JP2006052347A - Method for producing cyclic olefin-based addition copolymer, cyclic olefin-based addition copolymer and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a cyclic olefin-based addition polymer, with which addition polymerization is readily carried out up to a high polymerization conversion ratio even if an alkyl substituent group-containing bicyclo[2.2.1]hept-2-ene with a coexisting stereoisomer, especially an alkyl substituent group-containing bicyclo[2.2.1]hept-2-ene comprising a large amount of endo isomer is used as a monomer, molecular weight is controlled by a molecular weight modifier, an obtained addition polymer has transparency in a form such as sheet, film, etc., and has flexibility and toughness and to obtain a cyclic olefin-based addition polymer and a film or sheet composed of the cyclic olefin-based addition polymer. <P>SOLUTION: The method for producing the cyclic olefin-based addition copolymer comprises subjecting a monomer composition having 20-80 mol% of an alkyl substituent group-containing bicyclo[2.2.1]hept-2-ene compound and a specific cyclic olefin-based compound in all monomers to addition copolymerization in the presence of a palladium-based catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a cyclic olefin addition polymer, a cyclic olefin addition copolymer and its use. Specifically, the present invention is obtained by addition copolymerization of a cyclic olefin compound having an alkyl substituent with a specific cyclic olefin compound, which has both flexibility and excellent transparency, and is used as a hydrocarbon solvent. The present invention relates to a cyclic olefin addition polymer suitable for production of a soluble and transparent film or sheet, a production method thereof, and use thereof.

  An addition polymer of bicyclo [2.2.1] hept-2-ene (norbornene) is a polymer having excellent transparency, and it is conventionally known that it can be produced using a nickel catalyst or a palladium catalyst. . However, this addition polymer has a very high glass transition temperature of 370 to 390 ° C. and is difficult to mold, and when molded into a film or the like, it has no toughness and is brittle. For this reason, a cyclic olefin addition polymer having excellent moldability and toughness has been desired.

  Bicyclo [2.2.1] hept-2-ene addition polymers having an alkyl substituent have been proposed as addition polymers of cyclic olefin resins having flexibility (Patent Documents 1 to 3). reference). Bicyclo [2.2.1] hept-2-ene having an alkyl substituent, which is a raw material for such an addition polymer, is usually synthesized by a Diels-Alder reaction of cyclopentadiene and α-olefin. The resulting bicyclo [2.2.1] hept-2-ene having an alkyl substituent has a stereoisomer ratio of 60/40 to 90 in the endo form (endo form) and exo form (exo form). It is in the range of / 5, and the ratio of the endo form is large.

  By the way, when monomers such as bicyclo [2.2.1] hept-2-enecarboxylic acid ester and dicyclopentadiene are subjected to addition polymerization using a palladium catalyst, polymerization activity is obtained in the endo and exo forms. However, the exo form is known to have a high polymerization rate and the endo form is slow (see Patent Document 1, Non-Patent Documents 1 to 4). However, regarding the addition polymerization of bicyclo [2.2.1] hept-2-ene having an alkyl substituent, the difference due to stereoisomers has not been known.

  The present inventor examined the addition polymerization of a bicyclo [2.2.1] hept-2-ene having an alkyl substituent, and found that the bicyclo [2.2.1] hept-2-ene having an alkyl substituent In the addition polymerization, as in the addition polymerization of bicyclo [2.2.1] hept-2-ene, it was confirmed that the behavior of the polymerization reaction and the properties of the polymer produced differ depending on the catalyst used.

  That is, in polymerization using a nickel catalyst, a large amount of catalyst is required, but as a monomer, an alkyl substituent having a stereoisomeric endo-isomer / exo-isomer ratio of 60/40 to 95/5. Even in the case of using bicyclo [2.2.1] hept-2-ene having a polymerization system, the polymerization system was uniformly transparent until the conversion rate to the polymer exceeded 90%. However, in this case, the resulting bicyclo [2.2.1] hept-2-ene addition polymer having an alkyl substituent is optically transparent, but mechanical strength and toughness when a film is formed. It was inferior to.

On the other hand, when bicyclo [2.2.1] hept-2-ene having an alkyl substituent is addition-polymerized in a hydrocarbon solvent in the presence of a molecular weight regulator using a palladium catalyst, a polymerization reaction of the exo form In the first half of the polymerization in which the exo form is present, the polymerization rate is fast, the polymerization system is uniformly transparent, the film formed from the polymer recovered at this stage is also transparent, and the nickel catalyst is used. It was found that it was superior in terms of mechanical strength, elongation and the like and tougher than the case of using it. However, as the exo monomer disappears in the latter half of the polymerization reaction and a polymer derived from the endo monomer is produced, the polymerization system becomes opaque, and the film formed from the recovered polymer is also opaque. It became a thing. From these results, it was found that when a palladium catalyst is used, an optically transparent addition polymer can be obtained by stopping the polymerization in the first half of the polymerization. This is economically disadvantageous because many unreacted monomers are left unreacted, and there is a problem that the operation for separating and removing unreacted monomers from the polymerization system is required and the operation for recovering the produced polymer is complicated. is there.

  As a technique for addition polymerization of bicyclo [2.2.1] hept-2-ene having an alkyl substituent, bicyclo [2.2.1] hept-2-ene having an alkyl substituent and triethoxysilylbicyclo [ 2.2.1] Addition polymerization of hepta-2-ene in a system in which no molecular weight regulator is present has been proposed (see Patent Document 4). According to this document, it is described that a thin film polymerized and cast on glass or a silicon wafer is transparent. However, when the film is thick, the transparency, the molecular weight of the polymer, The conversion rate to coalescence is unknown.

  In addition, as a method of increasing the exo isomer ratio of bicyclo [2.2.1] hept-2-ene having an alkyl substituent, an endo of dicyclopentadiene can be obtained by addition of hydrogen bromide and elimination of bromine by alkali. Isomerization of isomers to exo isomers [G. L. Nelson et al., Synthesis, 105 (1975)], which can change the ratio of endo / exo to about 50/50. However, even in the case of using a monomer having an increased exo mass by such a complicated process, the addition polymerization using a palladium catalyst still has the above-mentioned problems. In addition, since there is almost no difference in boiling point between the endo isomer and the exo isomer in the monomer, it is difficult to completely separate them by distillation.

For this reason, bicyclo [2.2.1] hepta having an alkyl substituent in which stereoisomers coexist, such as when the ratio of endo isomer / exo isomer that is a stereoisomer is 60/40 to 95/5. -2-ene is used as a monomer to produce an addition polymer that is transparent and flexible in the form of sheets, films, etc., even when polymerized to a high conversion. The appearance of a method to do is desired.
Japanese Patent No. 3476466 Japanese Patent No. 3534127 JP 2002-12624 A US Pat. No. 6,455,650 Organometallics Vol. 20, 2802-2812 (2001) Macromol. Symp. Vol. 89, 433-442 (1995) Macromol. Symp. Vol. 133, 1-10 (1998) J. Polymer Sci. B Vol. 41, 2185-2199 (2003)

The present invention relates to bicyclo [2.2.1] hept-2-ene having an alkyl substituent in which stereoisomers coexist, and in particular, bicyclo [2.2.1] hepta having an alkyl substituent containing a large number of endo isomers. Even when 2-ene is used as a monomer, addition polymerization can be easily performed up to a high polymerization conversion rate, and the molecular weight can be controlled by a molecular weight regulator or the like. The resulting addition polymer is a sheet, A method for producing a cyclic olefin-based addition polymer, a cyclic olefin-based addition polymer, and a film comprising the cyclic olefin-based addition polymer, which have transparency in the form of a film, etc., and also have flexibility and toughness The issue is to provide seats.

In the production method of the cyclic olefin addition copolymer of the present invention,
20-80 mol% of a compound represented by the following formula (1),
1 to 20 mol% of a compound represented by the following formula (2), and 10 to 70 mol% of a compound represented by the following formula (3)
The monomer composition contained is subjected to addition copolymerization using a palladium-based catalyst.

(In the formula ^(1), A 1 ~A ⁴ are each independently a hydrogen atom, a halogen atom, atom or a group selected from alkyl groups such as methyl group or 2 to 10 carbon atoms, of A ¹ to A ⁴ At least one represents an alkyl group having 2 to 10 carbon atoms.)

[In the formula (2), B ^{1 to} B ⁴ are each independently a hydrocarbon group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group, and B ¹ and B ^2. Or B ¹
And B ³ cyclic ester groups, acid anhydride groups and N-alkyl or cycloalkyl substituted carbonimido groups, and the general formula — (CHR ¹ ) _k —X
Wherein X is selected from an alkoxycarbonyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon trialkylsiloxycarbonyl groups, and an alkoxy group having 1 to 3 carbon atoms alkoxysilyl group. And R ¹ is a hydrogen atom or a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group, and k represents an integer of 0 to 5.)
An atom or group selected from the group consisting of polar groups represented by: ]

(In formula (3), C ^{1 to} C ⁴ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group, and a halogen atom.)
In such a method for producing a cyclic olefin-based addition copolymer of the present invention, the compound represented by the formula (1) has an endo / exo ratio of 60/40 to 95/5. 2-10 monoalkyl-substituted bicyclo [2.2.1] hept-2-ene is preferable, and the compound represented by the formula (1) has an endo / exo ratio of 60. It is preferably 5-butylbicyclo [2.2.1] hept-2-ene of / 40 to 95/5.

In the method for producing a cyclic olefin addition polymer of the present invention, in formula (2), B ¹ to
At least one of B ⁴ is selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxycarbonyl group having an alkoxy group having 1 to 3 carbon atoms, and a trialkoxysilyl group having an alkoxy group having 1 to 3 carbon atoms. It is preferably a group.

In the method for producing a cyclic olefin addition copolymer of the present invention, the compound represented by the formula (3) is preferably bicyclo [2.2.1] hept-2-ene.
In the method for producing the cyclic olefin addition copolymer of the present invention, the palladium catalyst is,
1) palladium compound,
2) A phosphine compound having a group selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group, and having a cone angle of 170 to 200, a phosphonium salt of the phosphine compound, and the above At least one selected from complexes of phosphine compounds and organoaluminum compounds,
3) A multicomponent catalyst containing an ionic boron compound or an ionic aluminum compound is preferred.

The cyclic olefin addition copolymer of the present invention is
20 to 80 mol% of a structural unit represented by the following formula (4),
1 to 20 mol% of a structural unit represented by the following formula (5), and 10 to 70 mol% of a structural unit represented by the following formula (6)
It is characterized by containing.

(In the formula ^(4), A ¹ ~A 4 are each independently a hydrogen atom, a halogen atom, atom or a group selected from alkyl groups such as methyl group or 3 to 10 carbon atoms, of A ¹ to A ⁴ At least one represents an alkyl group having 2 to 10 carbon atoms.)

[In formula (5), B ^{1 to} B ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and B ¹ and B ^2. Or B ¹
And B ³ cyclic ester groups, acid anhydride groups and N-alkyl or cycloalkyl substituted carbonimido groups, and the general formula — (CHR ¹ ) _k —X
Wherein X is selected from an alkoxycarbonyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon trialkylsiloxycarbonyl groups, and an alkoxy group having 1 to 3 carbon atoms alkoxysilyl group. And R ¹ is a hydrogen atom or a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group, and k represents an integer of 0 to 5.)
An atom or group selected from the group consisting of polar groups represented by: ]

(In formula (6), C ^{1 to} C ⁴ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group, and a halogen atom).
Such a cyclic olefin addition copolymer of the present invention has a polystyrene-equivalent number average molecular weight (Mn) of 10,000 to 200,000 and a polystyrene-equivalent weight average molecular weight (Mw) of 30,000 to 500,000. It is preferable that

The film or sheet of the present invention is characterized by comprising the above-mentioned cyclic olefin addition copolymer of the present invention.
The film or sheet of the present invention is characterized in that the cyclic olefin-based addition copolymer of the present invention is formed by a solution casting method.

  According to the present invention, even when bicyclo [2.2.1] hept-2-ene having an alkyl substituent in which stereoisomers coexist is used as a monomer, it is easy to add addition to a high polymerization conversion. A method for producing a cyclic olefin addition copolymer that can be polymerized and whose molecular weight can be controlled by a molecular weight regulator or the like can be provided. Further, the addition copolymer according to the present invention can be dissolved in an alicyclic hydrocarbon solvent or an aromatic hydrocarbon solvent and can be molded by a solution casting method, and is transparent in the form of a sheet, a film, or the like. And has low hygroscopicity and also has flexibility and toughness.

Hereinafter, the present invention will be specifically described.
・ Method for producing cyclic olefin-based addition copolymer <monomer composition>
In the method for producing a cyclic olefin-based addition copolymer of the present invention, 20 to 80 mol of a compound represented by the following formula (1) (hereinafter also referred to as a specific monomer (1)) is added to all monomers. %, A compound represented by the following formula (2) (hereinafter also referred to as a specific monomer (2)) in an amount of 1 to 20 mol%, and a compound represented by the following formula (3) (hereinafter referred to as a specific monomer). (3)) is added to a monomer composition containing 10 to 70 mol% in an addition copolymerization.

(In the formula ^(1), A 1 ~A ⁴ are each independently a hydrogen atom, a halogen atom, atom or a group selected from alkyl groups such as methyl group or 2 to 10 carbon atoms, of A ¹ to A ⁴ At least one represents an alkyl group having 2 to 10 carbon atoms),

[In the formula (2), B ^{1 to} B ⁴ are each independently a hydrocarbon group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group, and B ¹ and B ^2. Or B ¹
And B ³ cyclic ester groups, acid anhydride groups and N-alkyl or cycloalkyl substituted carbonimido groups, and the general formula — (CHR ¹ ) _k —X
Wherein X is selected from an alkoxycarbonyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon trialkylsiloxycarbonyl groups, and an alkoxy group having 1 to 3 carbon atoms alkoxysilyl group. And R ¹ is a hydrogen atom or a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group, and k represents an integer of 0 to 5.)
An atom or group selected from the group consisting of polar groups represented by: ],

(In formula (3), C ^{1 to} C ⁴ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group, and a halogen atom.)
The specific monomer (1) used in the present invention is an alkyl-substituted cyclic olefin compound represented by the above formula (1), and specific examples thereof are not particularly limited. The compounds mentioned can be exemplified.
5-methyl-6-ethylbicyclo [2.2.1] hept-2-ene,
5-ethyl-bicyclo [2.2.1] hept-2-ene,
5,6-diethylbicyclo [2.2.1] hept-2-ene,
5-propyl-bicyclo [2.2.1] hept-2-ene,
5-butyl-bicyclo [2.2.1] hept-2-ene,
5-pentyl-bicyclo [2.2.1] hept-2-ene,
5-hexyl-bicyclo [2.2.1] hept-2-ene,
5-octyl-bicyclo [2.2.1] hept-2-ene,
5-decyl-bicyclo [2.2.1] hept-2-ene,
5-chloro-6-butylbicyclo [2.2.1] hept-2-ene,
5-Fluoro-6-butylbicyclo [2.2.1] hept-2-ene and the like.

As such a specific monomer (1), any of the compounds represented by the above formula (1) is preferably used. In the above formula (1), only one of A ^{1 to} A ⁴ is used. A compound having 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms, wherein A ^{1 to} A ⁴ are hydrogen atoms, that is, a monoalkyl-substituted bicyclo [2. 2.1] hept-2-ene is preferable, monoalkyl-substituted bicyclo [2.2.1] hept-2-ene having 3 to 6 carbon atoms is more preferable, and 5-butylbicyclo [ 2.2.1] Hept-2-ene is particularly preferred.

When the specific monomer (1) is a monoalkyl-substituted bicyclo [2.2.1] hept-2-ene having 2 to 10 carbon atoms, a stereoisomer of an endo form and an exo form is selected. It is usually a mixture of both. In the present invention, the ratio of the stereoisomers of the specific monomer (1) to be subjected to addition copolymerization is not particularly limited, but those that do not separate the stereoisomers can be preferably used. Those having a ratio of / exo body in the range of 60/40 to 95/5 are more preferably used. When the specific monomer (1) has a stereoisomer in such a range, the compound corresponding to the specific monomer (1) synthesized by Diels-Alder reaction or the like may be used as it is. Therefore, it is preferable because the raw material is easily available and economical.

Such a specific monomer (1) may be used individually by 1 type, and may be used in combination of 2 or more type.
The ratio of the specific monomer (1) used in the method for producing the cyclic olefin addition copolymer of the present invention is 20 to 80 mol%, preferably 30 to 70 mol% in all monomers.

  When the proportion of the specific monomer (1) is less than 20 mol% in all monomers, the toughness may be inferior when the film or sheet is used, and when it exceeds 80 mol%, the film or sheet In such a case, sufficient transparency may not be obtained.

The specific monomer (2) used in the present invention is a cyclic olefin compound represented by the above formula (2), and specific examples thereof are not particularly limited. For example, the compounds listed below Can be illustrated.
Tetracyclo [6.2.1.1. ^3,6 0. ^2,7 ] Dec-9-ene,
4-methyltetracyclo [6.2.1.1. ^3,6 0 ^2,7 ] Dec-9-ene,
4-Ethyltetracyclo [6.2.1.1. ^3,6 0. ^2,7 ] Dec-9-ene,
4-propyltetracyclo [6.2.1.1. ^3,6 0. ^2,7 ] Dec-2-ene,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4-carboxylate, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate,
4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4-carboxylic acid methyl 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] ethyl dodeca-9-ene-4-carboxylate,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodec-9-ene-4,5-dicarboxylate,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylate methyl-5-carboxylate t-butyl,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-N-cyclohexylcarbonimide,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-N-ethylcarbonimide,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,4-N-cyclohexylsuccinimidetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride,
4-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-triethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-methyldimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene,
4-methyldiethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene.

As such a specific monomer (2), any of the compounds represented by the above formula (2) is preferably used. In the above formula (2), at least one of B ^{1 to} B ⁴ is a carbon number. It is more preferably a group selected from the group consisting of 1 to 3 alkyl groups, an alkoxycarbonyl group having 1 to 3 carbon atoms, and a trialkoxysilyl group having 1 to 3 carbon atoms.

Since these specific monomers (2) are cyclododecene monomers, the specific monomer (1) endo isomer remaining after the exo isomer of the specific monomer (1) is consumed by polymerization and Since the copolymerizability is good, it is possible to prevent the formation of an opaque polymer due to the chain of the endo form. In this invention, a specific monomer (2) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The ratio of the specific monomer (2) used in the method for producing the cyclic olefin-based addition copolymer of the present invention is 1.0 to 20 mol%, preferably 2.0 to 15 mol% in all monomers. More preferably, it is 3 to 10 mol%.

  If the ratio of the specific monomer (2) is less than 1.0 mol% in all monomers, an optically transparent film or sheet may not be obtained, and if it exceeds 20 mol%, polymerization occurs. In some cases, the activity is reduced, and the film or sheet of the produced polymer is not tough.

The specific monomer (3) used in the present invention is a cyclic olefin compound represented by the above formula (3), and specific examples thereof are not particularly limited. For example, the compounds listed below Can be illustrated.
Bicyclo [2.2.1] hept-2-ene,
5-methyl-bicyclo [2.2.1] hept-2-ene,
5,5-dimethyl-bicyclo [2.2.1] hept-2-ene,
5,6-dimethyl-bicyclo [2.2.1] hept-2-ene,
5-chloro-bicyclo [2.2.1] hept-2-ene,
5-fluoro-bicyclo [2.2.1] hept-2-ene,
5-Methoxy-bicyclo [2.2.1] hept-2-ene.

  As the specific monomer (3), any of the compounds represented by the above formula (3) is preferably used, and among them, when bicyclo [2.2.1] hept-2-ene is used, The resulting addition copolymer is preferable because the mechanical strength is particularly excellent. In this invention, a specific monomer (3) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The ratio of the specific monomer (3) used in the method for producing a cyclic olefin addition copolymer of the present invention is 10 to 70 mol%, preferably 20 to 60 mol%, more preferably in all monomers. 30 to 50 mol%.

  When the ratio of the specific monomer (3) is less than 10 mol% in all monomers, the film or sheet formed from the resulting addition copolymer is inferior in mechanical strength and optically opaque. In addition, if it exceeds 70 mol%, it may be difficult to remove the residual solvent from the film or sheet formed from the resulting addition copolymer.

  In the method for producing a cyclic olefin addition copolymer of the present invention, the monomer composition has a cyclic olefin type monomer capable of addition polymerization other than the specific monomers (1), (2) and (3) described above. The monomer may be contained in a range not impairing the object of the present invention.

Specifically, for example, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, tricyclo [5.2.1.0 ^2,6 ] dec-3,8-diene, and the like. Decene monomers
It can be used in order to improve the toughness of the resulting addition polymer in the range of 5 to 30 mol% in all monomers. Among these, when tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene is used as a monomer, carbon / carbon of the produced addition polymer is used to prevent heat degradation. It is desirable to hydrogenate at least 95% of the unsaturated bonds.

Further, for example, monomers such as 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene and 5-triethoxysilylbicyclo [2.2.1] hept-2-ene In order to improve the adhesion and adhesion of the resulting addition polymer in the range of 0.2 to 10 mol% in the monomer, an acid generator is added to the resulting film or sheet to crosslink the addition polymer. Can be used to make a body.
<Palladium catalyst>
In the method for producing a cyclic olefin-based addition copolymer of the present invention, the above-described addition copolymerization reaction of the monomer composition is performed in the presence of a palladium-based catalyst.

In the present invention, any palladium-based catalyst capable of addition copolymerization with a cyclic olefin-based monomer can be used.
1) palladium compound,
2) a phosphine compound having a group selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group and having a cone angle of 170 to 200, a phosphonium salt of the phosphine compound, and At least one selected from a complex of the phosphine compound and an organoaluminum compound,
3) A multicomponent catalyst (hereinafter referred to as multicomponent catalyst (1)) containing an ionic boron compound or an ionic aluminum compound is preferable.
Multi-component catalyst (1)
The multicomponent catalyst (1) contains the components 1), 2) and 3) described above.
1) Palladium compound Examples of the palladium compound constituting the multi-component catalyst (1) include palladium organic carboxylates, organic phosphites, organic phosphates, organic sulfonates, beta diketone compounds, halides and the like. Among these, palladium organic carboxylates, beta diketone compounds, and dibenzylidene acetone compounds are preferably used because they are compounds that are easily dissolved in a hydrocarbon solvent and have high polymerization activity.

Specific examples of these palladium compounds include palladium acetate, propionate, maleate, fumarate, butyrate, adipate, 2-ethylhexanoate, naphthenate, oleate, and dodecane. Organic carbonates of palladium such as acid salts, neodecanoate, 1,2-cyclohexanedicarboxylate, 5-norbornene-2-carboxylate, benzoate, phthalate, terephthalate, naphthoate, Organic carboxylic acid complexes of palladium such as tricyclohexylphosphine complex of palladium acetate, tri (o-tolyl) phosphine complex of palladium acetate, tricyclohexylphosphine complex of palladium acetate, palladium dibutyl phosphite, dibutyl phosphate, dioctyl Phosphites such as phosphate and dibutyl phosphate , Phosphate, palladium dodecylbenzenesulfonate, palladium organic sulfonate such as p-toluenesulfonate, bis (acetylacetonato) palladium, bis (hexafluoroacetylacetonato) palladium, bis (ethylacetate) Acetate) palladium, bis (phenylacetoacetate) palladium beta diketone compounds such as dichlorobis (triphenylphosphine) palladium, dichlorobis [tri (m-tolylphosphine)] palladium, dibromobis [tri (m-tolylphosphine)] palladium , dichlorobis [tri (m-xylyl) phosphine] palladium, dibromobis [tri (m-xylyl) phosphine] palladium, imidazole complex represented by _{[C 3 H 5 N 2]} 2 [PdCl 4] _{, [Ph 3 PCH 2 C (} O) C
Palladium halide complexes such as an acetonyltriphenylphosphonium complex represented by H ₃ ] ₂ [Pd ₂ Cl ₆ ] can be mentioned.

In addition, a combination of dibenzylideneacetone palladium [Pd ₂ (dba) ₃ ] and the like (dba represents dibenzylideneacetone), halides such as aryl chloride, benzyl chloride, bromobenzene, chlorobenzene, and bromonaphthalene, which will be described later. Also included are zerovalent palladium compounds that form aryl or allyl palladium halides in the presence of certain phosphine compounds.

In the preparation of the multi-component catalyst (1), such a palladium compound may be used alone or in combination of two or more.
2) a phosphine compound having a group selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group and having a cone angle of 170 to 200, a phosphonium salt of the phosphine compound, and The phosphine compound that can constitute the multicomponent catalyst (1) selected from a complex of the phosphine compound and an organoaluminum compound is a group selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group And a cone angle (Cone Angle θdeg) of 170 to 200.

Here, the cone angle θdeg (Cone Angle θdeg) of the tertiary phosphine compound is C
. A. Calculated by Tolman (Chem. Rev. Vol. 77, 313 (1977)), measured with a model formed by three substituents of metal and phosphorus atoms, assuming that the bond distance between metal atoms and phosphorus atoms is 2.28 mm. Is the cone angle θ.

Examples of the phosphine compound having a cone angle θdeg of 170 to 200 preferably used in the present invention include tricyclohexylphosphine, di-t-butylphenylphosphine, trineopentylphosphine, tri (t-butyl) phosphine, and tri (pentafluoro). Specific examples include phenyl) phosphine and tri (o-tolyl) phosphine. Di-t-butyl-2-biphenylphosphine, di-t-butyl-2′-dimethylamino-2-biphenylphosphine, dicyclohexyl-2-biphenylphosphine, dicyclohexyl-2′-i-propyl-2-biphenylphosphine And so on.

The phosphonium salt that can constitute the multi-component catalyst preferably used in the present invention is a phosphonium salt of the above specific phosphine compound, the above specific phosphine compound that is an electron-donating phosphorus compound, a super strong acid, a sulfonic acid, and It is a phosphonium salt obtained by reacting with a protonic acid selected from carboxylic acids and the like. Specific examples of such phosphonium salts include tricyclohexylphosphonium tetra (pentafluorophenyl) borate,
Tri-t-butylphosphonium tetra (pentafluorophenyl) borate,
Tricyclohexylphosphonium tetrafluoroborate,
Tricyclohexylphosphonium octanoate,
Tricyclohexylphosphonium acetate,
Tricyclohexylphosphonium trifluoromethanesulfonate,
Tri-t-butylphosphonium trifluoromethanesulfonate,
Tricyclohexylphosphonium p-toluenesulfonate,
Tricyclohexylphosphonium hexafluoroacetylacetonate,
Tricyclohexylphosphonium hexafluoroantimonate,
Tricyclohexylphosphonium hexafluorophosphonate,
Etc.

  The complex of the phosphine compound and the organoaluminum compound that can constitute the multicomponent catalyst (1) is a complex having a molar ratio of the specific phosphine compound and the organoaluminum compound of 1: 1. Here, as the organoaluminum compound, a trialkylaluminum compound or a dialkylaluminum compound is preferable.

As such a complex, specifically, for example,
Tricyclohexylaluminum complex of tricyclohexylphosphine triethylaluminum complex of tricyclohexylphosphine triisobutylaluminum complex of tricyclohexylphosphine diisobutylaluminum hydride complex of tricyclohexylphosphine triethylaluminum complex of tri (pentafluorophenyl) phosphine triethyl of tri (o-tolyl) phosphine An aluminum complex etc. are mentioned.

In the multi-component catalyst (1), these phosphine compounds, phosphonium salts, and compounds selected from complexes of phosphine compounds and organoaluminum compounds may be used alone or in combination of two or more. .
3) Ionic boron compound or ionic aluminum compound Specific examples of the ionic boron compound that can constitute the multicomponent catalyst (1) include, for example, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium. Tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenylcarbenium tetrakis (2,4,6-trifluorophenyl) borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis (pentafluorophenyl) Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diphenylanilinium Examples include tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) borate.

Moreover, as a specific example of the ionic aluminum compound which can comprise a multicomponent catalyst (1), for example,
Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate,
Triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] aluminate,
And triphenylcarbenium tetrakis (2,4,6-trifluorophenyl) aluminate.

These ionic boron compounds or ionic aluminum compounds may be used alone or in combination of two or more.
4) Organoaluminum compound In addition to the catalyst components 1) to 3) described above, the multi-component catalyst (1), which is a palladium catalyst preferably used in the present invention, further improves the activity of the catalyst and protects against oxygen. In order to reduce the influence, 4) It is also preferable to contain an organoaluminum compound.

Examples of the organoaluminum compound that can be contained in the above multi-component catalyst include alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, and butylalumoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, and diisobutylaluminum. Examples thereof include trialkylaluminum compounds such as hydride, diethylaluminum butoxide, diethylaluminum chloride and diethylaluminum fluoride, dialkylaluminum hydride compounds, dialkylaluminum alkoxide compounds and dialkylaluminum halides.

Although a multicomponent catalyst (1) is not specifically limited, It is preferable to contain each catalyst component mentioned above in the following ratios.
1) Palladium compound: 0.0005 to 0.02 mmol Pd atom with respect to 1 mol of the monomer,
2) A phosphine compound having a group selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group and having a cone angle of 170 to 200, a phosphonium salt of the phosphine compound, or Complex of phosphine compound and organoaluminum compound: 0.2 to 3.0 gram atom in terms of phosphine atom with respect to Pd1 gram atom of palladium compound 1),
3) Ionic boron compound or ionic aluminum compound: 0.1 to 10 mol per gram atom of Pd of the palladium compound,
4) Organoaluminum compound: It is a component that is used as necessary, but it may not be contained. When it is contained, it is preferably 0.1 to 20 mol per gram atom of Pd in the palladium compound 1).

The multi-component catalyst (1) may be prepared by adding each of the catalyst components 1) to 3) and 4) as necessary to a mixture of a monomer and a solvent simultaneously or sequentially. Well, 1,3-cyclohexadiene, bicyclo [2.2.1] hepta-2,5-diene, bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, tetracyclo [6.2.1.1 ^3,6 . 0 ^{2, 7} ]] in the presence of a cyclic diene or cyclic olefin such as dodeca-4-ene, or a linear diene compound such as 1,3-butadiene, 1,4-pentadiene, and the like Depending on the above, each catalyst component of 4) may be added simultaneously or sequentially and further ripened for preparation.
Multi-component catalyst (2)
In the present invention, as the palladium-based catalyst,
2-1) Organometallic compound of palladium having a palladium-carbon bond,
2-2) a phosphine compound,
2-3) A multi-component catalyst (2) containing an ionic boron compound can also be used.

2-1) Specific examples of organometallic compounds of palladium having a palladium-carbon bond include (allyl) palladium chloride dimer, (allyl) palladium trifluoroacetate dimer, (allyl) palladium (tricyclohexylphosphine). ) Chloride, (allyl) palladium (tricyclohexylphosphine) triflate, (methallyl) palladium chloride, (phenyl) palladium (tricyclohexylphosphine) triflate, (phenyl) palladium chloride, (1,5-cyclooctadiene) palladium ( Methyl) chloride, (bicyclo [2.2.1] hepta-2,5-diene) palladium chloride dimer, and the like. These compounds may be used alone or in combination of two or more. It can have.

2-2) As the phosphine compound, the phosphine compound mentioned in the catalyst component 2) of the multicomponent catalyst (1), that is, a substituent selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group A phosphine compound having a cone angle (Cone Angle θdeg) of 170 to 200 is preferable, among which tricyclohexylphosphine and tri-o-tolylphosphine are preferable. In the multi-component catalyst (2), when the phosphine compound is included as a ligand of the organometallic complex compound having a palladium-carbon bond as the component (2-1), it is not necessary to include it separately.

2-3) The ionic boron compound is the same as the ionic boron compound mentioned in the catalyst component 3) of the multi-component catalyst (1), and among these, an ionic boron compound of an alkali cation is preferable. Specifically, for example,
Lithium tetrakis (pentafluorophenyl) borate,
Sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Lithium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Examples thereof include potassium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate.

Although a multicomponent catalyst (2) is not specifically limited, It is preferable to contain each catalyst component mentioned above in the following ratios.
2-1) Organometallic compound of palladium having a palladium-carbon bond: 0.0005 to 0.02 mmol Pd atom with respect to 1 mol of the monomer,
2-2) Phosphine compound: 0.2 to 3.0 gram atom in terms of phosphine atom with respect to Pd1 gram atom of palladium organometallic compound 2-1),
2-3) Ionic boron compound: 0.1 to 10 mol per gram atom of Pd of organometallic compound 2-1) of palladium.
Single complex catalyst (3)
In the present invention, a single complex catalyst (3) having no palladium-carbon bond can also be used as the palladium-based catalyst.

Specific examples include complexes represented by the following general formula.
[(RCN) ₄ Pd] [CA] ₂
In the above formula, R is methyl, ethyl, iso-propyl, tert-butyl, phenyl, tolyl, naphthyl, cyclohexyl, bicyclo [2.2.1] heptanyl, bicyclo [2.2. .1] represents an alkyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, such as a hepta-2-enyl group,
CA represents a counter anion of a super strong acid represented by BF ₄ ⁻ , PF ₆ ⁻ , CF ₃ C (O) O ⁻ , CF ₃ SO ₃ ⁻ , and the like.

Such a single complex catalyst (3) of palladium is used in the range of 0.01 to 5.0 mmol Pd atoms with respect to 1 mol of the monomer.
In the present invention, the above-mentioned multi-component catalyst (1), (2) and single complex catalyst (3), or any other palladium catalyst can be used as the palladium catalyst. Catalyst (3) has relatively poor solubility in hydrocarbon solvents and has a slightly low polymerization activity, and multi-component catalyst (2) has a complicated process for synthesizing the complex of catalyst component 2-1). Since the complex is unstable in the air, it is particularly preferable to use the multicomponent catalyst (1).
<Production of cyclic olefin addition copolymer>
Addition Copolymerization In the method for producing a cyclic olefin addition polymer of the present invention, the above monomer composition is subjected to addition copolymerization using a palladium catalyst.

  The addition copolymerization according to the present invention is usually performed in a polymerization solvent. The solvent for polymerization is not particularly limited, but cycloaliphatic hydrocarbon solvents such as cyclohexane, cyclopentane and methylcyclopentane, aliphatic hydrocarbon solvents such as hexane, heptane and octane, toluene, benzene and xylene. , Aromatic hydrocarbon solvents such as mesitylene, solvents such as halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethylene, 1,1-dichloroethylene, tetrachloroethylene, chlorobenzene, dichlorobenzene, alone or 2 It can be used in combination of more than one species. Of these, alicyclic hydrocarbon solvents and aromatic hydrocarbon solvents are preferred. Such a polymerization solvent can be used normally in the range of 50 to 2,000 parts by weight with respect to 100 parts by weight of the monomer composition.

The addition copolymerization according to the present invention is preferably performed in the presence of a molecular weight regulator. When addition copolymerization is carried out in the presence of a molecular weight regulator, the resulting addition copolymer and other molecular weight distributions can be suitably controlled, and the solution viscosity should be controlled at the time of molding into a film or sheet. Can do.

  In the present invention, as a molecular weight regulator, ethylene, propylene, 1-butene, 1-hexene, 1-octene, α-olefin compounds such as trimethylsilylethylene, hydrogen, triethylsilane, tributylsilane, methanol, isopropanol, tert-butanol Etc. can be used. These molecular weight regulators can be suitably used in the range of 0.001 to 10 mol% with respect to the total monomers.

  In the present invention, diisobutylaluminum hydride, borane ether complex, alane ether complex or the like may be used as a molecular weight regulator. These molecular weight regulators can be suitably used in the range of 5 to 1000 moles with respect to 1 mole of palladium atoms of the palladium-based catalyst.

  In the addition copolymerization of the present invention, these molecular weight regulators may be used alone or in combination of two or more. In this invention, it is preferable to use an alpha olefin compound among the molecular weight regulators mentioned above, and it is more preferable to use ethylene.

In the addition copolymerization according to the present invention, the polymerization temperature is usually in the range of 0 to 150 ° C, preferably 50 to 150 ° C, more preferably 70 to 100 ° C.
In the present invention, any of the above-described method of batch-adding the respective components of the monomer composition and the method of sequential addition can be adopted. However, in the batch polymerization method, the monomer (1) and the single monomer are used. A method is preferred in which the polymerization is started with a monomer composition consisting of the whole amount of the body (2) and a part of the monomer (3), and the remaining monomer (3) is charged sequentially or continuously.
Further, in the continuous polymerization method (a vertical reactor, a tower reactor), it is preferable to charge each component at once or introduce a monomer composition in which each component is mixed in advance into the polymerization system. As the polymerization process method, either a batch polymerization method or a continuous polymerization method can be employed.

  In the present invention, any of the above-described method of batch-adding each component of the monomer composition and the sequential addition method can be employed. It is preferable to introduce a premixed monomer composition into the polymerization system. Moreover, as a polymerization process system, either a batch polymerization system or a continuous polymerization system can be adopted, but it is preferable to employ a batch polymerization system.

  In the production method of the present invention, the compound represented by the above formula (1) is obtained by addition copolymerization of the monomer composition containing each compound represented by the above formula (1) to (3). The structural unit represented by the following formula (4) derived from the above, the structural unit represented by the following formula (5) derived from the compound represented by the above formula (2), and the above formula (3) An addition copolymer containing a structural unit represented by the following formula (6) derived from the compound represented by

(In the formula ^(4), A ¹ ~A 4 are each independently a hydrogen atom, a halogen atom, atom or a group selected from alkyl groups such as methyl group or 3 to 10 carbon atoms, of A ¹ to A ⁴ At least one represents an alkyl group having 2 to 10 carbon atoms.)

[In formula (5), B ^{1 to} B ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and B ¹ and B ^2. Or B ¹
And B ³ cyclic ester groups, acid anhydride groups and N-alkyl or cycloalkyl substituted carbonimido groups, and the general formula — (CHR ¹ ) _k —X
Wherein X is selected from an alkoxycarbonyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon trialkylsiloxycarbonyl groups, and an alkoxy group having 1 to 3 carbon atoms alkoxysilyl group. And R ¹ is a hydrogen atom or a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group, and k represents an integer of 0 to 5.)
An atom or group selected from the group consisting of polar groups represented by: ]

(In formula (6), C ^{1 to} C ⁴ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group, and a halogen atom.)
The cyclic olefin addition copolymer obtained by the production method of the present invention is a structural unit represented by the above formula (5) in a proportion of usually 20 to 80 mol% of the structural unit represented by the above formula (4). 1.0 to 20 mol%, preferably 1.0 to 15 mol%, more preferably 2 to 10 mol%, and the structural unit represented by the above formula (6) is usually 10 to 70 mol%, Preferably it contains 20-60 mol%, More preferably, it contains in the ratio of 30-50 mol%, respectively.

When the proportion of the structural unit represented by the above formula (5) is less than 1.0 mol% in the obtained cyclic olefin addition copolymer, an optically transparent film or sheet may not be obtained. Moreover, when it exceeds 20 mol%, the toughness of the polymer obtained will fall and a film or a sheet | seat may become weak. Further, when the proportion of the structural unit represented by the above formula (6) is less than 10 mol%, the mechanical strength of the film or sheet may be small and optically opaque. If it exceeds mol%, it may be difficult to remove the remaining solvent from the film or sheet.
Hydrogenated cyclic olefin addition copolymer obtained by the production method of the present invention is obtained when a cyclic olefin monomer having an olefin unsaturated bond as a side chain substituent is used in the monomer composition. When an olefinically unsaturated bond is present in the resulting addition copolymer, it is preferable to hydrogenate (hydrogenate) the olefinically unsaturated bond. The higher the hydrogen conversion rate, the better, and it is usually 90% or higher, preferably 95% or higher, more preferably 99% or higher.

The method for hydrogenation is not particularly limited, and a known method for hydrogenating olefinically unsaturated bonds can be appropriately employed. For example, hydrogenation can be carried out in an inert solvent at a hydrogen gas pressure of 0.5 to 15 MPa and a reaction temperature of 0 to 200 ° C. in the presence of a hydrogenation catalyst. Decatalyst In the method for producing a cyclic olefin-based addition copolymer of the present invention, the palladium-based catalyst used for the addition copolymerization reaction and the catalyst used for the hydrogenation reaction carried out as necessary are removed by decatalysis. Is preferred. The method of decatalysis is not particularly limited, and can be appropriately selected depending on the nature and shape of the catalyst used. For example, a solution of a polymer obtained by stopping polymerization or a hydrogenated product thereof is converted into an oxycarboxylic acid such as lactic acid, glycolic acid, β-methyl-β-oxypropionic acid, γ-oxybutyric acid, or triphenylphosphine. Add sodium sulfonate, dipyridyl, quinoline, triethanolamine, dialkylethanolamine, ethylenediaminetetraacetate, etc., and extract and separate catalyst components by water, alcohols, ketones or esters or by coagulation separation of polymers. The catalyst can be removed by removing or treating with an adsorbent such as diatomaceous earth, silica, alumina, activated carbon and the like. By such a method, the addition copolymer obtained by this invention can remove the palladium atom derived from a catalyst normally to 5 ppm or less, Preferably it is 2 ppm or less, More preferably, it is 0.5 ppm or less.
Recovery In the production method of the present invention, the method for recovering the obtained cyclic olefin-based addition copolymer is not particularly limited, but an antioxidant is added to the obtained polymer solution as necessary. Examples thereof include a method of solidifying a polymer in a poor solvent such as alcohol or ketone and then recovering the polymer by drying, a method of recovering the polymer by heating the polymer solution and evaporating the solvent. Moreover, the solution containing the obtained cyclic olefin type addition copolymer can be used as a raw material as it is, and it can also collect | recover by shape | molding into a film and a sheet | seat by the solution casting method (cast method).

  The cyclic olefin addition copolymer obtained by the production method of the present invention has transparency. In the present invention, the cyclic olefin-based addition copolymer has “transparency” means that a polymer solution obtained by dissolving the copolymer in cyclohexane at 25 ° C. so as to be 10% by weight has an optical path length of 1 cm. Means that the light transmittance at 400 nm is 85% or more, measured using a quartz cell, and when the light transmittance is less than 85%, it is judged as “opaque” or “has turbidity”. .

  The molecular weight of the cyclic olefin-based addition copolymer obtained by the production method of the present invention is usually 10,000 to 200,000 in terms of polystyrene equivalent number average molecular weight (Mn) and 30,000 in terms of polystyrene equivalent weight average molecular weight (Mw). ˜500,000 (hereinafter, “polystyrene conversion” is omitted), preferably the number average molecular weight is 30,000 to 100,000, the weight average molecular weight is 50,000 to 300,000, and more preferably the number average molecular weight is 40. 1,000 to 70,000 and a weight average molecular weight of 100,000 to 200,000.

  When the number average molecular weight of the cyclic olefin-based addition copolymer is less than 10,000, the mechanical strength is weak when the film or sheet is formed, and the cyclic olefin addition copolymer may be easily broken. On the other hand, when the number average molecular weight exceeds 200,000, the viscosity of the polymer solution composition increases, and it may be difficult to form a film or sheet.

The glass transition temperature (Tg) of the cyclic olefin addition copolymer obtained by the production method of the present invention is usually from 150 to 450 ° C, preferably from 200 to 400 ° C. When the glass transition temperature of the polymer is less than 150 ° C., the heat resistance is inferior, which is not preferable. On the other hand, when it exceeds 450 ° C., the toughness may be inferior when it is formed into a film or sheet, and it may be easily broken. The glass transition temperature includes the types of A ^{1 to} A ⁴ of the structural unit represented by the above formula (4), the types of substituents of C ^{1 to} C ⁴ of the structural unit represented by the above formula (6), and fat. It can be easily adjusted depending on the kind of the aromatic and / or aromatic cyclic substituent.
-Cyclic olefin addition copolymer The cyclic olefin addition copolymer according to the present invention is:
20 to 80 mol% of a structural unit represented by the following formula (4),
1 to 20 mol%, preferably 2 to 15 mol%, more preferably 3 to 10 mol% of a structural unit represented by the following formula (5), and 10 to 10 of a structural unit represented by the following formula (6) 70 mol%, preferably 20-60 mol%, more preferably 30-50 mol%
It contains in the ratio.

(In the formula ^(4), A ¹ ~A 4 are each independently a hydrogen atom, a halogen atom, atom or a group selected from alkyl groups such as methyl group or 2 to 10 carbon atoms, of A ¹ to A ⁴ At least one represents an alkyl group having 2 to 10 carbon atoms.)

[In formula (5), B ^{1 to} B ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and B ¹ and B ^2. Or B ¹
And B ³ cyclic ester groups, acid anhydride groups and N-alkyl or cycloalkyl substituted carbonimido groups, and the general formula — (CHR ¹ ) _k —X
Wherein X is selected from an alkoxycarbonyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon trialkylsiloxycarbonyl groups, and an alkoxy group having 1 to 3 carbon atoms alkoxysilyl group. And R ¹ is a hydrogen atom or a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group, and k represents an integer of 0 to 5.)
An atom or group selected from the group consisting of polar groups represented by: ]

(In formula (6), C ^{1 to} C ⁴ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group, and a halogen atom.)
When the proportion of the structural unit represented by the above formula (5) is less than 1.0 mol% in the cyclic olefin addition copolymer of the present invention, an optically transparent film or sheet cannot be obtained. Moreover, when it exceeds 20 mol%, the toughness of the polymer obtained will fall and the film or sheet may become brittle. Further, when the proportion of the structural unit represented by the above formula (6) is less than 10 mol%, the mechanical strength of the film or sheet may be small and optically opaque. If it exceeds mol%, it may be difficult to remove the remaining solvent from the film or sheet.

  The cyclic olefin addition copolymer of the present invention can be preferably produced by the above-described method for producing the cyclic olefin addition copolymer of the present invention. In addition, each structural unit represented by the general formulas (4), (5) and (6) of the cyclic olefin addition copolymer of the present invention has a single amount having an olefinically unsaturated bond as a side chain substituent. It may be formed by hydrogenating the resulting polymer after addition polymerization of the product.

The cyclic olefin addition copolymer of the present invention has transparency.
As for the molecular weight of the cyclic olefin addition copolymer of the present invention, the number average molecular weight (Mn) in terms of polystyrene is usually 10,000 to 200,000, and the weight average molecular weight (Mw) in terms of polystyrene is 30,000 to 500,000 ( Hereinafter, “polystyrene conversion” is omitted), preferably the number average molecular weight is 30,000 to 100,000, the weight average molecular weight is 50,000 to 300,000, and more preferably the number average molecular weight is 40,000 to 70,000. And a weight average molecular weight of 100,000 to 200,000.

  When the number average molecular weight of the cyclic olefin-based addition copolymer is less than 10,000, the mechanical strength is weak when the film or sheet is formed, and the cyclic olefin addition copolymer may be easily broken. On the other hand, when the number average molecular weight exceeds 200,000, the viscosity of the polymer solution composition increases, and it may be difficult to form a film or sheet.

The glass transition temperature (Tg) of the cyclic olefin-based addition copolymer of the present invention is usually from 150 to 450 ° C, preferably from 200 to 400 ° C. When the glass transition temperature of the polymer is less than 150 ° C., the heat resistance is inferior, which is not preferable. On the other hand, when it exceeds 450 ° C., the toughness may be inferior when it is formed into a film or sheet, and it may be easily broken. The glass transition temperature includes the types of A ^{1 to} A ⁴ of the structural unit represented by the above formula (4), the types of substituents of C ^{1 to} C ⁴ of the structural unit represented by the above formula (6), and fat. It can be easily adjusted depending on the kind of the aromatic and / or aromatic cyclic substituent.
<Molding>
The cyclic olefin addition copolymer obtained by the production method of the present invention and the cyclic olefin addition copolymer of the present invention (hereinafter referred to as the cyclic olefin addition copolymer according to the present invention) are not particularly limited. Although it can shape | mold by well-known various shaping | molding methods, it is preferable to shape | mold into a film, a sheet | seat, or a thin film by the solution casting method (cast method).

  Production of a film or sheet by the solution casting method can be performed, for example, as follows. That is, the solid content of the cycloolefin addition copolymer according to the present invention, a solvent, and optionally additives such as an acid generator, an antioxidant, and a filler, is 5 to 50% by weight, preferably 15 to A 40% by weight, more preferably 20 to 35% by weight, cyclic olefin-based addition copolymer solution composition is prepared, and this solution composition is bar coater, T-die, T-die with bar, doctor knife, roll coat, die coat. The polymer solution composition is cast on a heat-resistant material such as polyethylene terephthalate, a steel belt, or a support such as a flat plate or roll such as a metal foil. Thereafter, the polymer solution composition on the support varies depending on the type of the solvent, but the residual solvent is 20% by weight or less, preferably 10% by weight or less in the temperature range of 20 to 100 ° C., preferably 30 to 80 ° C. Evaporate to dryness. Thereafter, the film or sheet is peeled off from the formed support and further evaporated and dried.

  When the cyclic olefin addition copolymer according to the present invention has, as a side chain substituent, an easily acid-decomposable carboxylic acid ester group or an alkoxysilyl group that is easily hydrolyzed and condensed with an acid as a substituent. When a film or sheet is produced, a thermal acid generator or a photoacid generator is added to form a film or sheet by a solution casting method, and then heat treatment or light irradiation is performed to generate an acid to crosslink. To form a film or sheet of a crosslinked cyclic olefin addition copolymer having solvent resistance and chemical resistance.

The thermal acid generator is preferably a thermal acid generator that generates an acid at 50 ° C. or higher, and examples thereof include the following compounds 1) or 2).
1) An aromatic sulfonium salt, aromatic ammonium salt, aromatic pyridinium salt, aromatic phosphonium salt in which the counter anion is selected from BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , B (C ₆ F ₅ ) _4, etc. A compound that generates an acid when heated to 50 ° C. or higher, such as an aromatic iodonium salt, a hydrazinium salt, or an iron salt of a metallocene.

  2) Trialkyl phosphites, triaryl phosphites, dialkyl phosphites, monoalkyl phosphites, hypophosphites, secondary or tertiary alkyl esters of arylphosphonic acids or cyclo Alkyl ester, secondary or tertiary alkyl ester or cycloalkyl ester of organic phosphoric acid, silyl ester of organic carboxylic acid, tertiary alkyl ester or cycloalkyl ester, secondary or tertiary alkyl of organic sulfonic acid A compound that generates an acid by heating to 50 ° C. or higher in the presence or absence of water or water vapor, such as an ester or a cycloalkyl ester.

Among these, the compound 2) is preferable because it has good compatibility with the cyclic olefin addition polymer used in the present invention and is excellent in storage stability of the composition solution.
Photoacid generators include diazonium salts, ammonium salts, and iodonium salts that generate Bronsted acids or Lewis acids upon irradiation with ultraviolet rays such as g rays, h rays, and i rays, far ultraviolet rays, X rays, and electron rays. , Onium salts such as sulfonium salts, phosphonium salts, arsonium salts, oxonium salts, halogenated organic compounds such as halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing benzophenone compounds, others, quinonediazide compounds, α, α-bis (Sulphonyl) diazomethane compounds, α-carbonyl-α-sulfonyldiazomethane compounds, sulfonyl compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds and the like can be mentioned.

  These acid generators may be used alone or in combination of two or more, and can be preferably used in the range of about 0.001 to 5 parts by weight per 100 parts by weight of the addition copolymer.

  The cyclic olefin-based addition copolymer according to the present invention includes a phenol-based antioxidant, a lactone-based antioxidant, a phosphorus-based antioxidant, a thioether-based oxidation, in order to further improve oxidation resistance and coloration resistance. At least one selected from the inhibitors can be blended at a ratio of 0.001 to 5 parts by weight per 100 parts by weight of the cyclic olefin addition copolymer.

For example, as an antioxidant, 2,6-di-t-butyl-4-methylphenol, 4,4′-thiobis- (6-t-butyl-3-methyl-phenyl), 1,1-bis (4 -Hydroxyphenyl) cyclohexane, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), tetrakis [methylene-3-3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearate, 2,5-di-t-butylhydroquinone, pentaerythrityl-tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl)] propionate, phenolic antioxidants, hydroquinone antioxidants, and bis- (2,6-di-t-butyl-4-methyl) Phenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl phosphite), tetrakis (2,4-di-t-butyl-5-methylphenyl) 4,4′-biphenylene diphosphonite, 3,5-di-
t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tris (4-methoxy-3,5-diphenyl) phosphite, tris Phosphorus secondary antioxidants such as (nonylphenyl) phosphite, sulfur secondary antioxidants such as dilauryl-3,3′-thiodipropionate, 2-mercaptobenzimidazole, and the like can be added.

  The cyclic olefin addition copolymer according to the present invention is provided with, for example, an ITO electrode, an oxygen, water vapor barrier film, a hard coat laminated film, etc. as necessary, and a liquid crystal display element substrate, a light guide plate, a polarizing plate protective film , Retardation film, liquid crystal backlight, liquid crystal touch panel, polarizing plate, transparent conductive film, coated film, optical fiber, lens, optical disk, etc. It can also be used for insulating layer materials for electronic parts, adhesives, medical devices, containers and the like.

  Furthermore, since the cyclic olefin addition copolymer according to the present invention has excellent heat resistance and excellent adhesion and adhesion to other materials, such as plastic, copper, silver, gold, aluminum, etc. It is a thin film coating material on the surface of ceramics such as metal, glass, silica, titania, zirconia, alumina, etc., an interlayer coating material or an adhesive material of a multilayer material, and is very useful in the field where heat resistance is required.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

The molecular weight, glass transition temperature, total light transmittance, and water absorption were measured or evaluated by the following methods for film cracking, tensile strength, proportion of structural units in the copolymer, and NMR spectrum.

(1) Number average molecular weight, weight average molecular weight 150C type gel permeation chromatography device (GPC) manufactured by WATERS
) Was measured at 120 ° C. using o-dichlorobenzene as a solvent using an H type column manufactured by Tosoh Corporation. The obtained molecular weight is a standard polystyrene equivalent value.

(2) Glass transition temperature (Tg)
The glass transition temperature is measured by dynamic viscoelasticity. That is, the peak temperature of temperature dispersion of Tanδ (ratio of storage elastic modulus E ′ and loss elastic modulus E ″, Tanδ = E ″ / E ′) was defined as Tg.

  The measurement of dynamic viscoelasticity uses Leo Vibron DDV-01FP (manufactured by Orientec Co., Ltd.), the measurement frequency is 10 Hz, the heating rate is 4 ° C./min, the excitation mode is a single waveform, and the excitation amplitude is 2. Under the condition of 5 μm, the peak temperature of Tan δ was measured.

(3) Total light transmittance Based on ASTM-D1003, it was set as the film of thickness 100 micrometers, and the light transmittance in wavelength 400nm was measured.

(4) Water absorption rate After the polymer film was immersed in water at 23 ° C for 24 hours, the water absorption rate was measured by the change in weight before and after the immersion.

(5) Evaluation of film cracking A film having a thickness of about 100 μm was bent at 180 degrees on a 10 cm long steel rod having a diameter of 3 mm, and the film cracking was determined.

As a result, a film bent at 180 degrees was evaluated as “no crack”, and a film that was not bent at 180 degrees and had a crack was evaluated as “cracked”.
(6) Tensile strength, elongation According to JIS K7113, the test piece was pulled at a pulling speed of 3 mm / min. Measured with

(7) The proportion of the structural unit in the copolymer was determined by measuring the residual monomer present in the polymer solution after the completion of polymerization with a cas chromatogram (GC).
(8) ¹ H-NMR spectrum A 270 MHz ¹ H-NMR (proton nuclear magnetic resonance) apparatus manufactured by JEOL Ltd.
Measurement was performed using S (tetramethylsilane) and deuterated benzene (C ₆ D ₆ ) as a solvent.

(9) ¹³ C-NMR spectrum The ¹³ C-NMR spectrum was measured with a 67.8 MHz ¹³ C-NMR (nuclear magnetic resonance) apparatus manufactured by JEOL, Ltd., using deuterated benzene (C ₆ D ₆ ) as a solvent.

Cyclohexane 41.0 dehydrated in a 100 ml glass pressure bottle under nitrogen atmosphere
g, 4.6 g of toluene, and then 50.0 mmol (7.51 g) of 5-butylbicyclo [2.2.1] hept-2-ene with an endo / exo ratio of 80/20, bicyclo [ 2.
2.1] Hept-2-ene 26.0 mmol (2.45 g), 4-methyltetracyclo [6.3.1.1 ^3,6 . 0 ^2,7 . ] 5.0 mmol of methyl dodeca-9-ene-4-carboxylate was charged and sealed with a crown with a rubber seal. To this pressure bottle, 7 ml of gaseous 0.1 MPa ethylene was added as a molecular weight regulator, and 0.
333 × 10 ⁻³ mmol, tricyclohexylphosphine 0.25 × 10 ⁻³ mmol were added, and finally triphenylcarbenium tetrakis (pentafluorophenyl) borate 0.333 × 10 ⁻³ mmol was added at 75 ° C. Polymerization was started by isothermal polymerization. Two hours after the start of polymerization, 12 mmol of bicyclo [2.2.1] hept-2-ene was added, and after 4 hours, 7 mmol was added, and polymerization was carried out for 6 hours. The conversion ratio of all monomers to the polymer was 93%.

Conversion of 5-butylbicyclo [2.2.1] hept-2-ene to polymer was 90%, 4-methyltetracyclo [6.3.1.1 ^3,6 . 0 ^2,7 . The conversion of methyl dodeca-9-ene-4-carboxylate to polymer was 60%.

The polymer solution was poured into 1 L of isopropanol to solidify the polymer. This polymer was dissolved in cyclohexane, poured again into isopropanol, and purified by reprecipitation. The polymer was dried under reduced pressure at 80 ° C. for 17 hours to obtain a polymer A.

The ¹ H-NMR spectrum of the obtained polymer A is shown in FIG. 1, and the ¹³ C-NMR spectrum is shown in FIG.
Respectively.
This polymer dissolved transparently in cyclohexane, methylcyclohexane and o-dichlorobenzene at 25 ° C., but dissolved in toluene at 25 ° C., but was cloudy.

The number average molecular weight of this polymer was 68,000, and the weight average molecular weight was 156,000.
From the gas chromatographic analysis of the residual monomer in the polymer solution, the proportion of structural units derived from 5-butylbicyclo [2.2.1] hept-2-ene in the polymer was 48.4 mol%, 4 -Methyltetracyclo [6.3.1.1 ^3,6 . 0 ^2,7 . The proportion of structural units derived from methyl dodeca-9-ene-4-carboxylate was 3.2 mol%.

5 g of this polymer, 0.025 g of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate as an antioxidant,
A polymer solution was prepared by dissolving 0.025 g of 2,4-di-t-butylphenyl phosphite in 20 g of a solvent of cyclohexane / toluene (95/5 volume ratio). A film with a residual solvent of 8% was formed by casting, and further contacted with superheated steam at 180 ° C. for 90 minutes to remove the residual solvent, thereby obtaining a film FA-1 having a thickness of 100 μm.

  The physical property evaluation results are shown in Table 1.

In Example 1, as a monomer, 5-butylbicyclo [2.2.1] hept-2-ene
50.0 mmol (7.51 g), bicyclo [2.2.1] hept-2-ene 26.0
Mmol (2.45 g), 4-methyltetracyclo [6.3.1.1 ^3,6 . 0 ^2,7 . ] 3.0 mmol of methyl dodeca-9-ene-4-carboxylate and 1.65 mmol of 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene were charged, polymerized, and 2
After 12 hours, 12 mmol of bicyclo [2.2.1] hept-2-ene and 0.9 mmol of 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene were added. Further, after 4 hours from the start of polymerization, 7.0 mmol of bicyclo [2.2.1] hept-2-ene and 5-
0.45 mmol of trimethoxysilylbicyclo [2.2.1] hept-2-ene was added. Others were performed in the same manner as in Example-1. Polymerization was stopped after 6 hours from the start of polymerization, and solidified and dried in the same manner as in Example 1 to obtain a polymer B. The conversion to polymer was 92% from the measurement of the solid content of the polymer solution.

The ¹ H-NMR spectrum of the obtained polymer B is shown in FIG.
From these, the proportion of structural units derived from 5-butylbicyclo [2.2.1] hept-2-ene in the polymer was 48.9 mol%, and 4-methyltetracyclo [6.3.1.1]. ^3,6 . 0 ^2,7 . The proportion of structural units derived from methyl dodec-9-ene-4-carboxylate is 2.2 mol%, and structural units derived from 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene The ratio was 2.2 mol%.

The number average molecular weight of the polymer B was 84,000, and the weight average molecular weight was 143,000.
5 g of this polymer B, 0.025 g of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate as an antioxidant, tris (2,4-di-t -0.025 g of butylphenyl phosphite and 0.035 g of p-methylcyclohexyl p-toluenesulfonate as a thermal acid generator were dissolved in 20 g of a solvent of cyclohexane / toluene (95/5 volume ratio) to obtain a polymer solution. A film with a residual solvent of 8% was formed by casting, and further contacted with superheated steam at 180 ° C. for 90 minutes to remove the residual solvent to obtain a film FB-1 having a thickness of 100 μm. .

  The physical property evaluation results are shown in Table-1.

In the production of the film of Example 2, the same procedure as in Example 2 was performed except that the polymer A was used instead of the polymer B, and 4-methyltetracyclo [6.3.1.1 ^{3, 6} ． 0 ^2,7 . And a polymer containing 0.1 mol% of a structural unit in which a structural unit derived from methyl dodeca-9-ene-4-carboxylate is partially hydrolyzed and a carboxylmethyl group is hydrolyzed to a carboxyl group. A film FA-2 having a thickness of 100 μm was obtained.

  The physical property evaluation results are shown in Table-1.

In Example 1, 4-methyltetracyclo [6.3.1.1 ^3,6 . 0 ^2,7 . ] Dodeca-9-ene-4-carboxylate 4-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 . ^0,7 ] dodec-9-ene was used in the same manner as in Example 1 except that 5.0 mmol of polymer was used.

The conversion ratio of all monomers to the polymer was 94%. Conversion of 5-butylbicyclo [2.2.1] hept-2-ene to polymer was 89%, 4-trimethoxysilyltetracyclo [6.3.1.1 ^3,6 . 0 ^2,7 . The conversion of dodec-9-ene to polymer was 90%.

This polymer dissolved transparently in cyclohexane, methylcyclohexane and o-dichlorobenzene at 25 ° C., but dissolved in toluene at 25 ° C., but was cloudy.
The number average molecular weight of the polymer C was 64,000, and the weight average molecular weight was 149,000.

The proportion of structural units derived from 5-butylbicyclo [2.2.1] hept-2-ene in the polymer was 47.3 mol%, 4-trimethoxysilyltetracyclo [6.3.1.1 ^{3 , 6} . 0 ^2,7 . The proportion of structural units derived from dodeca-9-ene was 4.8 mol%.

  Next, in the same manner as in Example 1, a 100 μm film FC-1 was obtained. The evaluation results are shown in Table-1.

Instead of 5-butylbicyclo [2.2.1] hept-2-ene in Example 1
Using 5-ethylbicyclo [2.2.1] hept-2-ene with an endo / exo ratio of 78/22, the addition time of bicyclo [2.2.1] hept-2-ene was started. Thereafter, polymer D was obtained in the same manner as in Example 1 except that 2 hours later was changed 1.5 hours later, 4 hours later 3 hours later.

The ¹ H-NMR spectrum of the resulting polymer D is shown in FIG.
The number average molecular weight of this polymer D was 58,000, and the weight average molecular weight was 143,000.

The proportion of structural units derived from 5-ethylbicyclo [2.2.1] hept-2-ene in the polymer D was 48.8 mol%, 4-methyltetracyclo [6.3.1.1 ^{3, 6} ． 0 ^2,7 . The proportion of structural units derived from methyl dodeca-9-ene-4-carboxylate was 3.2 mol%.

  Next, a 100 μm film FD-1 was obtained in the same manner as in Example 1. The evaluation results are shown in Table-1.

In Example 1, in place of 5-butylbicyclo [2.2.1] hept-2-ene, 5-hexylbicyclo [2.2.1] hepta having an endo / exo ratio of 82/18 is used. A polymer E was obtained in the same manner as in Example 1 except that 2-ene was used.

A ¹ H-NMR spectrum of the obtained polymer E is shown in FIG.
The number average molecular weight of this polymer E was 38,000, and the weight average molecular weight was 123,000.

The proportion of structural units derived from 5-hexylbicyclo [2.2.1] hept-2-ene in polymer E was 48.0 mol%, 4-methyltetracyclo [6.3.1.1 ^{3, 6} ． 0 ^2,7 . The proportion of structural units derived from methyl dodeca-9-ene-4-carboxylate was 3.3 mol%.

  Next, a 100 μm film FE-1 was obtained in the same manner as in Example 1. The evaluation results are shown in Table-1.

  In Example 1, 30.0 mmol of 5-butylbicyclo [2.2.1] hept-2-ene and 65 mmol of bicyclo [2.2.1] hept-2-ene are charged before the start of polymerization. Otherwise, the same procedure as in Example 1 was conducted to obtain a polymer F with a conversion rate to a polymer of 95%.

The proportion of structural units derived from 5-butylbicyclo [2.2.1] hept-2-ene in polymer E was 29.5 mol%, 4-methyltetracyclo [6.3.1.1 ^{3, 6} ． 0 ^2,7 . The proportion of structural units derived from methyl dodeca-9-ene-4-carboxylate was 3.1 mol%.

The number average molecular weight of this polymer F was 54,000, and the weight average molecular weight was 158,000.
Next, a 100 μm film FF-1 was obtained in the same manner as in Example 1. The evaluation results are shown in Table-1.
Comparative Example 1
In Example 1, the catalyst of Example 1 was used by using only 100 mmol of 5-butylbicyclo [2.2.1] hept-2-ene having a ratio of endo / exo as 80/20 as a monomer. Was used for polymerization at 75 ° C.

The polymer solution 1 hour after the start of the polymerization was transparent, the conversion rate to the polymer was 65%, and the remaining 5-butylbicyclo [2.2.1] hept-2-ene endo / exo Body ratio is 95 /
It was 5. Further, after 2 hours from the start of polymerization, the polymer solution became cloudy, the conversion rate to the polymer was 70%, and the remaining endo-form of 5-butylbicyclo [2.2.1] hept-2-ene / The ratio of exo-form was 100/0 and only endo-form. Further, after 6 hours from the start of the polymerization, the conversion to the polymer was 80% and the turbidity of the polymer solution increased. The conversion to a polymer 10 hours after the start of polymerization was 82%, and the polymerization was hardly progressed. Here, the polymerization was stopped, and the polymer G was obtained by coagulation and drying in the same manner as in Example 1.

  Even though the polymer F was dissolved in cyclohexane, toluene, chlorobenzene, or o-dichlorobenzene, a transparent solution was not obtained. Therefore, a film FG-1 having a film thickness of 90 to 110 μm was obtained in the same manner as in Example 1. The film was very poor in transparency.

The evaluation results are shown in Table 1.
Comparative Example 2
As a monomer in Example 1, 50 mmol of 5-butylbicyclo [2.2.1] hept-2-ene having an endo / exo ratio of 80/20 at the start of polymerization and bicyclo [2.2.1]. ] Same as Example 1 except that only 31 mmol of hepta-2-ene was used and 12 mmol of bicyclo [2.2.1] hept-2-ene was added after 2 hours after the start of polymerization and 4 mmol after 4 hours. Went to. However, the polymer solution after 4 hours began to become cloudy. The polymerization was stopped after 6 hours. The conversion to polymer was 95%, and the conversion of 5-butylbicyclo [2.2.1] hept-2-ene to polymer was 90%.

The ratio of the structural unit derived from 5-butylbicyclo [2.2.1] hept-2-ene in the polymer H was 47.4 mol%.
The number average molecular weight of the polymer H was 44,000, and the weight average molecular weight was 153,000.

A film was produced in the same manner as in Example 1 to obtain a 100 μm film FH-1.
The evaluation results are shown in Table 1.
Comparative Example 3
Cyclohexane 41.0 dehydrated in a 100 ml glass pressure bottle under nitrogen atmosphere
g, 4.6 g of toluene, and then 90 mmol of 5-butylbicyclo [2.2.1] hept-2-ene having an endo / exo ratio of 80/20, 4-methyltetracyclo [6.3 .
1.1 ^3,6 . 0 ^2,7 . ] 10 mmol of methyl dodeca-9-ene-4-carboxylate was charged and sealed with a crown with a rubber seal. To this pressure bottle, 7 ml of gaseous 0.1 MPa ethylene was added as a molecular weight regulator, and 0.666 × 10 ⁻³ mmol of palladium acetate and 0.50 × 10 ⁻³ mmol of tricyclohexylphosphine were added. Finally, triphenylcarbenium tetrakis (pentafluorophenyl) borate 0.666
Polymerization was started by adding isothermal polymerization at 75 ° C. after adding × 10 ⁻³ mmol. 1.5 hours after the start of the polymerization, the conversion rate to the polymer was 65%, and the polymer solution began to become cloudy. The polymerization was further continued, but the conversion rate to the polymer after 4 hours was 70%, the conversion rate to the polymer after 10 hours was 75%, and the polymerization rate decreased rapidly in the latter half of the polymerization. Polymerization was stopped in 10 hours to obtain a polymer I.

The number average molecular weight of the polymer I is 42,000, the weight average molecular weight is 148,000, and 4-methyltetracyclo [6.3.1.1 ^3,6 . 0 ^2,7 . The proportion of structural units derived from methyl dodeca-9-ene-4-carboxylate was 5.8 mol%.

Next, a 100 μm film FI-1 was obtained in the same manner as in Example 1.
The evaluation results are shown in Table 1.
Reference example 1
Cyclohexane 41.0 dehydrated in a 100 ml glass pressure bottle under nitrogen atmosphere
g, 4.6 g of toluene, and then 50.0 mmol (7.51 g) of 5-butylbicyclo [2.2.1] hept-2-ene with an endo / exo ratio of 80/20, bicyclo [ 2.
2.1] 26.0 mmol (2.45 g) hept-2-ene, 4-methyltetracyclo [6.3.1.1 ^3,6 . 0 ^2,7 . ] 5.0 mmol of methyl dodeca-9-ene-4-carboxylate was charged and sealed with a crown with a rubber seal. As a molecular weight regulator, 1 mmol of 1-hexene was added to the pressure bottle, and the catalyst nickel octoate 0.04 mmol, triphenylcarbenium tetrakis (pentafluorophenyl) borate 0.048 mmol, triethylaluminum 0.20 The polymerization was initiated by isothermal polymerization at 25 ° C. with the addition of mmol. One hour after the start of polymerization, 12 mmol of bicyclo [2.2.1] hept-2-ene was added, and 7 mmol was added after 1.5 hours, and polymerization was carried out for 3 hours. The conversion ratio of all monomers to the polymer was 88%.

Conversion of 5-butylbicyclo [2.2.1] hept-2-ene to polymer was 84%, 4-methyltetracyclo [6.3.1.1 ^3,6 . 0 ^2,7 . The conversion of methyl dodeca-9-ene-4-carboxylate to polymer was 60%.

The polymer solution was poured into 1 L of isopropanol to solidify the polymer. This polymer was dissolved in cyclohexane, poured again into isopropanol, and purified by reprecipitation. The polymer was dried under reduced pressure at 80 ° C. for 17 hours to obtain a polymer J.

This polymer was transparently dissolved in cyclohexane, methylcyclohexane and o-dichlorobenzene at 25 ° C.
The number average molecular weight of this polymer was 38,000, and the weight average molecular weight was 116,000.

From the gas chromatographic analysis of the residual monomer in the polymer solution, the proportion of structural units derived from 5-butylbicyclo [2.2.1] hept-2-ene in the polymer was 47.7 mol%, 4 -Methyltetracyclo [6.3.1.1 ^3,6 . 0 ^2,7 . The proportion of structural units derived from methyl dodeca-9-ene-4-carboxylate was 3.4 mol%.

Next, a film FJ-1 having a thickness of 100 μm was obtained in the same manner as in Example 1.
The evaluation results are shown in Table 1.

  According to the present invention, a cyclic olefin addition copolymer suitable for optical materials having easy toughness, transparency, heat resistance and low water absorption can be obtained. The form of the optical material is preferably a film or a sheet. For example, an ITO electrode, oxygen, water vapor barrier film, coat laminated film, etc. are applied, and a liquid crystal display element substrate, a light guide plate, a polarizing plate protective film, a retardation film, a liquid crystal backlight, a liquid crystal touch panel, a transparent conductive film, It can be used in applications such as coated films, optical fibers, lenses, and optical disks. It can also be used for insulating layer materials for electronic parts, adhesives, medical devices, containers and the like.

FIG. 1 shows the ¹ H-NMR spectrum of the polymer A obtained in Example 1. FIG. 2 shows the ¹³ C-NMR spectrum of the polymer A obtained in Example 1. FIG. 3 shows the ¹ H-NMR spectrum of the polymer B obtained in Example 2. FIG. 4 shows the ¹ H-NMR spectrum of polymer D obtained in Example 5. FIG. 5 shows the ¹ H-NMR spectrum of the polymer E obtained in Example 6.

Claims (10)

In all monomers,
20-80 mol% of a compound represented by the following formula (1),
1 to 20 mol% of a compound represented by the following formula (2), and 10 to 70 mol% of a compound represented by the following formula (3)
A method for producing a cyclic olefin-based addition copolymer, wherein the monomer composition is subjected to addition copolymerization using a palladium-based catalyst;

(In the formula ^(1), A 1 ~A ⁴ are each independently a hydrogen atom, a halogen atom, atom or a group selected from alkyl groups such as methyl group or 2 to 10 carbon atoms, of A ¹ to A ⁴ At least one represents an alkyl group having 2 to 10 carbon atoms),

[In the formula (2), B ^{1 to} B ⁴ are each independently a hydrocarbon group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group, and B ¹ and B ^2. Or B ¹
And B ³ cyclic ester groups, acid anhydride groups and N-alkyl or cycloalkyl substituted carbonimido groups, and the general formula — (CHR ¹ ) _k —X
Wherein X is selected from an alkoxycarbonyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon trialkylsiloxycarbonyl groups, and an alkoxy group having 1 to 3 carbon atoms alkoxysilyl group. And R ¹ is a hydrogen atom or a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group, and k represents an integer of 0 to 5.)
An atom or group selected from the group consisting of polar groups represented by: ],

(In formula (3), C ^{1 to} C ⁴ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group, and a halogen atom).   The compound represented by the formula (1) is a C3-C6 monoalkyl-substituted bicyclo [2.2.1] hepta having an endo / exo ratio of 60/40 to 95/5. It is 2-ene, The manufacturing method of the cyclic olefin type addition copolymer of Claim 1 characterized by the above-mentioned.   The compound represented by the formula (1) is 5-butylbicyclo [2.2.1] hept-2-ene having an endo / exo ratio of 60/40 to 95/5. The method for producing a cyclic olefin-based addition polymer according to claim 1 or 2. In the formula (2), at least one of B ^{1 to} B ⁴ is an alkyl group having 1 to 3 carbon atoms, an alkoxycarbonyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. The method for producing a cyclic olefin addition copolymer according to any one of claims 1 to 3, which is a group selected from the group consisting of trialkoxysilyl groups.   The cyclic olefin addition copolymer according to any one of claims 1 to 4, wherein the compound represented by the formula (3) is bicyclo [2.2.1] hept-2-ene. Manufacturing method. Palladium-based catalyst
1) palladium compound,
2) a phosphine compound having a group selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group and having a cone angle of 170 to 200, a phosphonium salt of the phosphine compound, and At least one selected from a complex of the phosphine compound and an organoaluminum compound,
3) The method for producing a cyclic olefin addition copolymer according to any one of claims 1 to 5, which is a multicomponent catalyst containing an ionic boron compound or an ionic aluminum compound. 20 to 80 mol% of a structural unit represented by the following formula (4),
1 to 20 mol% of a structural unit represented by the following formula (5), and 10 to 70 mol% of a structural unit represented by the following formula (6)
A cyclic olefin-based addition copolymer comprising:

(In the formula ^(4), A ¹ ~A 4 are each independently a hydrogen atom, a halogen atom, atom or a group selected from alkyl groups such as methyl group or 2 to 10 carbon atoms, of A ¹ to A ⁴ At least one represents an alkyl group having 2 to 10 carbon atoms),

[In formula (5), B ^{1 to} B ⁴ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and B ¹ and B ^2. Or B ¹
And B ³ cyclic ester groups, acid anhydride groups and N-alkyl or cycloalkyl substituted carbonimido groups, and the general formula — (CHR ¹ ) _k —X
Wherein X is selected from an alkoxycarbonyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon trialkylsiloxycarbonyl groups, and an alkoxy group having 1 to 3 carbon atoms alkoxysilyl group. And R ¹ is a hydrogen atom or a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group, and k represents an integer of 0 to 5.)
An atom or group selected from the group consisting of polar groups represented by: ],

(In formula (6), C ^{1 to} C ⁴ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group, and a halogen atom).   The cyclic olefin according to claim 7, wherein the polystyrene-equivalent number average molecular weight (Mn) is 10,000 to 200,000, and the polystyrene-equivalent weight average molecular weight (Mw) is 30,000 to 500,000. -Based addition copolymer.   A film or sheet comprising the cyclic olefin-based addition copolymer according to claim 7 or 8. A film or sheet obtained by molding the cyclic olefin addition copolymer according to claim 7 or 8 by a solution casting method.

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