, and the metal complex is represented by the following general formula (IE): 【Chemistry 9】 where each Z is independently -CH ３ , -benzyl, -Si(CH ３ ) ３ , -CH ２ -Si(CH ３ ) ３ , -phenyl, -O-phenyl; １～１２ -Alkyl, -N(C １～１２ -alkyl) ２ , -F, -Cl, and -Si(C １～１２ -alkyl) ３ -phenyl and -O-phenyl substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of: R6, R7, R8, R9, and R10 are each independently -H and -CH ３ A metal complex selected from R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' represent residues selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, trifluoromethyl, and combinations thereof, where at least two of R1, R2, R3, R4 and R5 represent hydrogen and at least two of R1', R2', R3', R4' and R5' represent hydrogen; R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' represent residues selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, trifluoromethyl and combinations thereof, where at least three of R1, R2, R3, R4 and R5 represent H and at least three of R1', R2', R3', R4' and R5' represent hydrogen; 2. A metal complex according to claim 1, characterized in that R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' represent hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, trifluoromethyl and combinations thereof, wherein either R1, R2, R3, R4 and R5 all represent hydrogen or R1', R2', R3', R4' and R5' all represent hydrogen.

10. The metal complex according to any one of claims 1 to 9, wherein the metal M is titanium.

11. Z is -CH ３ The metal complex according to any one of claims 1 to 9,

12. 1. A method for preparing a polymer comprising the steps of: (a) providing a monomer composition comprising ethylene; (b) contacting at least a portion of said monomer composition with a catalyst composition comprising at least one metal complex according to any one of claims 1 to 9 to produce a polymer comprising units derived from ethylene.

13. 13. The method of claim 12, wherein the polymer is an ethylene / α-olefin copolymer having units derived from ethylene and at least one α-olefin having from 3 to 20 carbon atoms, and optionally at least one non-conjugated diene having from 6 to 30 carbon atoms and having at least one cyclic unit, the monomer composition comprising ethylene, propylene, and optionally at least one α-olefin having from 3 to 20 carbon atoms, and optionally at least one non-conjugated diene having from 6 to 30 carbon atoms and having at least one cyclic unit, and preferably the copolymer has a weight average molecular weight of at least 200,000 g / mole as determined by gel permeation chromatography.

14. 13. The method of claim 12, wherein the polymer is an ethylene / propylene / diene copolymer comprising units derived from a diene selected from 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), dicyclopentadiene (DCPD), and combinations thereof.

15. Use of a composition comprising a metal complex according to any one of claims 1 to 9 as a polymerization catalyst for the preparation of a polymer comprising units derived from ethylene.

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