Method for producing norbornane skeleton-containing polymer, and norbornane skeleton-containing polymer

Abstract

To provide: a method for producing a norbornane skeleton-containing polymer which has excellent transparency and adhesiveness to a polyimide resin and contains, in the same manner as the conventionally known copolymer of norbornane and a linear olefin, a norbornane skeleton and an alkylene chain derived from the linear olefin in the molecular chain; and a norbornane skeleton-containing polymer which can be produced by the production method.SOLUTION: A norbornane skeleton-containing polymer is produced by polymerizing one or two or more 2-alkyl norbornenes using, as a metal-containing catalyst, a metal compound comprising an atom of a Periodic Table Group 10 transition metal element.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a polymer containing a norbornane skeleton and a polymer containing a norbornane skeleton.

Background Art

[0002] Cyclic olefin homopolymers and cyclic olefin copolymers have low moisture absorption and high transparency, and are used in various applications, including the field of optical materials such as optical disk substrates, optical films, and optical fibers.

[0003] As a typical cyclic olefin copolymer, there is a copolymer of a cyclic olefin and ethylene, which is widely used as a transparent resin. Since the glass transition temperature of the copolymer of a cyclic olefin and ethylene can be changed according to the copolymerization composition of the cyclic olefin and ethylene, it is possible to produce a copolymer in which the glass transition temperature (Tg) is adjusted in a wide temperature range (see, for example, Non-Patent Document 1).

Prior Art Documents

Non-Patent Documents

[0004]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Regarding a film made of the above cyclic olefin copolymer, it is assumed that it is used by being laminated with a polyimide film excellent in mechanical properties, dimensional stability, and low dielectric properties in a high frequency band. However, according to a conventionally known method as described in Patent Document 1, there is a problem that it is difficult to obtain a cyclic olefin copolymer excellent in transparency and adhesiveness to a polyimide resin.

[0006] The present invention has been made in view of the above problems, and is excellent in transparency and adhesion to a polyimide resin, and has a norbornane skeleton and an alkylene chain derived from a chain olefin in its molecular chain, similar to a copolymer of a conventionally known norbornene and a chain olefin. An object of the present invention is to provide a method for producing a norbornane skeleton-containing polymer capable of producing a norbornane skeleton-containing polymer, and a norbornane skeleton-containing polymer that can be produced by the production method.

Means for Solving the Problems

[0007] The present inventors have found that the above problems can be solved by polymerizing one or more 2-alkylnorbornenes using a metal compound containing an atom of a Group 10 transition metal element of the periodic table as a metal-containing catalyst to produce a norbornane skeleton-containing polymer, and have completed the present invention. More specifically, the present invention provides the following.

[0008] (1) A method for producing a norbornane skeleton-containing polymer, comprising polymerizing one or more 2-alkylnorbornenes in the presence of a metal-containing catalyst to produce a norbornane skeleton-containing polymer, wherein the metal-containing catalyst is a metal compound containing an atom of a Group 10 transition metal element of the periodic table.

[0009] (2) The method for producing a norbornane skeleton-containing polymer according to (1), wherein the 2-alkylnorbornene is one or more selected from the compounds represented by the following formula (a1).

Chemical formula

[0010] (3) The obtained norbornane skeleton-containing polymer contains one or more structural units selected from the structural units represented by the following formula (a2), and the DSC curve obtained by measuring a sample of the norbornane skeleton-containing polymer with a differential scanning calorimeter according to the method described in JIS K7121 under a nitrogen atmosphere at a heating rate of 20 ° C / min does not have a melting point peak in the range of 200 ° C to 300 ° C. The method for producing a norbornane skeleton-containing polymer according to (2).

Chemical formula

[0011] (4) Using deuterated chloroform as a solvent 13 Of the norbornane skeleton-containing polymer obtained by 13C NMR measurement 13 In the 13C NMR spectrum, there is a peak in the range of 48 ppm to 55 ppm. The method for producing a norbornane skeleton-containing polymer according to any one of (1) to (3).

[0012] (5) The Group 10 transition metal element of the periodic table is nickel or palladium. The method for producing a norbornane skeleton-containing polymer according to any one of (1) to (4).

[0013] (6) The metal compound has a ligand derived from a diimine compound. The method for producing a norbornane skeleton-containing polymer according to any one of (1) to (5).

[0014] (7) A norbornane skeleton-containing polymer containing a structural unit represented by the following formula (A), The DSC curve obtained by measuring a sample of the norbornane skeleton-containing polymer with a differential scanning calorimeter according to the method described in JIS K7121 under a nitrogen atmosphere at a heating rate of 20 ° C / min does not have a melting point peak in the range of 200 ° C to 300 ° C. Norbornane skeleton-containing polymer.

Chemical formula

[0015] (8) The norbornane skeleton-containing polymer according to (7), wherein the structural unit represented by formula (A) is one or more structural units selected from the structural units represented by the following formula (a2). [Chemical formula] (In formula (a2), n2 is an integer of 0 or more and 5 or less.)

[0016] (9) Using deuterated chloroform as a solvent 13 Obtained by 13C NMR measurement 13 In the 13C NMR spectrum, the norbornane skeleton-containing polymer according to (7) or (8), in which a peak exists in the range of 48 ppm to 55 ppm.

[0017] (10) The norbornane skeleton-containing polymer containing a portion in which a norbornane-2,3-diyl group and one or more alkylene groups are alternately repeated in the molecular chain, and using deuterated chloroform as a solvent 13 Obtained by 13C NMR measurement 13 In the 13C NMR spectrum, the norbornane skeleton-containing polymer in which a peak exists in the range of 48 ppm to 55 ppm. [Effect of the invention]

[0018] According to the present invention, there can be provided a method for producing a norbornane skeleton-containing polymer capable of producing a norbornane skeleton-containing polymer excellent in transparency and adhesiveness to a polyimide resin and containing a norbornane skeleton and an alkylene chain derived from a chain olefin in a molecular chain in the same manner as a copolymer of a conventionally known norbornene and a chain olefin, and a norbornane skeleton-containing polymer produced by the production method. [Mode for carrying out the invention]

[0019] ≪Method for Producing Polymer Containing Norbornane Skeleton≫ The method for producing a polymer containing a norbornane skeleton includes polymerizing one or more 2-alkylnorbornenes in the presence of a metal-containing catalyst to produce a polymer containing a norbornane skeleton. In the above method, as the metal-containing catalyst, a metal compound containing an atom of a Group 10 transition metal element of the periodic table is used.

[0020] According to the above method, due to the progress of polymerization through the so-called chain walking mechanism in which β-hydrogen elimination and reinsertion occur immediately, a polymer chain containing a structure in which trans-norbornane-2,3-diyl units and alkylene groups derived from alkyl groups of 2-alkylnorbornenes are alternately and regularly arranged is generated.

[0021] The polymer containing a norbornane skeleton obtained by the above method is excellent in transparency and adhesiveness to a polyimide resin. On the other hand, a cyclic olefin copolymer such as a copolymer of a cyclic olefin and an olefin such as ethylene produced by a conventionally known method is excellent in transparency but inferior in adhesiveness to a polyimide resin.

[0022] Here, when a cyclic olefin copolymer is obtained by copolymerizing a cyclic olefin and an olefin such as ethylene, an alicyclic block in which alicyclic units derived from the cyclic olefin are continuous is inevitably generated.

[0023] Considering the molecular chain structures of the polymer containing a norbornane skeleton obtained by the above method and a cyclic olefin copolymer such as a copolymer of a cyclic olefin and ethylene, the alicyclic block in which alicyclic units derived from the cyclic olefin are continuous has an adverse effect on the adhesiveness to a polyimide resin, and the polymer containing a norbornane skeleton obtained by the above method is considered to be excellent in adhesiveness to a polyimide resin because it consists of a polymer chain containing a structure in which trans-norbornane-2,3-diyl units and alkylene groups derived from alkyl groups of 2-alkylnorbornenes are alternately and regularly arranged.

[0024] The norbornane skeleton-containing polymer obtained by the above method is further excellent in barrier properties.

[0025] In the above method, only one kind of 2-alkylnorbornene may be homopolymerized, or two or more kinds of 2-alkylnorbornenes may be copolymerized. Further, in the above polymerization reaction, within a range where the desired effect is not impaired, 2-alkylnorbornene and an olefin compound other than 2-alkylnorbornene copolymerizable with 2-alkylnorbornene may be copolymerized.

[0026] <2-alkylnorbornene> The 2-alkylnorbornene is not particularly limited as long as it is a norbornene compound having an alkyl group at the 2-position on the norbornene ring. The alkyl group at the 2-position on the norbornene ring may be linear or branched, and a linear one is preferred.

[0027] The 2-alkylnorbornene may have a substituent at a position other than the 2-position on the norbornene ring as long as it does not inhibit the desired polymerization reaction. Examples of the substituent include an alkyl group, an alkoxy group, an ester group, a carboxyl group, a hydroxy group, an amino group, and a halogen atom. The 2-alkylnorbornene preferably has no substituent at a position other than the 2-position on the norbornene ring.

[0028] As the 2-alkylnorbornene, a compound represented by the following formula (a1) is preferred from the viewpoints of easy availability and easy polymerization.

Chemical formula

[0029] The compound represented by formula (a1) can be prepared, for example, by reacting norbornene with potassium tert-butoxide and n-butyllithium according to the method described in J. Huang, et al., Chem. Commun., 2017, 53, 4589, and then further reacting with an alkyl bromide represented by RBr. The method for producing the compound represented by formula (a1) is not limited to the above method.

[0030] Specifically, the compound represented by formula (a1) is 2-methylnorbornene, 2-ethylnorbornene, 2-n-propylnorbornene, 2-n-butylnorbornene, 2-n-pentylnorbornene, or 2-n-hexylnorbornene.

[0031] <Olefin compounds other than 2-alkylnorbornene> Olefin compounds other than 2-alkylnorbornene that can copolymerize with 2-alkylnorbornene are not particularly limited as long as the desired effects are not impaired. Preferable examples of olefin compounds other than 2-alkylnorbornene include cyclic olefin compounds not corresponding to 2-alkylnorbornene, ethylene, and α-olefins.

[0032] Examples of cyclic olefin compounds not corresponding to 2-alkylnorbornene include cycloalkenes and compounds represented by the following formula (I). [Chemical formula] (In the formula, R 1 ~R 12 may be the same or different and are each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, R 9 and R 10 , R 11 and R 12 may combine to form a divalent hydrocarbon group, R 9 or R 10 and, R 11or R 12 may form a ring with each other. Also, n represents 0 or a positive integer, and when n is 2 or more, R 5 ~R 8 in each repeating unit may be the same or different from each other. However, when n = 0, at least one of R 1 ~R 4 and R 9 ~R 12 is not a hydrogen atom.)

[0033] The cyclic olefin compound represented by formula (I) will be described. R in formula (I) 1 ~R 12 may be the same or different from each other and is selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

[0034] R 1 ~R 8 Specific examples thereof include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, bromine; an alkyl group having 1 to 20 carbon atoms, etc. These may be different from each other, partially different, or all the same.

[0035] Also, specific examples of R 9 ~R 12 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a substituted or unsubstituted aromatic hydrocarbon group such as a phenyl group, a tolyl group, an ethylphenyl group, an isopropylphenyl group, a naphthyl group, an anthryl group; an aralkyl group in which an aryl group is substituted for an alkyl group such as a benzyl group, a phenethyl group, etc. These may be different from each other, partially different, or all the same.

[0036] R 9 and R 10 , or R 11 and R 12Specific examples of the case where they are integrated to form a divalent hydrocarbon group include, for example, alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group.

[0037] R 9 or R 10 and R 11 or R 12 When they form a ring with each other, the formed ring may be a monocyclic ring, a polycyclic ring, a polycyclic ring having a bridge, a ring having a double bond, or a ring composed of a combination of these rings. Further, these rings may have a substituent such as a methyl group.

[0038] Specific examples of the cyclic olefin compound represented by the general formula (I) include bicyclic cyclic olefins such as 5-methyl-bicyclo[2.2.1]hepta-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hepta-2-ene, 5-ethyl-bicyclo[2.2.1]hepta-2-ene, 5-butyl-bicyclo[2.2.1]hepta-2-ene, 5-ethylidene-bicyclo[2.2.1]hepta-2-ene, 5-hexyl-bicyclo[2.2.1]hepta-2-ene, 5-octyl-bicyclo[2.2.1]hepta-2-ene, 5-octadecyl-bicyclo[2.2.1]hepta-2-ene, 5-methylidene-bicyclo[2.2.1]hepta-2-ene, 5-vinyl-bicyclo[2.2.1]hepta-2-ene, and 5-propenyl-bicyclo[2.2.1]hepta-2-ene; Tricyclo[4.3.0.1 2,5 deca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 2,5 deca-3-ene; tricyclo[4.4.0.1 2,5 undeca-3,7-diene or tricyclo[4.4.0.1 2,5 undeca-3,8-diene or a partially hydrogenated product thereof (or an adduct of cyclopentadiene and cyclohexene), which is tricyclo[4.4.0.1 2,5Undeca-3-ene; tricyclic olefins such as 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexenylbicyclo[2.2.1]hept-2-ene, 5-phenyl-bicyclo[2.2.1]hept-2-ene; Tetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene (also simply called tetracyclododecene), 8-methyltetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-methylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-ethylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-vinyltetracyclo[4,4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 tetracyclic olefins such as dodeca-3-ene; 8-cyclopentyl-tetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene; tetracyclo[7.4.1 3,6 .0 1,9 .0 2,7 tetradeca-4,9,11,13-tetraene (also called 1,4-methano-1,4,4a,9a-tetrahydrofluorene), tetracyclo[8.4.1 4,7 .01,10 .0 3,8 Pentadeca-5,10,12,14-tetraene (also known as 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene); Pentacyclo[6.6.1.1 3,6 .0 2,7 .0 9,14 -4-hexadecene, Pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 -4-pentadecene, Pentacyclo[7.4.0.0 2,7 .1 3,6 .1 10,13 -4-pentadecene; Heptacyclo[8.7.0.1 2,9 .1 4,7 .1 11,17 .0 3,8 .0 12,16 -5-eicosene, Heptacyclo[8.7.0.1 2,9 .0 3,8 .1 4,7 .0 12,17 .1 13,l6 -14-eicosene; Polycyclic cyclic olefins such as tetramers of cyclopentadiene can be mentioned.

[0039] Among them, alkyl-substituted norbornenes (for example, bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups), alkylidene-substituted norbornenes (for example, bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups) are preferred, and 5-ethylidene-bicyclo[2.2.1]hept-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidene norbornene) is particularly preferred.

[0040] As the α-olefin, C3-C12 α-olefins are preferred. The C3-C12 α-olefins are not particularly limited, and examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 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, 1-octene, 1-decene, and 1-dodecene.

[0041] In the norbornane skeleton-containing polymer obtained by the above method, for example, in the case of a structural unit represented by the following formula (a2), the ratio of the structural unit derived from 2-alkylnorbornene to all the structural units is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.

[0042] <Metal-containing catalyst> As the metal-containing catalyst, a metal compound containing an atom of a Group 10 transition metal element of the periodic table is used. In terms of high catalytic activity and easy progress of the desired polymerization reaction, as the Group 10 transition metal element of the periodic table, nickel, palladium, and platinum are preferred, nickel and palladium are more preferred, and palladium is particularly preferred.

[0043] As the metal compound containing an atom of a Group 10 transition metal element of the periodic table, the following formula (a-1): L m M(X)2 ··· (a-1) (In the formula, L is a ligand, and X is independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an aralkyloxy group, or an aryloxy group. M is an atom of a Group 10 transition metal element of the periodic table, and m is the number of ligands.) The compound represented by the formula is preferred.

[0044] The ligand is not particularly limited as long as the desired polymerization reaction proceeds. From the viewpoint of facilitating the progress of the desired polymerization reaction, a metal-containing catalyst such as the metal compound represented by the formula (a-1) preferably has a ligand derived from a diimine compound.

[0045] Among the metal compounds represented by the formula (a-1), the following formula (a-2):

Chemical formula

[0046] In the formula (a-2), R a1 , and R a2 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an aralkyloxy group or an aryloxy group. R a1 , and R a2 may be linked to each other to form a ring. The alkyl group, cycloalkyl group, aralkyl group, aryl group, alkoxy group, cycloalkoxy group, aralkyloxy group, or aryloxy group may have a substituent.

[0047] In formula (a-2), R a1 , and R a2 Examples of the halogen atom as R

[0048] In formula (a-2), R a1 , and R a2 The alkyl group as R a1 , and R a2 The number of carbon atoms of the alkyl group as R Preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, and an n-hexyl group. Among these, the methyl group is particularly preferred. R a1 , and R a2 The alkyl group as R

[0049] In formula (a-2), R a1 , and R a2 The number of carbon atoms of the cycloalkyl group as R a1 , and R a2 Preferred examples of the cycloalkyl group as R

[0050] r a1 , and R a2The number of carbon atoms of the aralkyl group as [substituent] is preferably 7 or more and 12 or less. R a1 and R a2 Preferable examples of the aralkyl group as [substituent] include a benzyl group and a phenethyl group. Among these, the benzyl group is particularly preferable. R a1 and R a2 The aralkyl group as [substituent] may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, a silyl group, and a cyano group.

[0051] R a1 and R a2 The number of carbon atoms of the aryl group as [substituent] is preferably 6 or more and 20 or less, more preferably 6 or more and 12 or less. R a1 and R a2 Preferable examples of the aryl group as [substituent] include a phenyl group, a naphthyl group, a 4-tolyl group, a mesityl group, and a 4-phenylphenyl group. Among these, the phenyl group, the 4-tolyl group, and the mesityl group are preferable. R a1 and R a2 The aryl group as [substituent] may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, a silyl group, and a cyano group.

[0052] In formula (a-2), the alkoxy group as [substituent] may be linear or branched. a1 and R a2 The number of carbon atoms of the alkoxy group as [substituent] is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 6 or less. a1 and R a2 ​Preferable examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Among these, a methoxy group, an ethoxy group, an isopropyloxy group, and a tert-butyloxy group are particularly preferable. R a1 , and R a2 The alkoxy group as and may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, a silyl group, and a cyano group.

[0053] In formula (a-2), R a1 , and R a2 The cycloalkoxy group as preferably has 3 to 20 carbon atoms, more preferably 4 to 10 carbon atoms. Preferable examples of the cycloalkoxy group as and include a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. a1 , and R a2 In formula (a-2), R

[0054] , and R a1 , and R a2 The aralkyloxy group as preferably has 7 to 20 carbon atoms. R a1 , and R a2Preferable examples of the aralkyloxy group as such include benzyloxy group, (2-methylphenyl)methoxy group, (3-methylphenyl)methoxy group, (4-methylphenyl)methoxy group, (2,3-dimethylphenyl)methoxy group, (2,4-dimethylphenyl)methoxy group, (2,5-dimethylphenyl)methoxy group, (2,6-dimethylphenyl)methoxy group, (3,4-dimethylphenyl)methoxy group, (3,5-dimethylphenyl)methoxy group, (2,3,4-trimethylphenyl)methoxy group, (2,3,5-trimethylphenyl)methoxy group, (2,3,6-trimethylphenyl)methoxy group, (2,4,5-trimethylphenyl)methoxy group, (2,4,6-trimethylphenyl)methoxy group, (3,4,5-trimethylphenyl)methoxy group, (2,3,4,5-tetramethylphenyl)methoxy group, (2,3,4,6-tetramethylphenyl)methoxy group, (2,3,5,(6 - Tetramethylphenyl)methoxy group, (pentamethylphenyl)methoxy group, (2 - ethylphenyl)methoxy group, (3 - ethylphenyl)methoxy group, (4 - ethylphenyl)methoxy group, (2 - n - propylphenyl)methoxy group, (3 - n - propylphenyl)methoxy group, (4 - n - propylphenyl)methoxy group, (2 - isopropylphenyl)methoxy group, (3 - isopropylphenyl)methoxy group, (4 - isopropylphenyl)methoxy group, (2 - n - butylphenyl)methoxy group, (3 - n - butylphenyl)methoxy group, (4 - n - butylphenyl)methoxy group, (2 - sec - butylphenyl)methoxy group, (3 - sec - butylphenyl)methoxy group, (4 - sec - butylphenyl)methoxy group, (2 - tert - butylphenyl)methoxy group, (3 - tert - butylphenyl)methoxy group, (4 - tert - butylphenyl)methoxy group, (2 - n - hexylphenyl)methoxy group, (3 - n - hexylphenyl)methoxy group, (4 - n - hexylphenyl)methoxy group, (2 - n - octylphenyl)methoxy group, (3 - n - octylphenyl)methoxy group, (4 - n - octylphenyl)methoxy group, (2 - n - decylphenyl)methoxy group, (3 - n - decylphenyl)methoxy group, (4 - n - decylphenyl)methoxy group, naphthalen - 1 - ylmethoxy group, and naphthalen - 2 - ylmethoxy group, etc. are mentioned. Among these, the benzyl group is preferable., R a1 and R a2 The aralkyloxy group as may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, a silyl group, and a cyano group, etc.

[0055] In formula (a - 2), R a1 and R a2 The number of carbon atoms of the aryloxy group as is preferably 6 or more and 20 or less. R a1 and R a2Preferable examples of the aryloxy group as such include a phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, 2-ethylphenoxy group, 3-ethylphenoxy group, 4-ethylphenoxy group, 2-n-propylphenoxy group, 3-n-propylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 3-isopropylphenoxy group, 4-isopropylphenoxy group, 2-n-butylphenoxy group, 3-n-butylphenoxy group, 4-n-butylphenoxy group, 2-sec-butylphenoxy group, 3-sec-butylphenoxy group, 4-sec-butylphenoxy group, 2-tert-butylphenoxy group, 3-tert-butylphenoxy group, 4-tert-butylphenoxy group, 2-n-hexylphenoxy group, 3-n-hexylphenoxy group, 4-n-hexylphenoxy group, 2-n-octylphenoxy group, 3-n-octylphenoxy group, 4-n-octylphenoxy group, 2-n-decylphenoxy group, 3-n-decylphenoxy group, 4-n-decylphenoxy group, naphthalen-1-yloxy group, and naphthalen-2-yloxy group may be mentioned., R a1 , and R a2 The aryloxy group as and R may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, a silyl group, and a cyano group etc.

[0056] R in formula (a-2) a1 , and R a2 are preferably a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom, a halogen atom, or an unsubstituted linear alkyl group having 1 to 12 carbon atoms, and particularly preferably a chlorine atom or a methyl group.

[0057] R in formula (a-2) a3 ~R a10is, independently of each other, a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an aralkyloxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an amino group, a carbamoyl group, or a hydrocarbylthio group. These groups may have substituents.

[0058] R in formula (a-2) a3 ~R a10 As the halogen atom, alkyl group, cycloalkyl group, aralkyl group, alkoxy group, cycloalkoxy group, aralkyloxy group, and aryloxy group for R a3 ~R a10 is the same as these groups for R

[0059] R in formula (a-2) a3 ~R a10 Preferable examples of the acyl group for R R a3 ~R a10 The acyl group for R may have substituents. Examples of the substituents include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, a silyl group, and a cyano group.

[0060] R in formula (a-2) a3 ~R a10 Preferable examples of the alkoxycarbonyl group for R R a3 ~R a10 The alkoxycarbonyl group for R may have substituents. Examples of the substituents include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, a silyl group, and a cyano group.

[0061] R in formula (a-2) a3 ~R a10 Preferable examples of the aralkyloxycarbonyl group as ~R include a 2-phenylethyloxycarbonyl group, a benzyloxycarbonyl group, a 1-phenylethyloxycarbonyl group, a 3-phenylpropyloxycarbonyl group, a 4-phenylbutyloxycarbonyl group, and the like. R a3 ~R a10 The aralkyloxycarbonyl group as ~R may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, a silyl group, and a cyano group, and the like.

[0062] R in formula (a-2) a3 ~R a10 Preferable examples of the aryloxycarbonyl group as ~R include a phenyloxycarbonyl group, a 2-methylphenyloxycarbonyl group, a 4-methylphenyloxycarbonyl group, a 4-methoxyphenyloxycarbonyl group, a naphthalen-1-yloxycarbonyl group, a 2-methylnaphthalen-1-yloxycarbonyl group, a 3-methylnaphthalen-1-yloxycarbonyl group, a 4-methylnaphthalen-1-yloxycarbonyl group, a 6-methylnaphthalen-1-yloxycarbonyl group, a naphthalen-2-yloxycarbonyl group, a 1-methylnaphthalen-2-yloxycarbonyl group, a 3-methylnaphthalen-2-yloxycarbonyl group, a 4-methylnaphthalen-2-yloxycarbonyl group, and a 6-methylnaphthalen-2-yloxycarbonyl group, and the like. R a3 ~R a10 The aryloxycarbonyl group as ~R may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, a silyl group, and a cyano group, and the like.

[0063] R in formula (a-2) a3 ~R a10The amino group as such may be an unsubstituted amino group (-NH2), an N-monosubstituted amino group, or an N,N-disubstituted amino group. As the N-monosubstituted amino group, an N-alkylamino group or an N-cycloalkylamino group is preferable. As the N,N-disubstituted amino group, an N,N-dialkylamino group, an N,N-dicycloalkylamino group, and an N-alkyl-N-cycloalkylamino group are preferable. The alkyl group contained in these groups may be linear or branched. Preferable specific examples of the N-alkylamino group include an N-methylamino group, an N-ethylamino group, an N-n-propylamino group, an N-isopropylamino group, an N-n-butylamino group, an N-isobutylamino group, and an N-tert-butylamino group. Examples of the N-cycloalkylamino group include an N-cyclopentylamino group, an N-cyclohexylamino group, an N-cycloheptylamino group, and an N-cyclooctylamino group. Preferable specific examples of the N,N-dialkylamino group include an N,N-dimethylamino group, an N,N-diethylamino group, an N,N-di-n-propylamino group, an N,N-diisopropylamino group, an N,N-di-n-butylamino group, and an N,N-di-tert-butylamino group. Preferable specific examples of the N,N-dicycloalkylamino group include an N,N-dicyclopentylamino group, an N,N-dicyclohexylamino group, an N,N-dicycloheptylamino group, and an N,N-dicyclooctylamino group. R a3 ~R a10 The amino group as such may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, and a cyano group.

[0064] R in formula (a-2) a3 ~R a10 The carbamoyl group as such may be an unsubstituted carbamoyl group (-CONH2), an N-monosubstituted carbamoyl group, or an N,N-disubstituted carbamoyl group. R in formula (a-2) a3 ~R a10 Preferable examples of the carbamoyl group as ~R a10 include an unsubstituted carbamoyl group (-CONH2); N-monosubstituted carbamoyl groups such as N-methylcarbamoyl group, N-ethylcarbamoyl group, N-n-propylcarbamoyl group, N-isopropylcarbamoyl group, N-n-butylcarbamoyl group, N-isobutylcarbamoyl group, N-tert-butylcarbamoyl group, N-n-pentylcarbamoyl group, N-neopentylcarbamoyl group, N-cyclopentylcarbamoyl group, N-cyclohexylcarbamoyl group, N-cycloheptylcarbamoyl group, and N-cyclooctylcarbamoyl group; and N,N-disubstituted carbamoyl groups such as N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group, N-methyl-N-ethylcarbamoyl group, N-ethyl-N-n-butylcarbamoyl group, and N-n-butyl-N-n-hexylcarbamoyl group. R a3 ~R a10 When the amino group as ~R a10 has an organic group bonded to the nitrogen atom, the organic group may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, and a cyano group.

[0065] R in formula (a-2) a3 ~R a10 Preferable examples of the hydrocarbylthio group as ~R a10 include an alkylthio group, a cycloalkylthio group, an arylthio group, and an aralkylthio group. Examples of the alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, and a tert-butylthio group. Examples of the cycloalkylthio group include a cyclopentylthio group, a cyclohexylthio group, a cycloheptylthio group, and a cyclooctylthio group. Examples of the arylthio group include a phenylthio group, a naphthalen-1-ylthio group, and a naphthalen-2-ylthio group. Examples of the aralkylthio group include a benzylthio group and the like. R a3 ~R a10 The hydrocarbylthio group as ~R may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonate group, and a cyano group.

[0066] R in formula (a-2) a3 and R a4 are each independently preferably a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may be an alkyl group, a cycloalkyl group, or an aryl group. The alkyl group may be linear or branched. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, a linear alkyl group having 1 to 12 carbon atoms is more preferable, and a methyl group and an ethyl group are even more preferable. Examples of the linear alkyl group include a methyl group, an ethyl group, and an n-butyl group. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a tert-butyl group, and a neopentyl group. As the cycloalkyl group, a cycloalkyl group having 3 to 20 carbon atoms is preferable, and a cycloalkyl group having 5 to 12 carbon atoms is more preferable. Examples of the cycloalkyl group include a cyclohexyl group and a cyclooctyl group. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 12 carbon atoms is more preferable, and a phenyl group or a mesityl group is even more preferable. Examples of the aryl group include a phenyl group, a naphthalen-1-yl group, a naphthalen-2-yl group, a 4-tolyl group, and a mesityl group. The hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonyl group, and a silyl group.

[0067] R in formula (a-2) a3 , and R a4 may be linked to each other to form a ring. The ring formed may be an aliphatic ring or an aromatic ring. R a3 , and R a4 Examples of the divalent group formed by the linkage of R and R include an ethane-1,2-diyl group, an ethylene-1,2-diyl group, a cyclohexane-1,2-diyl group, a norbornane-1,2-diyl group, a butane-2,3-diyl group, a 2,3-dimethylbutane-2,3-diyl group, a pentane-2,4-diyl group, a benzene-1,2-diyl group, a naphthalene-1,8-diyl group, and the like.

[0068] R in formula (a-2) a5 , and R a8 are preferably alkyl groups, more preferably alkyl groups having 1 to 12 carbon atoms, and still more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a tert-butyl group.

[0069] R in formula (a-2) a6 , and R a7 are each independently preferably an aryl group having 7 to 20 carbon atoms. Preferable examples of the aryl group include 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, naphthyl group, 2-methylnaphthalen-1-yl group, 3-methylnaphthalen-1-yl group, 4-methylnaphthalen-1-yl group, 2,3-dimethylnaphthalen-1-yl group, 2,4-dimethylnaphthalen-1-yl group, 2,5-dimethylnaphthalen-1-yl group, 2,6-dimethylnaphthalen-1-yl group, 3,4-dimethylnaphthalen-1-yl group, 3,5-dimethylnaphthalen-1-yl group, 3,6-dimethylnaphthalen-1-yl group, anthracen-1-yl group, anthracen-10-yl group, 2-methylanthracen-1-yl group, 3-methylanthracen-10-yl group, 4-methylanthracen-10-yl group, 2,3-dimethylanthracen-10-yl group, 2,4-dimethylanthracen-10-yl group, 2,5-dimethylanthracen-10-yl group, 2,6-dimethylanthracen-10-yl group, 3,4-dimethylanthracen-10-yl group, 3,5-dimethylanthracen-10-yl group, 3,6-dimethylanthracen-10-yl group, and 2-methylanthracen-10-yl group, etc.

[0070] R in formula (a-2) a9 , and R a10 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and still more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group.

[0071] Preferable specific examples of the compound represented by formula (a-2) include the following compounds. In the following formula, Me is a methyl group, Et is an ethyl group, Ph is a phenyl group, Mes is a mesityl group, OMe is a methoxy group, iPr is an isopropyl group, and M is an atom of a Group 10 transition metal element in the periodic table. In the following compounds, M is preferably nickel or palladium, and more preferably palladium.

Chemical formula

[0072]

Chemical formula

[0073]

Chemical formula

[0074]

Chemical formula

[0075] In addition, the following compounds can also be suitably used as the metal-containing catalyst. In the following formula, Me is a methyl group and M is an atom of a Group 10 transition metal element in the periodic table.

Chemical formula

[0076] The amount of the metal-containing catalyst described above is not particularly limited as long as the polymerization reaction of the monomer containing 2-ethylnorbornene proceeds well. The amount of the metal-containing catalyst is preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, and even more preferably 1.5 parts by mass or more and 6 parts by mass or less with respect to 100 parts by mass of the monomer containing 2-ethylnorbornene.

[0077] <Polymerization method> The polymerization of monomers containing 2-alkylnorbornene in the presence of a metal-containing catalyst is typically carried out in an organic solvent. The polymerization reaction may be carried out batchwise or continuously.

[0078] The organic solvent is not particularly limited as long as it does not inhibit the polymerization reaction. Preferred organic solvents include hydrocarbon solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, and halogenated hydrocarbon solvents. Specific examples of preferred solvents include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, and decahydronaphthalene (decalin), aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.

[0079] The amount of the organic solvent used is not particularly limited as long as the polymerization reaction proceeds to the desired extent. The amount of the organic solvent used is preferably 50 parts by mass or more and 5000 parts by mass or less, more preferably 100 parts by mass or more and 3000 parts by mass or less, and even more preferably 150 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the monomer containing 2-alkylnorbornene.

[0080] The polymerization temperature is not particularly limited as long as the polymerization proceeds to the desired extent. The polymerization temperature is preferably -50°C or higher and 200°C or lower, more preferably -30°C or higher and 100°C or lower, and even more preferably -10°C or higher and 50°C or lower.

[0081] When carrying out the polymerization, a cocatalyst may be used together with the metal-containing catalyst. Preferred examples of the cocatalyst include organic aluminum compounds and boron compounds.

[0082] (Organic aluminum compound) Examples of the organic aluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride.

[0083] Preferable specific examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, and tri-n-hexylaluminum.

[0084] Preferable specific examples of the dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisobutylaluminum chloride, and di-n-hexylaluminum chloride.

[0085] Preferable specific examples of the alkylaluminum dichloride include methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, isobutylaluminum dichloride, and n-hexylaluminum dichloride.

[0086] Preferable specific examples of the dialkylaluminum hydride include dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, diisobutylaluminum hydride, and di-n-hexylaluminum hydride.

[0087] In addition, aluminoxane is also preferable as the organoaluminum compound. As the aluminoxane, alkylaluminoxane is preferably used. Examples of the alkylaluminoxane include compounds represented by the following formula (b1-1) or (b1-2). The alkylaluminoxane represented by the following formula (b1-1) or (b1-2) is a product obtained by the reaction of trialkylaluminum and water.

[0088]

Chemical formula

[0089] Examples of the alkylaluminoxane include methylaluminoxane and modified methylaluminoxane in which a part of the methyl groups of methylaluminoxane are substituted with other alkyl groups. Examples of the modified methylaluminoxane preferably include modified methylaluminoxane having an alkyl group having 2 or more and 4 or less carbon atoms such as an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group as the alkyl group after substitution. Particularly, modified methylaluminoxane in which a part of the methyl groups is substituted with an isobutyl group is more preferable. Specific examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane, etc. Among them, methylaluminoxane and methylisobutylaluminoxane are preferable.

[0090] The alkylaluminoxane can be prepared by a known method. Also, a commercially available product may be used as the alkylaluminoxane. Examples of the commercially available product of the alkylaluminoxane include MMAO-3A, TMAO-200 series, TMAO-340 series, solid MAO (all manufactured by Tosoh Finechem Corporation), and methylaluminoxane solution (manufactured by Albemarle Corporation), etc.

[0091] (Boron compound) As the boron compound, boron compounds that have conventionally been used as cocatalysts in the polymerization of olefins can be used without particular limitation.

[0092] Specific examples of the boron compound as a cocatalyst 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, phenylbis(pent Tetrafluorophenyl)borane, lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, potassium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, silver tetrakis(pentafluorophenyl)borate, ferrocenium tetrakis(pentafluorophenyl)borate, 1,1'-dimethylferrocenium tetrakis(pentafluorophenyl)borate, tetrabutylphosphonium tetrakis(pentafluorophenyl)borate, tetraphenylphosphonium tetrakis(pentafluorophenyl)borate, tetramethylammonium tetrakis(pentafluorophenyl)borate, trimethylsulfonium tetrakis(pentafluorophenyl)borate, diphenyliodonium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, diisopropylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, and tri(dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, etc. can be mentioned.

[0093] The amount of the organoaluminum compound used is typically preferably 0.1 mol or more and 10,000 mol or less, more preferably 5 mol or more and 2,000 mol or more, per 1 mol of the metal-containing catalyst. The amount of the boron compound used is typically preferably 0.01 mol or more and 100 mol or less, more preferably 0.5 mol or more and 10 mol or less, per 1 mol of the metal-containing catalyst.

[0094] <Norbornane skeleton-containing polymer> According to the method described above, a norbornane skeleton-containing polymer containing a structural unit represented by the following formula (A) can be obtained. [Chemical formula] (In formula (A), R 1 is an alkylene group, n1 is 0 or 1, and the alkylene group as R 1 in a plurality of structural units may be only one kind or two or more kinds.)

[0095] When measuring a sample of the norbornane skeleton-containing polymer by a differential scanning calorimeter under a nitrogen atmosphere at a heating rate of 20 ° C / min according to the method described in JIS K7121, a DSC curve having no melting point peak in the range of 200 ° C to 300 ° C can be obtained. The presence of a melting point peak in the DSC curve on the orthogonal coordinate plane having an axis related to the value of heat flow and an axis related to the value of temperature can be confirmed from the dDSC curve which is the temperature differential curve of the obtained DSC curve. Specifically, in the dDSC curve, the presence of a melting point peak in the DSC curve can be confirmed by the continuous presence of a positive peak (a peak convex upward) and a negative peak (a peak convex downward) from the low temperature side to the high temperature side of the axis related to temperature.

[0096] As described above, conventional cyclic olefin copolymers such as copolymers of cyclic olefins and ethylene inevitably contain in the molecular chain an alicyclic block in which alicyclic units derived from cyclic olefins are continuous. This alicyclic block enhances the crystallinity of the cyclic olefin copolymer. Therefore, when measuring a sample of a conventional cyclic olefin copolymer using a differential scanning calorimeter, the resulting DSC curve has a melting point peak based on crystal melting. On the other hand, the molecular chain of the norbornene skeleton-containing polymer obtained by the above method contains a structure in which trans-norbornane-2,3-diyl units and alkylene groups derived from alkyl groups of 2-alkylnorbornene are alternately and regularly arranged, and contains little or no alicyclic block in which alicyclic units are continuous. Therefore, when measuring a sample of the norbornene skeleton-containing polymer obtained by the above method using a differential scanning calorimeter, it is considered that the resulting DSC curve does not have a melting point peak based on crystal melting.

[0097] That is, the fact that the resulting DSC curve does not have a melting point peak based on crystal melting indicates that the norbornene skeleton-containing polymer contains little or no alicyclic block in which alicyclic units are continuous. As described above, the norbornene skeleton-containing polymer containing little or no alicyclic block in which alicyclic units are continuous has excellent adhesiveness to the polyimide resin. Also, when the DSC curve does not have a melting point peak based on crystal melting, the norbornene skeleton-containing polymer tends to have excellent transparency.

[0098] The structural unit represented by the above formula (A) is preferably one or more structural units selected from the structural units represented by the following formula (a2). [Chemical formula] (In formula (a2), n2 is an integer of 0 or more and 5 or less.)

[0099] In the norbornane skeleton-containing polymer obtained by the above method, the content of the structural unit represented by the above formula (A) is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.

[0100] Further, according to the method described above, in the molecular chain, there is a part in which norbornane-2,3-diyl groups and one or more alkylene groups are alternately repeated, and deuterated chloroform is used as a solvent. 13 Obtained by 13C NMR measurement 13 In the 13C NMR spectrum, a norbornane skeleton-containing polymer in which peaks exist in the range of 48 ppm to 55 ppm is obtained.

[0101] 13 The presence of peaks in the range of 48 ppm to 55 ppm in the 13C NMR spectrum means the presence of trans-norbornane-2,3-diyl groups in the molecular chain. Therefore, the part in which norbornane-2,3-diyl groups and one or more alkylene groups are alternately repeated corresponds to the part in which the structural unit represented by the above formula (A) is repeated.

[0102] In terms of the norbornane skeleton-containing polymer maintaining good mechanical properties, the number average molecular weight Mn of the norbornane skeleton-containing polymer measured as a polystyrene equivalent value by gel permeation chromatography is preferably 10,000 g / mol or more, and more preferably 20,000 g / mol or more. Also, in terms of the good processability of the norbornane skeleton-containing polymer, based on the weight average molecular weight Mw and the number average molecular weight Mn measured as polystyrene equivalent values by gel permeation chromatography, the molecular weight distribution of the norbornane skeleton-containing polymer defined as Mw / Mn is preferably 1.1 or more, and more preferably 1.2 or more.

[0103] The glass transition temperature of the norbornane skeleton-containing polymer is not particularly limited, but from the viewpoint of processability, for example, 185°C or lower is preferable, 160°C or lower is more preferable, 130°C or lower is even more preferable, 120°C or lower is even more preferable, and 100°C or lower is particularly preferable. The longer the alkylene chain connecting two norbornane-2,3-diyl groups, the lower the glass transition temperature of the norbornane skeleton-containing polymer tends to be.

[0104] The norbornane skeleton-containing polymer described above can be well processed into molded articles by various melt processing methods such as extrusion molding and injection molding.

[0105] Since the norbornane skeleton-containing polymer is transparent, it is suitably used, for example, for molding films, sheets, or lenses. Also, as described above, since the norbornane skeleton-containing polymer has excellent adhesiveness to polyimide resins, it is suitably used as an electronic material such as a modifier for polyimide films and a modifier for rigid substrates.

Examples

[0106] Hereinafter, examples are shown to specifically describe the present invention, but the present invention is not limited to these examples.

[0107] [Example 1] Into a reaction vessel, 0.122 g of 2-ethylnorbornene, 0.0055 g of a metal-containing catalyst (Catalyst C1) of the following formula, 0.0106 g of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (NaBARF), and 0.5 mL of dichloromethane were added, and then the reaction solution in the vessel was stirred at room temperature for 20 minutes to carry out polymerization. After the reaction, the reaction solution was poured into methanol, and the insoluble portion was filtered to obtain 0.107 g of a norbornane skeleton-containing polymer.

Chemical formula

[0108] [Example 2] Into a reaction vessel, 0.244 g of 2-ethylnorbornene, 0.0120 g of a metal-containing catalyst (Catalyst C2) of the following formula, 0.0212 g of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (NaBARF), and 1.0 mL of dichloromethane were added. After that, the reaction solution in the vessel was stirred at room temperature for 30 minutes to carry out polymerization. After the reaction, the reaction solution was poured into methanol, and the insoluble part was filtered to obtain 0.230 g of a norbornane skeleton-containing polymer.

Chemical formula

[0109] 〔Example 3〕 Into a reaction vessel, 0.108 g of 2-methylnorbornene, 0.0055 g of the metal-containing catalyst (Catalyst C1) used in Example 1, 0.0106 g of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (NaBARF), and 0.5 mL of dichloromethane were added. After that, the reaction solution in the vessel was stirred at room temperature for 20 minutes to carry out polymerization. After the reaction, the reaction solution was poured into methanol, and the insoluble part was filtered to obtain 0.0817 g of a norbornane skeleton-containing polymer.

[0110] Regarding the obtained norbornane skeleton-containing resin, using deuterated chloroform as a solvent 13 When 13C NMR measurement was carried out, in the 13 13C NMR spectrum obtained, peaks were present in the range of 48 ppm to 55 ppm.

[0111] Regarding the obtained norbornane skeleton-containing polymer, measurement was carried out with a differential scanning calorimeter according to JIS K7121 under the following conditions. As a result, a DSC curve having no melting point peak in the range of 200 °C to 300 °C was obtained. DSC apparatus: Differential scanning calorimeter (DSC-Q1000 manufactured by TA Instrument) Measurement atmosphere: Nitrogen Temperature rising condition: 20 °C / min

[0112] Regarding the obtained polymer containing a norbornane skeleton, the transparency, adhesion to a polyimide resin, and barrier properties were evaluated according to the following methods. These evaluation results are shown in Table 1.

[0113] Transparency: The obtained resin containing a norbornane skeleton was melted. The melted resin containing a norbornane skeleton was formed into a film on a glass substrate and then cooled to prepare a film sample with a thickness of 100 μm. The film sample was visually observed to evaluate the transparency of the film sample. The case of transparency was marked as ○, and the case of opacity was marked as ×.

[0114] Adhesion to polyimide resin: A melt press using the resin containing a norbornane skeleton on a Kapton film was performed to obtain a laminated film having a film of the resin containing a norbornane skeleton on the Kapton film. In the obtained laminated film, the film of the resin containing a norbornane skeleton was peeled off from the Kapton film, and the adhesion of the resin containing a norbornane skeleton to the polyimide resin was evaluated based on the ease of peeling from the Kapton film. The case of being difficult to peel off was marked as ○, and the case of being easy to peel off was marked as ×.

[0115] Water vapor barrier property: In the same manner as the evaluation of transparency, a film sample of the resin containing a norbornane skeleton with a thickness of 100 μm was obtained. Using the obtained film sample, the water vapor barrier property was evaluated under the conditions of 40 °C and 90% RH according to the method of JIS Z0208. The water vapor barrier property was evaluated in the unit of g / m 2 / 24h. The case of 4 g / m 2 / 24h or less was marked as ○, and the case of exceeding 4 g / m 2 / 24h was marked as ×.

[0116] 〔Comparative Example 1〕 The polymerization of 2-ethylnorbornene was carried out in the same manner as in Example 1 except that the catalyst C1 was changed to the catalyst C3 which is the following compound, but the polymerization reaction did not proceed.

Chemical formula

[0117] [Comparative Example 2] In Comparative Example 2, Catalyst C3 used in Comparative Example 1 was used. 56 g of toluene and 8.5 g of 2-norbornene were added to a well-dried 150 mL stainless steel autoclave containing a stir bar. Next, 2 mL of a 9.0 mass% (in terms of Al atom content) TMAO-211 toluene solution (a solution of methylaluminoxane, manufactured by Tosoh Finechem Corporation, containing 26 mol% of trimethylaluminum with respect to all Al) was added into the autoclave. Then, after heating the autoclave to 90 °C, a toluene solution of the catalyst was added into the autoclave so that the catalyst amount became 10 μmol. Next, an ethylene pressure of 0.7 MPa as gauge pressure was applied into the autoclave. 30 seconds after the start of pressurization was taken as the polymerization start point. Thereafter, the reaction solution in the container was stirred for 15 minutes to conduct polymerization. After the reaction, the reaction solution was poured into methanol, and the insoluble part was filtered to obtain 2.7 g of an ethylene-norbornene copolymer. Regarding the obtained ethylene-norbornene copolymer, using deuterated chloroform as a solvent 13 13C NMR measurement was performed, and as a result, in the 13 13C NMR spectrum, no peak was present in the range of 48 ppm to 55 ppm. Regarding the obtained ethylene-norbornene copolymer, in the same manner as in Example 1, transparency, adhesion to the polyimide resin, and barrier properties were evaluated. These evaluation results are shown in Table 1.

[0118] [Comparative Example 3] In Comparative Example 3, catalyst C4 having the following structure was used. 56 g of toluene and 8.5 g of 2-norbornene were added to a 150 mL stainless steel autoclave containing a stir bar and well dried. Next, 2 mL of a 9.0 mass% (in terms of Al atom content) TMAO-211 toluene solution (a solution of methylaluminoxane, manufactured by Tosoh Finechem Corporation, containing 26 mol% of trimethylaluminum with respect to all Al) was added into the autoclave. Then, after heating the autoclave to 90°C, a toluene solution of the catalyst was added into the autoclave such that the catalyst amount became 0.1 μmol. Next, an ethylene pressure of 0.7 MPa as gauge pressure was applied into the autoclave. The start point of polymerization was set at 30 seconds after the start of pressurization. Thereafter, the reaction solution in the container was stirred for 15 minutes to conduct polymerization. After the reaction, the reaction solution was poured into methanol, and the insoluble part was filtered to obtain 1.1 g of an ethylene-norbornene copolymer. Regarding the obtained ethylene-norbornene copolymer, using deuterated chloroform as a solvent 13 C NMR measurement was carried out, and as a result, 13 in the obtained 13C NMR spectrum, no peak was present in the range of 48 ppm to 55 ppm. Regarding the obtained ethylene-norbornene copolymer, in the same manner as in Example 1, transparency, adhesion to the polyimide resin, and barrier properties were evaluated. These evaluation results are shown in Table 1.

Chemical formula

[0119] 〔Comparative Example 4〕 In Comparative Example 4, catalyst C5 having the following structure was used. 56 g of toluene and 8.5 g of 2-norbornene were added to a 150 mL stainless steel autoclave containing a stir bar, which was well dried. Next, 2 mL of a 9.0 mass% (in terms of the content of Al atoms) TMAO-211 toluene solution (a solution of methylaluminoxane, manufactured by Tosoh Finechem Corporation, and containing 26 mol% of trimethylaluminum with respect to all Al) was added into the autoclave. Then, after heating the autoclave to 90 °C, a toluene solution of the catalyst was added into the autoclave so that the catalyst amount became 0.1 μmol. Next, an ethylene pressure of 0.7 MPa as the gauge pressure was applied into the autoclave. The start point of polymerization was defined as 30 seconds after the start of pressurization. Thereafter, the reaction solution in the container was stirred for 15 minutes to conduct polymerization. After the reaction, the reaction solution was poured into methanol, and the insoluble portion was filtered to obtain 2.0 g of an ethylene-norbornene copolymer. Regarding the obtained ethylene-norbornene copolymer, deuterated chloroform was used as a solvent. 13 When 13C NMR measurement was carried out, the obtained 13 In the 13C NMR spectrum, no peak was present in the range of 48 ppm to 55 ppm. Regarding the obtained ethylene-norbornene copolymer, the transparency, the adhesion to the polyimide resin, and the barrier property were evaluated in the same manner as in Example 1. The results of these evaluations are shown in Table 1.

Chemical formula

[0120]

Table 1

[0121] According to Table 1, it can be seen that only the norbornane skeleton-containing polymers of Examples 1 to 3 obtained by polymerizing 2-ethylnorbornene or 2-methylnorbornene using catalyst C1 or catalyst C2 containing Pd, which is a Group 10 transition metal element of the periodic table, have both good transparency and good adhesion to the polyimide resin. In addition, the norbornane skeleton-containing polymers of Examples 1 to 3 13 have peaks in the range of 48 ppm to 55 ppm in the 13C NMR spectrum, and thus contain trans-norbornane-2,3-diyl groups in the molecular chain. In addition, considering that the polymerization proceeds by the so-called chain walking mechanism for Catalysts C1 and C2, it can be said that the norbornane skeleton-containing polymer of Example 1 contains a portion in which the structural unit represented by the formula (a2) and having n = 1 is repeated.

[0122] On the other hand, the ethylene-norbornene copolymers of Comparative Examples 2 to 4, which are copolymers of ethylene and norbornene, were inferior in at least one of transparency and adhesion to the polyimide resin.

Claims

1. Polymerizing one or two or more 2-alkyl-2-norbornenes in the presence of a metal-containing catalyst to produce a polymer containing a norbornane skeleton, wherein the alkyl group of the 2-alkyl-2-norbornene has 1 to 6 carbon atoms, the 2-alkyl-2-norbornene optionally has a substituent at a position other than the 2-position on the norbornene ring, the substituent is an alkyl group, an alkoxy group, an ester group, a carboxyl group, a hydroxy group, an amino group, or a halogen atom, and the metal-containing catalyst is a metal compound containing an atom of a Group 10 transition metal element of the periodic table. A method for producing a polymer containing a norbornane skeleton.

2. The method for producing a polymer containing a norbornane skeleton according to claim 1, wherein the 2-alkyl-2-norbornene is one or more selected from the compounds represented by the following formula (a1). 【Chemical 1】 (In formula (a1), n2 is an integer of 0 or more and 5 or less.)

3. The resulting polymer containing a norbornane skeleton contains one or more structural units selected from the structural units represented by the following formula (a2), and a sample of the polymer containing a norbornane skeleton is measured by a differential scanning calorimeter according to the method described in JIS K7121 under a nitrogen atmosphere at a heating rate of 20 ° C. / min. The obtained DSC curve does not have a melting point peak in the range of 200 ° C. to 300 ° C. The method for producing a polymer containing a norbornane skeleton according to claim 2. 【Chemical 2】 (In formula (a2), n2 is an integer of 0 or more and 5 or less.)

4. Using heavy chloroform as a solvent １３ Of the norbornane skeleton-containing polymer obtained by 13C NMR measurement １３ The method for producing a norbornane skeleton-containing polymer according to any one of claims 1 to 3, wherein a peak exists in the range of 48 ppm to 55 ppm in the 13C NMR spectrum.

5. The method for producing a polymer containing a norbornane skeleton according to any one of claims 1 to 4, wherein the Group 10 transition metal element of the periodic table is nickel or palladium.

6. The method for producing a polymer containing a norbornane skeleton according to any one of claims 1 to 5, wherein the metal compound has a ligand derived from a diimine compound.

7. A polymer containing a norbornane skeleton and containing a structural unit represented by the following formula (A), wherein a sample of the polymer containing a norbornane skeleton is measured by a differential scanning calorimeter according to the method described in JIS K7121 under a nitrogen atmosphere at a heating rate of 20 ° C. / min. The obtained DSC curve does not have a melting point peak in the range of 200 ° C. to 300 ° C. A polymer containing a norbornane skeleton. [Chemical Formula 3] (In formula (A), n1 is 0 or 1, when n1 is 1, R 1 is an alkylene group having 1 to 5 carbon atoms, R in a plurality of structural units １ The alkylene group as ( ) may be only one kind or two or more kinds.)

8. The norbornane skeleton-containing polymer according to claim 7, wherein the structural unit represented by the formula (A) is one or more structural units selected from the structural units represented by the following formula (a2). 【Chemical 4】 (In the formula (a2), n2 is an integer of 0 or more and 5 or less.)

9. Using heavy chloroform as a solvent １３ Obtained by 13C NMR measurement １３ The norbornane skeleton-containing polymer according to claim 7 or claim 8, wherein a peak exists in the range of 48 ppm to 55 ppm in the 13C NMR spectrum.

10. It contains a part in which norbornane-2,3-diyl groups and one or more alkylene groups having 1 to 5 carbon atoms are alternately repeated in the molecular chain, and deuterated chloroform is used as a solvent. １３ Obtained by 13C NMR measurement １３ A norbornane skeleton-containing polymer in which a peak exists in the range of 48 ppm to 55 ppm in the 13C NMR spectrum.

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