TWI507431B - A cyclic olefin ring-opening polymer, a hydride thereof and the hydride composition, and tricyclopentadiene - Google Patents

Description

Cyclic olefin ring-opening polymer, hydride thereof and the hydride composition, and tricyclopentadiene

The present invention relates to a cyclic olefin ring-opening polymer having a high refractive index and a high abbe number for an optical material, a hydride thereof, a ring-opening polymerization hydride composition of the cyclic olefin, and a tricyclopentane Diene.

a cyclic olefin ring-opening polymer, especially a hydrogenated cyclic olefin ring-opening polymer (hereinafter, a cyclic olefin ring-opening polymer, a hydrogenated cyclic olefin ring-opening polymer comprising a copolymer, also referred to as a ring The olefin-opening polymer is attracting attention as a thermoplastic transparent resin excellent in light transmittance or heat resistance. The polymer is widely used in applications such as optical lenses or optical materials such as optical fibers and optical films. In addition, mobile devices such as mobile phones equipped with such optical lenses have been developed in the direction of further miniaturization and high performance. For this reason, the configuration of the device is required to be further miniaturized, lightweight, and highly functional. Therefore, a resin having a higher refractive index and a high Abbe number is also required for the lens resin to be functional even if it is small and thin.

On the other hand, as the optical lens is flaky, it is required to obtain a transparent resin which is not easily broken and has a high toughness. In order to secure the toughness of the resin, the molecular weight of the cyclic olefin ring-opening polymer must be a high molecular weight of a certain amount or more.

However, when the cyclic olefin ring-opening polymer is polymerized, the solubility of the polymer in the solvent is lowered during the polymerization and precipitates, so that it cannot be produced by the conventional solution polymerization and hydrogenation method.

It is necessary to realize a polymer having both high optical properties and high solubility in order to produce a polymer having a high refractive index and a high Abbe number and having a molecular weight required for a resin for a lens by using an existing solution polymerization process. design.

It is known that it is known to increase the solubility of a cyclic olefin ring-opening polymer by introducing a functional group such as an ester group into a side chain (Patent Document 1). In contrast, the presence of a functional group hinders the high refractive index. Therefore, the inventors of the present invention conducted a preliminary review of a polymer having both solubility and high refractive index by copolymerization with a monomer having no functional group. However, as a trifunctional ring represented by a monomer having no functional group [4.3.0.1 ^2,5 ]癸-3,7-diene (dicyclopentadiene) or tetracyclo[4.3.0.1 ^2,5 .1 ⁷ The refractive index improvement effect of ¹⁰ ] indole-3-ene (DMON) or the like is small, and only the refractive index value (n _D < 1.525) which is inferior to the existing resin can be achieved.

A technique in which a polymer having a functional group and a polystyrene are blended by a technique in which a high refractive index of a cyclic olefin ring-opening polymer and a solubility in a solvent are combined (Patent Document 2). Although this technique can achieve a high refractive index in a ratio in which the amount of polystyrene blended is large, on the other hand, there is a disadvantage that the Abbe number is lowered and the chromatic aberration of the lens is increased.

To this end, there is a need for a cyclic olefin ring-opening polymer which does not incorporate polystyrene but which has a high Abbe number and exhibits a high refractive index, only a cyclic olefin ring-opening polymer monomer. In other words, in order to achieve complete solubility in a solvent such as toluene, a high refractive index, and a high Abbe number, it is necessary to develop a novel monomer having a high refractive index improving effect, and to develop a characteristic for achieving the target. The monomer composition to be copolymerized.

Under the circumstances, the inventors of the present invention have discussed the monomers to be copolymerized to achieve a high refractive index and a high Abbe number. As a result, it was found that cyclopentadiene such as pentacyclo[6.5.1.0 ^2,7 .1 ^3,6 .0 ^9,13 ], heptacarbon-4,10-diene (tricyclopentadiene) The three-pentapolymers are copolymerized to achieve high refractive index and high Abbe number of the conventional monomers. Further, it has been found that solubility in a solvent can be ensured by being a copolymer having a suitable composition with a monomer having a functional group.

Furthermore, the present inventors have found that cyclopentadiene such as pentacyclo[6.5.1.0 ^2,7 .1 ^3,6 .0 ^9,13 ]pentacarbon-4,10-diene (tricyclopentadiene) The amount of geometric isomers in the third to pentamer has an influence on the refractive index of the obtained polymer, and thus the present invention has been completed.

As described above, the present inventors have found that a polymer of cyclopentadiene is polymerized as a constituent monomer of a cyclic olefin, and then the hydrogenated polymer can exhibit properties excellent in optical use. However, in the polymer of cyclopentadiene, when it is a tetramer or more, the reaction rate (polymerization yield) at the time of polymerization may be insufficient. Further, when there is an unreacted monomer, there is a problem that the amount of out gas at the time of molding is large, which may cause defects or the like and may not be used for an optical material or a medical material.

Further, when a polymer having a large amount of a quinoid type is contained in a polymer of a trimer or a trimer of cyclopentadiene, a crosslinking reaction occurs during the polymerization reaction. Therefore, there is a problem in that the obtained polymer is highly polymerized, causing disadvantages such as insolubilization and gelation.

As a method for producing tricyclopentadiene of a trimer of cyclopentadiene, for example, Patent Document 3 and the like are known. However, the tricyclopentadiene obtained by this method is 1,4,4a,4b,5,8,8a,9a-octahydro-1,4;5,8-dimethyl represented by the following formula (6). -1H-茀 and 3a,4,4a,5,8,8a,9,9a-octahydro-4,9;5,8-dimethylidene-1H-benzo[f) represented by formula (5) a mixture of isomers of hydrazine, which is represented by formula (6): 1,4,4a,4b,5,8,8a,9a-octahydro-1,4;5,8-dimethylene-1H- As described above, since a crosslinking reaction occurs during the polymerization reaction, the obtained polymer is high in molecular weight, solubility in a solvent is lowered, and problems such as gelation occur.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 1-240517

Patent Document 2: Japanese Patent Laid-Open No. Hei 1-158029

Patent Document 3: Japanese Patent Laid-Open Publication No. 2001-10983

An object of the present invention is to provide a cyclic olefin ring-opening copolymer having a refractive index and an Abbe number, having solubility in a solvent, a cyclic olefin ring-opening copolymer for use as an optical material, a hydrogenated product thereof, and a cyclic olefin ring-opening polymerization hydride composition, and Tricyclopentadiene.

The cyclic olefin ring-opening polymer of the present invention is obtained by polymerizing a cyclic olefin monomer containing the compound (1) represented by the following formula (1).

In the above formula (1), n is 1, 2 or 3,

The above compound (1) is a compound containing 55 mol% or more of each geometric isomer as n = 1 to 3 of the geometric isomer (2), wherein

When n=1, it is a compound represented by the following formula (2-1)

When n=2, it is a compound represented by the following formula (2-2)

When n=3, it is a compound represented by the following formula (2-3)

However, among the compounds, when the specular isomer is present, the compound of the specular isomer is also included.

[Chemical 1]

The above cyclic olefin monomer of the cyclic olefin ring-opening polymer of the present invention preferably further comprises a compound (3) represented by the following formula (3).

[Chemical 2]

In the formula (3), m is an integer of 0 to 3, and each of A ¹ to A ⁴ independently represents any one of the following (i) to (iv), and at least one of the above represents (iii),

(i) hydrogen atom

(ii) halogen atom

(iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amine group, and a thiol group,

(iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group which may be substituted by a halogen atom or the aforementioned polar group (iii).

The cyclic olefin monomer of the cyclic olefin ring-opening polymer of the present invention preferably further comprises a compound (4) represented by the following formula (4).

[Chemical 3]

(4) In the formula, B ¹ ~ B ⁴ are each independently represented by the following (i) ~ (iii) of any one, or represents (iv) or (v),

(i) hydrogen atom

(ii) halogen atom

(iii) an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a halogen atom, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group,

(iv) B ¹ and B ² , or B ³ and B ⁴ represent mutual bond formation to form an alkylene group, and B ¹ to B ⁴ independent of the above bonding are independent of each other to indicate that they are selected by the above (i) to (iii) ,

(v) B ¹ and B ³ , B ¹ and B ⁴ , B ² and B ³ , or B ² and B ⁴ are bonded to each other, together with the carbon atoms bonded to each other, form a cyclic structure, and bond with the above The irrelevant B ¹ to B ⁴ are independent of each other and are selected by the above (i) to (iii).

The cyclic olefin ring-opening polymerization hydride of the present invention is preferably obtained by hydrogenating the cyclic olefin ring-opening polymer described in any one of the above.

Further, the cyclic olefin ring-opening polymerization hydride composition of the present invention contains 90 to 99.99% by mass of a cyclic olefin ring-opening polymerization hydride and 10 to 0.01% by mass of a preparation which is incompatible with the hydride. The formulation component is dispersed in the hydride in a micro-block.

The tricyclopentadiene of the present invention is represented by the following formula (5).

The tricyclopentadiene has at least one characteristic represented by the following (a), (b), and (c).

(a) 1,4,4a,4b,5,8,8a,9a-octahydro-1,4;5,8-dimethylene-1H-indole represented by the following formula (6): 1% by mass or less ,

(b) The tricyclopentadiene represented by the following formula (5) is 3a, 4, 4a, 5, 8, 8a, 9, 9a-octahydro-4, 9 represented by the following formula (2-1); An endo body of 5,8-dimethyl-1H-benzo[f]pyrene with respect to the bridge body and 3a, 4, 4a, 5, 8, 8a represented by the following formula (2-1a), The total amount of 9,9a-octahydro-4,9;5,8-dimethylidene-1H-benzo[f]indole (exo) body contains 50 mol% or more,

(c) The content of the oxide contained in the total amount of the following formula (5) and the following formula (6) is 100 ppm or less.

In particular, it is preferred to have the characteristics represented by the above (a), (b) and (c).

[Chemical 4]

According to the present invention, it is possible to provide a cyclic olefin ring-opening polymer which is excellent in refractive index and Abbe number and which can be used in optical materials. Further, tricyclopentadiene having at least one of the characteristics represented by the above (a), (b), and (c) is excellent as a polymerization conversion ratio of a monomer for producing a cyclic olefin polymer. Further, the obtained polymer has a high refractive index and an Abbe number and is an excellent optical material.

Hereinafter, the present invention will be specifically described.

Cyclic olefin ring-opening polymer

The cyclic olefin ring-opening polymer of the present invention is produced by ring-opening polymerization of a cyclic olefin monomer containing a cyclic olefin compound.

<Cyclic olefin monomer>

The cyclic olefin monomer used in the present invention means a mixture comprising at least one compound (1) represented by the following formula (1) (hereinafter also referred to as "cyclic olefin compound (1)"). The olefin compound (1) is characterized by containing 55 mol% or more of each of the geometric isomers as n = 1 to 3 of the geometric isomer (2).

a compound represented by the following formula (2-1) when n=1

a compound represented by the following formula (2-2) when n=2

a compound represented by the following formula (2-3) when n=3

However, in the case of such compounds, the presence of a specular isomer also includes the form of the specular isomer.

[Chemical 5]

In the formula (1), n is an integer of 1 to 3.

In the method for producing a cyclic olefin ring-opening copolymer of the present invention, the amount of the cyclic olefin compound (1) contained in the cyclic olefin monomer is not particularly limited. The content of the preferred cyclic olefin compound (1) is from 10 to 90 mol%, preferably from 30 to 80 mol%, based on the cyclic olefin monomer. When the cyclic olefin compound (1) contains 10 mol% or more of the cyclic olefin monomer, the refractive index of the obtained ring-opening copolymer is preferably higher. Further, when the cyclic olefin compound (1) is contained in an amount of 90 mol% or less, the solubility of the ring-opening copolymer in a solvent such as toluene can be easily obtained, which is preferable.

Further, the geometric isomer (2) contained in the cyclic olefin compound (1) is 55 mol% or more, preferably 60 mol% or more, more preferably 80 mol% or more. The higher the proportion of the geometric isomer (2), the higher the refractive index of the resulting cyclic olefin ring-opening polymer.

Further, the cyclic olefin compound (1) is a pentacyclo [6.5.1.0 ^2,7 .1 ^3,6 .0 ^9,13] pentadeca-4,10-diene (three cyclopentadienyl, n = 1 ), seven rings [8.7.0.1 ^2,9 .1 ^4,7 .1 ^11,1 7.0 ^3,8 .0 ^12,16 ] twenty carbon-5,13-diene (tetracyclopentadiene, n= 2) and Jiuhuan [10.9.1.1 ^3,10 .1 ^5,8 .1 ^14,20 .0 ^2,11 .0 ^4,9 .0 ^13,21 .0 ^15,19 ] twenty-five carbon-6, 16-diene (pentacyclopentadiene, n=3).

In the cyclic olefin compound (1), n-cyclopentadiene of n = 1 will be further described.

The tricyclopentadiene of the present invention (hereinafter referred to as TCP) is subjected to a thermal addition reaction of a Diels-Alder reaction type of dicyclopentadiene (hereinafter referred to as DCP), or The target monomer is obtained by DCS synthesis with a Diels-Oder reaction of cyclopentadiene (hereinafter referred to as CPD), followed by purification by distillation. The TCP can be used as a monomer for producing a cyclic olefin ring polymer.

TCP has an isomer represented by the formula (5) and the formula (6) (hereinafter, the TCP represented by the formula (5) is also referred to as 6,6,5-TCP, and the TCP represented by the formula (6) is also called 6,5,6-TCP), in addition, there are isomers having a stereo configuration of an endo (hereinafter referred to as bridge) and an exo (hereinafter referred to as hanging) in the isomers. . The compound represented by the above formula (2-1) is a bridge of 6,6,5-TCP, and the compound represented by the above formula (2-1a) is a 6,6,5-TCP pendant. Further, the compound represented by the formula (2-1) and the formula (2-1a) is a mirror-containing body.

The Diels-Oder reaction of DCP and CPD is illustrated using Figure 1. In the DCP, there is a bridge-DCP which is a stereoisomer, and the bridge-DCP which is transferred by the heat of the bridge-DCP is transferred. For this reason, for the bridge-DCP, there are cases where the CPD is bridge-added to generate TCP (Fig. 1 (α)), and when the TCP is generated by the add-on (Fig. 1 (β)). Similarly, for the hanging-DCP, there are cases where the CPD is bridge-added (Fig. 1 (γ)), and the case of the add-on (Fig. 1 (δ)). Four kinds of adducts are generated as a total of TCP.

The above description is directed to the case where the CPD reacts with the norbornene ring side of the highly reactive DCP, but the reaction of CPD with the cyclopentene ring side of DCP is also theoretically possible. Compared with the reaction on the norbornene ring side, 6,5,6-TCP is formed upon reaction with the less reactive cyclopentene ring side. Therefore, the isomer of TCP theoretically has a total of eight stereoisomers.

However, according to the synthesis result of the conditions described below, it was found that the entangled adduct (β) for the bridge-DCP and the entangled addition (δ) for the hang-DCP were hardly generated. Accordingly, in the present specification, the bridge of 6,6,5-TCP means bridge adder to bridge-DCP, and the so-called 6,6,5-TCP mount means bridge to hang-DCP. Adult.

The TCP of the present invention has at least one of the following characteristics represented by (a), (b) and (c) in 6,6,5-TCP.

(a) The 6,5,6-TCP represented by the above formula (6) is 1% by mass or less, preferably 0.7% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.3% by mass or less. When the amount of 6,5,6-TCP exceeds 1% by mass, gelation occurs during polymerization of the monomer, and the molecular weight distribution of the obtained polymer becomes broad.

(b) The bridge body of 6,6,5-TCP represented by the above formula (2-1) is 50 mol% or more, preferably 55 mol% or more, more preferably 70 mol% or more, and still more preferably 80. More than Mole. When the bridge body is less than 50 mol%, the refractive index of the obtained polymer is lowered. Moreover, the disadvantage that the molecular weight distribution of the polymer is broadened also occurs. Here, the bridge body is 50 mol% or more, and the bridge/hang ratio is 50/50 or more.

(c) The content of the oxide contained in the total amount of the monomers represented by the above formula (5) and the above formula (6) is 100 ppm or less. When it exceeds 100 ppm, the polymerization activity is remarkably lowered. Therefore, the TCP of the present invention preferably adds about 10 ppm to 500 ppm of an antioxidant and is stored under a nitrogen atmosphere. Further, the oxide is considered to be the oxide of the above TCP.

The TCP of the present invention preferably has all of the characteristics shown by the above (a), (b) and (c). This kind of TCP can be manufactured by the following method.

The purity of DCP and/or CPD which is a raw material is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more. As for the impurities of DCP, mainly in addition to tetrahydromethyl hydrazine, most of them are C ₅ to C ₉ chain or cyclic diene compounds and dicyclopentadiene adducts, and the amount of these increases, so that the raw material DCP When the purity is less than 90% by mass, heavy by-products become large in the manufacturing process.

Further, the bridge/hang ratio in the DCP to be a raw material is preferably 80/20 or more, more preferably 90/10 or more, and still more preferably 95/5 or more. When the bridge/hang ratio is less than 80/20, the bridge/hang ratio in the TCP generated after the Deos-Oder reaction is reduced, so the bridge ratio in the 6,6,5-TCP after distillation is also lowered.

The reaction temperature of the Deos-Oder reaction condition is preferably from 120 ° C to 250 ° C, more preferably from 130 ° C to 230 ° C, more preferably from 150 ° C to 210 ° C, and the reaction time is preferably from 0.1 to 50 hours, more preferably. It is 0.5~10 hours.

Within the above reaction conditions, the conversion of DCP is preferably from about 30% to about 50%. When the DCP conversion rate exceeds 50%, since a large amount of a heavy boiling portion of CPD tetramer or more is generated, the selectivity of TCP is lowered, and when the reboiled portion is concentrated in distillation, precipitation solidification or line blockage may occur. . When the DCP conversion rate is less than 30%, the yield of TCP is lowered, and the production efficiency is lowered.

By the above-mentioned Dios-Oder reaction step, for example, DCP (bridge/hanging = 80/20 to 95/5) is obtained as 80 to 70% by mass, and 6,5,6-TCP is 4 to 6% by mass, 6 6,6-TCP (bridge/hanging=80/20~95/5) is 22 to 34% by mass, and the reboiled portion of CPD tetramer or more is about 4 to 10% by mass of crude TCP.

The above crude TCP was purified by a distillation purification step. The distillation method is not particularly limited, but is preferably purified by distillation using a two-stage distillation of a crude distillation column and a precision distillation column.

After removing the unreacted DCP, the crude distillation column preferably removes the reboiled portion of the CPD tetramer or more. By removing the reboiled portion of the CPD tetramer or more, the temperature of the still in the rectification can be lowered, and the reaction can be suppressed.

After crude distillation, for example, DCP is 0 to 5 mass%, 6,5,6-TCP is 10 to 20 mass%, and 6,6,5-TCP (bridge/hanging = 80/20 to 95/5) is 70~. 90% by mass, the reboiled portion of the CPD tetramer or more is about 0 to 5% by mass of the TCP before the precision distillation.

The DCP recovered in the crude distillation step can be reused as a raw material for the Dios-Od reaction step.

In the precision distillation column, precision distillation for removing 6,5,6-TCP represented by the formula (6) from the TCP content after the crude distillation is performed. The 6,5,6-TCP represented by the formula (6) is very close to the boiling point of the 6,6,5-TCP represented by the formula (5), and the relative volatility is small, so in order to separate by one distillation, it is preferred to A distillation column with a high theoretical number of plates is carried out under high vacuum. The number of theoretical plates is preferably 20 or more, more preferably 25 or more. The pressure at the top of the column is from 0.01 kPa to 10 kPa, preferably from 0.1 kPa to 5 kPa.

The temperature of the distillation still in the rectification is preferably 200 ° C or lower, more preferably 180 ° C or lower, and even more preferably 170 ° C or lower. When the temperature of the kettle exceeds 200 ° C, the decomposition of TCP is significantly caused in the distillation and the synthesis reaction is carried out to form a 6,5,6-TCP or CPD tetramer or more.

In batch distillation, 6,6,5-TCP with a high ratio of [(a little boiling point bridge) / (hang)]) can be recovered by increasing the reflux ratio at the 6,6,5-TCP recovery. By the above-described precision distillation step, it is possible to obtain 6,6,5-TCP having a bridge/hang ratio of 6,6,5-TCP of 1% by mass or less and a bridge of 6 or 6,6-TCP.

The purified 6,6,5-TCP is easily oxidized, and the polymerization activity is remarkably decreased when the amount of the oxide exceeds 100 ppm. Therefore, it is preferable to add an antioxidant of about 10 ppm to 1000 ppm, and to store it in an amount of oxide of 100 ppm or less in a nitrogen atmosphere. As the antioxidant, pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, dibutylhydroxytoluene or the like can be used.

The purified 6,6,5-TCP can be used as a monomer for producing a cyclic olefin polymer. 6,6,5-TCP may be used alone or as one of the copolymer components. Also, DCP can be used as a monomer.

The cyclic olefin monomer used in the present invention preferably further contains at least one cyclic olefin compound represented by the following formula (3) (hereinafter also referred to as "cyclic olefin compound (3)"). The cyclic olefin monomer can improve the solubility in a solvent by containing 4 to 45 mol% of the cyclic olefin compound (3).

[Chemical 6]

In the formula (3), m is an integer of 0 to 3, and each of A ¹ to A ⁴ independently represents any one of the following (i) to (iv), and at least one of the above represents (iii),

(i) hydrogen atom

(ii) halogen atom

(iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amine group, and a thiol group,

(iv) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group which may be substituted by a halogen atom or the aforementioned polar group (iii).

In addition, the cyclic olefin monomer used in the present invention may further contain at least one cyclic olefin compound represented by the following formula (4) (hereinafter also referred to as "cyclic olefin compound (4)"). The cyclic olefin monomer can easily adjust the glass transition point of the obtained copolymer by containing 0 to 50 mol% of the cyclic olefin compound (4).

[Chemistry 7]

In the formula (4), B ¹ to B ⁴ each independently represent any of the following (i) to (iii), or represent (iv) or (v),

(i) hydrogen atom

(ii) halogen atom

(iii) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group which may be substituted by a halogen atom.

(iv) B ¹ and B ² , or B ³ and B ⁴ are bonded to each other to form an alkylene group, and B ¹ to B ⁴ independently of the above-mentioned bonding are independent of each other and are selected by the above (i) to (iii).

(v) B ¹ and B ³ , B ¹ and B ⁴ , B ² and B ³ , or B ² and B ⁴ are bonded to each other to form a cyclic structure together with the carbon atoms bonded thereto, irrespective of the above bonding. B ¹ to B ⁴ are independent of each other and are selected by the above (i) to (iii).

In the cyclic olefin compound (3) and the cyclic olefin compound (4), the halogen atom is exemplified by a fluorine atom, a chlorine atom and a bromine atom.

In the cyclic olefin compound (3), examples of the polar group include an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amine group, and a thiol group. The alkoxy group is, for example, a methoxy group or an ethoxy group, and is preferably an alkoxy group having 1 to 10 carbon atoms. Examples of the ester group include an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, an aryloxycarbonyl group such as a phenoxycarbonyl group, a naphthyloxycarbonyl group, a decyloxycarbonyl group or a biphenyloxycarbonyl group. Good for carbon number 1~10. The amine group is preferably a primary amine group.

In the above cyclic olefin compounds (3) and (4), the aliphatic hydrocarbon group having 1 to 10 carbon atoms may, for example, be an alkyl group such as a methyl group, an ethyl group or a propyl group, or an alkene such as a vinyl group, an allyl group or a propylene group. base. The alicyclic hydrocarbon group is preferably a carbon number of 5 to 10, and examples thereof include a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. The alicyclic hydrocarbon group has no double bond in the ring. The aromatic hydrocarbon group is preferably a carbon number of 6 to 20, and examples thereof include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, an anthracenyl group, and an anthracenyl group.

As the cyclic olefin compound (3), specifically, the following compounds are exemplified.

5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonyl-bicyclo[2.2.1]hept-2-ene, 5-phenoxyethylcarbonyl-bicyclo[2.2 .1]hept-2-ene, 5-phenylcarbonyloxy-bicyclo[2.2.1]hept-2-ene, 5-trifluoromethyl-5-methoxycarbonyl-bicyclo[2.2.1]g 2-ene, 5-methyl-5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene, 5-methyl-5-phenoxycarbonyl-bicyclo[2.2.1]hept-2 - alkene, 5-methyl-5-phenoxyethylcarbonyl-bicyclo[2.2.1]hept-2-ene, 5-hydroxy-bicyclo[2.2.1]hept-2-ene, 5-hydroxyethyl -bicyclo[2.2.1]hept-2-ene, 5-cyano-bicyclo[2.2.1]hept-2-ene, 5-amino-bicyclo[2.2.1]hept-2-ene, 8-a Oxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-phenoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]10 Dicarbon-3-ene, 8-phenoxyethylcarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] ^dode -3-ene, 8-phenylcarbonyloxy-tetracyclo[ 4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]12 carbon 3-ene, 8-trifluoromethyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-methyl-8-benzene Oxycarbonyl-tetracyclo[4.4.0. 1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-methyl-8-phenoxyethylcarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]12 carbon 3-ene, 8-hydroxy-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-hydroxyethyl-tetracyclo[4.4.0.1 ^2,5 .1 ^{7 , 10} ] dodec-3-ene, 8-methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene, 8-cyano- Tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-amino-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene In the present invention, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene is preferably used as the cyclic olefin compound ( 3).

In the method for producing a cyclic olefin ring-opening copolymer of the present invention, the amount of the cyclic olefin compound (3) contained in the cyclic olefin monomer is not particularly limited. Preferably, the cyclic olefin compound (3) in the cyclic olefin monomer is contained in a proportion of 4 to 45 mol%. When the content ratio of the cyclic olefin compound (3) in the cyclic olefin monomer is 4 mol% or more, the obtained ring-opening copolymer is preferably soluble in a solvent such as p-toluene, and is preferably 45 mol. In the case of % by ear, it is preferred to suppress a decrease in the refractive index of the resulting ring-opening copolymer.

As the cyclic olefin compound (4), specifically, the following compounds are exemplified.

Bicyclo[2.2.1]hept-2-ene (norbornene), 5-methyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[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-hexyl-bicyclo[2.2.1]hept-2-ene , 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-hexyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hept-2-ene , 5-phenyl-bicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.1 ^2,5 ]non-3-ene, tricyclo[4.3.0.1 ^2,5 ]癸-3,7- Diene (dicyclopentadiene), tricyclo[4.4.0.1 ^2,5 ]undec-3-ene, 7-methyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7 -ethyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-cyclohexyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7-phenyl-tricyclo[4.3 .0.1 ^2,5 ]non-3-ene, 7-(4-biphenylyl)-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 7,8-dimethyl-tricyclo[4.3 .0.1 ^2,5 ]non-3-ene, 7,8,9-trimethyl-tricyclo[4.3.0.1 ^2,5 ]non-3-ene, 8-methyl-tricyclo[4.4.0.1 ^{2 ,5} ]undec-3-ene, 8-phenyl-tricyclo[4.4.0.1 ^2,5 ]undec-3-ene, 7,8-dichloro-tricyclo[4.3.0.1 ^2,5 ] indole-3-ene, 7,8,9-trichloro-tricyclo[4.3.0.1 ^2,5 ]non-3-ene.

Among them, bicyclo [2.2.1] hept-2-ene, tricyclo[4.3.0.1 ^2,5 ]non-3-ene and the like are preferably used.

The cyclic olefin monomer can easily adjust the cyclic olefin polymer of the present invention obtained by ring-opening copolymerization of a cyclic olefin monomer, and the glass of the hydride thereof by containing the cyclic olefin compound (4). Transfer temperature (Tg). For example, it can be a desired Tg temperature in the range of 110 ° C to 180 ° C which is desired as a molded article.

In the method for producing a cyclic olefin ring-opening copolymer of the present invention, when the cyclic olefin monomer (4) is contained in the cyclic olefin monomer, the more the cyclic olefin compound (4) is contained, the resulting ring-opening copolymer is obtained. Since Tg shows a tendency to decrease, the amount of the compound (1) and the compound (4) in the monomer can be appropriately adjusted, and the Tg of the ring-opening copolymer can be appropriately selected to be a desired temperature. Adjust the Tg.

The cyclic olefin monomer of the present invention may contain a copolymerizable monomer other than the above cyclic olefin compounds (1), (3) and (4), but the content thereof is preferably 20 mol% or less, preferably 10 Mole% or less.

<Open-loop copolymerization>

The cyclic olefin ring-opening polymer of the present invention is produced by subjecting a cyclic olefin monomer containing a cyclic olefin compound to ring-opening copolymerization.

The ring-opening copolymerization step can be used without limitation for the catalyst which can be used in the ring-opening copolymerization of the cyclic olefin compound. A preferred catalyst is a catalyst using the following catalyst components (a), (b) and (c).

(a) an organoaluminum compound,

(b) a compound selected from the group consisting of a nitrile group-containing compound, a ketone, an ether group-containing compound, an alcohol, and an ester,

(c) at least one compound selected from the group consisting of a tungsten compound, a molybdenum compound, a cerium compound, a vanadium compound, and a titanium compound.

The organoaluminum compound of the catalyst component (a) is preferably represented by the following formula (7).

[化8]

AlR _n X _3-n ‧‧‧(7)

In the formula (7), R represents a linear alkyl group or a branched alkyl group, and X represents a halogen atom.

Further, an aluminum oxy compound can also be used as the organoaluminum compound (a).

As the organoaluminum compound (a), specifically, for example, (C ₂ H ₅ ) ₃ Al, (i-Bu) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 (C ₂ H ₅ )AlCl ₂ , methylaluminoxane, and the like.

These organoaluminum compounds (a) may be used alone or in combination of two or more.

As the catalyst component (b), at least one compound selected from the group consisting of a nitrile group-containing compound, a ketone compound, an ether group-containing compound, an alcohol compound, and an ester compound can be used without particular limitation.

The nitrile group-containing compound is exemplified by, for example, acetonitrile, benzonitrile or the like.

The ketone compound is exemplified by, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone or the like.

The compound containing an ether group is exemplified by, for example, dimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl Ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, triethylene glycol Alcohol dimethyl ether and the like.

The alcohol compound is exemplified by, for example, methanol, ethanol, n-propanol, isopropanol, isobutanol or the like.

The ester compounds are exemplified by methyl acetate, ethyl acetate, butyl acetate, phenyl acetate, ethyl lactate, butyl lactate, methyl benzoate, ethyl benzoate, 5-methyl-5-methoxycarbonyl- Bicyclo[2.2.1]hept-2-ene, 2-methyl-2-methoxycarbonyl-bicyclo[2.2.1]heptane, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4. 0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 2-methyl-2-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane, and the like.

These catalyst components (b) may be used alone or in combination of two or more.

As the catalyst component (c), at least one compound selected from the group consisting of a tungsten compound, a molybdenum compound, a ruthenium compound, a vanadium compound, and a titanium compound can be used without particular limitation.

The compound which is preferably used as the catalyst component (C) is exemplified by a compound described in Olefin Metathesis and Metathesis Polymerization (KJ IVIN, JC MOL, Academic Press 1997), for example, WCl ₆ , WOCl ₄ , W(CO) ₆ , MoCl. ₅ , MoCl ₅ , MoO ₃ , Mo(CO) ₆ , ReCl ₅ , Re ₂ O ₇ , ReOCl ₃ , VCl ₄ , VOCl ₃ , V ₂ O ₅ , TiCl ₄ and the like. These may be used alone or in combination of two or more.

In the method for producing a cyclic olefin ring-opening copolymer of the present invention, the above-mentioned catalyst components (a), (b) and (c) are preferably used in combination as a ring-opening copolymerization catalyst. More preferably, a mixture (B) obtained by contacting the catalyst components (a) and (b) in advance and a mixture (B) obtained by contacting the catalyst components (b) and (c) in advance are used.

The catalyst components (a) and (b) are brought into contact, and the operation of preparing the mixture (A) can be carried out in an inert gas atmosphere such as nitrogen or argon at a temperature ranging from room temperature to 100 °C. The mixing ratio is not particularly limited, but in order to increase the activity of the catalyst, the molar of (b)/(a) is preferably in the range of 0.01/1 to 10/1. A hydrocarbon solvent such as toluene or cyclohexane can be used as the solvent to be used for the mixing. The mixture can be used in the polymerization immediately after preparation.

Further, the catalyst components (b) and (c) are brought into contact, and the operation of preparing the mixture (B) may be carried out in an inert gas atmosphere such as nitrogen or argon at a temperature ranging from room temperature to 100 °C. The mixing ratio is not particularly limited, but in order to improve the activity of the catalyst, the moir of (b)/(c) is preferably in the range of 1/1 to 100/1. The solvent used in the mixing is also the same, and a hydrocarbon solvent such as toluene or cyclohexane can be used. The mixed solution may be used in the polymerization immediately after the production. However, since it may be deteriorated with time depending on the type of the catalyst component (b) to be added, it is preferably used within 1 hour after the production, and more preferably 30. Use within minutes.

The ratio of use of the mixture (A) (component (a) + (b)) added to the polymerization system and the mixture (B) (component (b) + (c)) is not particularly limited, but to increase the catalytic activity, The metal atom (mole) of a)/(c) is preferably in the range of 0.5/1 to 50/1, and more preferably in the range of 1.5/1 to 30/1.

The amount of the catalyst component (C) relative to the cyclic olefin monomer is preferably in the range of more than 500/1, more preferably the molar ratio of the total monomer amount to the monomer component (c). Greater than 1,000/1 range. This ratio is small, and when the amount of the catalyst is large, the amount of the catalyst remaining in the obtained copolymer increases, which may affect the hue and deterioration of the polymer.

As the polymerization solvent, those obtained by dissolving or dispersing the cyclic olefin monomer and the catalyst components (a) to (c) can be used. Specific examples of the polymerization solvent include alkane such as pentane, hexane, heptane, octane, decane or decane, and cyclohexane such as cyclohexane, cycloheptane, cyclooctane, decahydronaphthalene or norbornane. An aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene or cumene, chlorobutane, bromohexane, dichloromethane, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform And a halogenated alkane such as tetrachloroethylene; a saturated carboxylic acid ester such as ethyl acetate, n-butyl acetate, isobutyl acetate or methyl propionate; or an ether such as dibutyl ether, tetrahydrofuran or dimethoxyethane. These polymerization solvents may be used singly or in combination of two or more.

In the method for producing a cyclic olefin ring-opening copolymer of the present invention, the obtained cyclic olefin copolymer can be adjusted to a suitable ring-opening copolymerization reaction condition to have a desired molecular weight corresponding to the use. Further, a molecular weight modifier may also be used in the ring-opening copolymerization reaction.

Specific examples of the molecular weight modifier which can be preferably used include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-anthracene. Alpha-olefins such as olefins, styrene, and the like. Among these, 1-butene and 1-hexene are preferred. These compounds may be used singly or in combination of two or more kinds as molecular weight modifiers.

The amount of the molecular weight modifier to be used is not particularly limited, but is preferably from 0.005 to 0.6 mol, more preferably from 0.02 to 0.5 mol, based on 1 mol of the cyclic olefin monomer supplied to the ring-opening copolymerization reaction. range.

The reaction time in the ring-opening copolymerization reaction is not particularly limited, but in order to improve productivity, it is preferably 0.1 to 10 hours, preferably 0.1 to 5 hours, more preferably 0.1 to 3 hours. Further, the reaction temperature is preferably from 50 to 180 ° C, preferably from about 70 to 160 ° C.

<Circular olefin ring-opening polymerization hydride>

As described above, the cyclic olefin ring-opening polymer which only cyclically polymerizes the cyclic olefin monomer can be used as it is, but has an olefinic unsaturated bond in the molecule. Therefore, since the heat resistance is insufficient as the application, hydrogenation (hydrogenation reaction) is preferably carried out to obtain a cyclic olefin ring-opening polymerization hydrogenated product.

The hydrogenation step in the present invention can be carried out by a conventional method. For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The catalyst, the solvent, the temperature conditions, and the like described in JP-A-2005-162, 371, JP-A-2007-196, pp. Hydrogenation step.

The hydrogenation rate of the olefinic unsaturated bond of the cyclic olefin ring-opening polymer is usually preferably 90 mol% or more, preferably 95 mol% or more, more preferably 99 mol% or more. Further, in the case where the hydrogenation in the present invention is an intramolecular olefinic unsaturated bond, and the cyclic olefin ring-opening polymer has an aromatic group, the aromatic group is advantageous in terms of optical properties such as refractive index or heat resistance. It does not have to be hydrogenated.

As described above, the cyclic olefin ring-opening polymer and the cyclic olefin ring-opening polymerization hydride obtained by ring-opening polymerization of a cyclic olefin monomer, if necessary, may be purified and removed by a conventional method as needed. It is used by treatment such as catalyst or solvent removal.

<Physical properties of cyclic olefin ring-opening polymer>

The molecular weight of the cyclic olefin ring-opening polymer of the present invention can be appropriately adjusted and produced depending on the use, and is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is compared. Good 20,000~150,000. When the molecular weight is less than 20,000, the strength of the molded article may be lowered. On the other hand, when the molecular weight exceeds 150,000, the solution viscosity or the melt viscosity becomes too high, and the productivity, formability, and workability of the cyclic olefin copolymer of the present invention may be deteriorated.

Further, the molecular weight distribution (Mw/Mn) of the cyclic olefin polymer of the present invention is not particularly limited. It is preferably 10 or less, more preferably 7 or less, still more preferably 4 or less. When the molecular weight distribution is wide and a large amount of a low molecular weight component is mixed, the strength of the molded article may be lowered.

The cyclic olefin ring-opening polymer of the present invention exhibits high refraction by using a cyclic olefin monomer (1) containing 55 mol%, preferably 60 mol% or more of the specific geometric isomer (2). Rate and high Abbe number. That is, the preferred refractive index n _D of the cyclic olefin ring-opening polymer of the present invention is preferably 1.531 or more. In the present invention, the refractive index n _D is determined by using a 稜鏡 coupler using a laser light source of 408 nm, 633 nm, and 830 nm, and measuring the refractive index of any five of the film samples, and calculating the value obtained by Cauchy's equation. The refractive index at 589 nm at 25 ° C was calculated and found.

Further, the preferred Abbé number of the cyclic olefin ring-opening polymer of the present invention is preferably 53 or more, more preferably 55 or more. The Abbe number (ν) in the present invention means a value calculated by the formula of ν = (n _D -1) / (n _{F -} n _C ). Here, n _D , n _F and n _C are refractive indices of 589.2 nm, 486.1 nm, and 656.3 nm obtained by the above regression calculation.

Further, the cyclic olefin ring-opening polymer of the present invention preferably has a Tg of from 125 ° C to 200 ° C, more preferably from 130 to 190 ° C. When the Tg is less than 125 ° C, the final product such as an optical lens is not practical. On the other hand, when the Tg exceeds 200 ° C, the injection molding temperature must be a high temperature of 300 ° C or higher, and the deterioration of the resin coloration becomes remarkable.

The cyclic olefin ring-opening polymer of the present invention can be preferably produced by the above-described method for producing a cyclic olefin ring-opening polymer.

<additive>

The cyclic olefin ring-opening polymer of the present invention can be used as it is, or can be used by adding an additive such as a conventional antioxidant or an ultraviolet absorber for improving heat deterioration resistance or light resistance. As the additive, for example, a conventional phenol compound, a thiol compound, a thioether compound, a disulfide compound, a phosphorus compound or the like which is an additive to a resin can be used, and when it is used, it can be added by adding to the present invention. 100 parts by mass of the cyclic olefin ring-opening polymer is 0.01 to 10 parts by mass of at least one of these compounds to improve properties such as heat deterioration resistance and light resistance.

Further, the cyclic olefin ring-opening polymer of the present invention may be used by adding other additives depending on the characteristics of the intended molded body or the like. For example, for the purpose of obtaining a colored film, a coloring agent such as a dye or a pigment may be added, or a leveling agent characterized by improving the smoothness of the obtained film may be added. The leveling agent is exemplified by, for example, a fluorine-based nonionic surfactant, a special acrylic resin-type admixture, a decane-based admixture, and the like.

<Ring olefin ring-opening polymerization hydride composition>

In order to obtain the strength or flexibility of the molded body, a compounding agent may be added to the cyclic olefin ring-opening polymerization hydride. The compounding agent is preferably a rubbery polymer.

The rubbery polymer is exemplified by, for example, a copolymer of an aromatic vinyl monomer and a conjugated diene monomer, a hydride thereof, and a norbornene which is incompatible with the ring-opening polymerization hydride of the cyclic olefin of the present invention. A rubbery polymer. The rubbery polymer and the cyclic olefin ring-opening polymerization hydride have good dispersibility, and are preferred.

The copolymer of the aromatic vinyl monomer and the conjugated diene monomer may be a block copolymer or a random copolymer. From the viewpoint of weather resistance, it is more preferable to partially hydrogenate an olefinic double bond other than the aromatic ring. Specifically, it is exemplified as styrene ‧ butadiene block copolymer, styrene ‧ butadiene ‧ styrene block copolymer, styrene ‧ ethylene butene ‧ styrene block copolymer, styrene ‧ isoprene a diene block copolymer, styrene ‧ isoprene, a styrene block copolymer, and the like, a hydride, a styrene ‧ butadiene random copolymer, and the like.

Further, in the case where the composition of the present invention is molded into a container, it is necessary to confirm the transparency of the amount or state of the content. Therefore, it is preferred that the compounding agent has a smaller difference in refractive index from the ring-opening polymerization hydride in which the cyclic olefin is added. When the mixed refractive index difference is large, it is likely to become opaque in addition to the amount of the invisible content when added in a large amount. In addition, when it is too small, the turbidity prevention by steam sterilization may become insufficient.

In the composition of the present invention, the compounding agent 10 is added to the cyclic olefin ring-opening polymerization hydride by 90 to 99.99% by mass, preferably 95 to 99.98% by mass, more preferably 99 to 99.95% by mass, and most preferably 99.5 to 99.9% by mass. ~0.01% by mass, preferably 5 to 0.02% by mass, more preferably 1 to 0.05% by mass, most preferably 0.5 to 0.1% by mass, and dispersed in the ring-opening polymerization hydride of the cyclic olefin. When the amount added is too large, the transparency of the resin, the glass transition temperature, and the heat resistance are lowered. If the amount added is too small, the effect of blending the compounding agent cannot be obtained.

The method of addition is not particularly limited as long as it is a method in which the preparation agent is sufficiently dispersed in the cyclic olefin ring-opening polymerization hydride to become a micro-block. For example, when a rubbery polymer is used as a compounding agent, a method of kneading a resin in a molten state by a kneader or a biaxial kneader, a method of dissolving and dispersing in a suitable solvent, a casting method, or a direct drying method may be employed. The method of removing the solvent, and the like.

When the micro-block is a rubbery polymer as a compounding agent, it is slightly spherical, and the particle diameter variation between the particles is small. It is usually 0.3 μm or less in diameter, preferably 0.2 μm or less. When the particle diameter is used, the transparency of the cyclic olefin ring-opening polymerization hydride composition is reduced by adding a rubbery polymer, which does not cause a problem. In the case of other compounding agents, the micro-blocks are preferably slightly spherical, and it is preferred that the particle diameters between the particles are not varied, and the diameter is preferably 0.3 μm or less, preferably 0.2 μm or less. Further, even if the micro-block is not spherical, the diameter of the smallest sphere which can close the micro-block is preferably 0.3 μm or less, preferably 0.2 μm or less.

<use>

The cyclic olefin ring-opening polymer of the present invention, in particular, a cyclic olefin ring-opening polymerization hydride of a hydride, can be formed into a desired shape such as a lens shape, a film shape or a flake shape by a known method, and can be suitably used. It is used for various optical components such as optical lenses, medical containers such as pre-filled syringes, and the like.

Example

The present invention will be more specifically described below based on the examples, but the present invention is not limited to the examples. In the following examples and comparative examples, each of the steps of the polymerization reaction, the catalyst preparation, and the hydrogenation reaction was carried out under a nitrogen atmosphere.

In the following examples and comparative examples, the measurement and evaluation of each property were carried out in accordance with the following methods. The measurement results and evaluation results are shown in Table 1.

Glass transfer temperature (Tg)

The glass transition initiation temperature (hereinafter referred to simply as the glass transition temperature (Tg)) was determined by extrapolation according to Japanese Industrial Standard K7121 using a differential scanning calorimeter (manufactured by Seiko-Instruments Co., Ltd., trade name: DSC6200).

Weight average molecular weight and molecular weight distribution

The weight average molecular weight (Mw) and molecular weight distribution (Mw/) in terms of polystyrene were measured by gel permeation chromatography (GPC, manufactured by TOSOH Co., Ltd., trade name: HLC-8020) using tetrahydrofuran (THF) as a solvent. Mn).

¹ H-NMR analysis

¹ H-NMR was measured in deuterated chloroform using a superconducting nuclear magnetic resonance absorption apparatus (NMR, manufactured by Bruker, trade name: AVANCE 500), and the copolymerization composition ratio and the hydrogenation ratio were calculated.

Monomer conversion analysis

The amount of residual monomers contained in the reaction solution was analyzed and calculated using a gas chromatograph (manufactured by Shimadzu Corporation, trade name: GC-2014).

Quantification of geometric isomers (2) in cyclic olefin compound (1)

The amount of the geometric isomer contained in the cyclic olefin compound (1) was analyzed using a gas chromatograph (manufactured by Shimadzu Corporation, trade name: GC-2014), and the geometric isomer (2) was calculated. In proportion to the whole.

Refractive index

The refractive index of any five points of the film sample was measured using a PC-2010 type 稜鏡 coupler manufactured by Metricon, and the average of three points except the maximum value and the minimum value was used. Further, the light source was a laser light source of 408 nm, 633 nm, and 830 nm, and a refractive index of 589 nm (25 ° C) was calculated from the obtained refractive index by a regression calculation using a Cauchy equation.

Abbe number

The Abbe number ν is calculated by the following formula.

ν=(n _D -1)/(n _F -n _C )

n _D , n _F , and n _C are refractive indices of 589.2 nm, 486.1 nm, and 656.3 nm obtained by regression calculation from the results of measurement of the refractive index.

Bending elastic modulus

The polymer was kneaded by a twin-shaft kneading machine (TEM-37BS manufactured by Toshiba Machine Co., Ltd., temperature: 280 ° C, screw rotation number: 100 rpm, feeder rotation number: 10 rpm, discharge amount: 18 kg/hr), and extruded to obtain pellet 1. Using this pellet 1, a test piece of 60 mm × 80 mm × 1.0 mm was produced by injection molding (S2000i100B manufactured by FANUC, mold binding pressure of 100 tons, resin temperature of 280 ° C, and mold temperature of 120 ° C).

Using this test plate, the bending elastic modulus was measured in accordance with JIS K7203 (bending test of hard plastic). The bending elastic modulus was measured at n = 10, and the average value thereof was ○ when it exceeded 2600 MPa, and was × when it was 2600 MPa or less.

[Example 1]

The compound represented by the formula (2-1) (which also contains a specular isomer, hereinafter also referred to as the compound (2-1)) as a cyclic olefin monomer in the geometric isomer is TCP (71.9). g, 363 mmol, content of geometric isomer other than compound (2-1): 18%), 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] Dodecyl-3-ene (37.5 g, 161 mmol, hereinafter also referred to as DMN), bicyclo [2.2.1] hept-2-ene (22.1 g, 235 mmol, hereinafter also referred to as NB), as a molecular weight regulator 1 - Butene (1.69 g, 30.1 mmol) was added to toluene (275 g), and the mixture was stirred under heating at 105 °C. Further, a toluene solution (0.28 mL) and WCl ₆ (38 μmol) in toluene (0.75 mL) of i-Bu ₃ Al (75 μmol) and methanol (11 μmol) were mixed at room temperature. A toluene solution of the above monomer was sequentially added with a mixed toluene solution of i-Bu ₃ Al and methanol, and a toluene solution of WCl _{6 to} initiate polymerization. After 1 hour of polymerization, LiOH (228 μmol) was added as a reaction terminator to obtain a toluene solution of the ring-opened copolymer [1]. The addition ratio of the monomer was measured to be 99%. A part of it was precipitated in a large amount of methanol, and dried under reduced pressure to obtain a ring-opened copolymer [1]. As a result of ¹ H-NMR analysis, the composition of the monomer derived from the polymer was 48.1 mol% derived from tricyclopentadiene, which was derived from 8-methyl-8-methoxycarbonyl-tetracyclo[4.4 .0.1 ^2,5 .1 ^7,10 ]Dodeca-3-ene is 21.4 mol %, derived from bicyclo [2.2.1] hept-2-ene is 30.5 mol %.

The toluene solution (353 g) of the ring-opening copolymer [1] obtained above was pipetted into a hydrogenation reaction vessel, and toluene (236 g) was added thereto and stirred to be a homogeneous solution, and a hydrogenation catalyst Ru[4-CH ₃ (CH) was added. ₂ ) ₄ C ₆ H ₄ CO ₂ ]H(CO)[P(C ₆ H ₅ ) ₃ ] (49.3 mg, 582 μmol). After the temperature was raised to 90 ° C and hydrogen gas was introduced to 7 MPa, the temperature was finally raised to 160 to 165 ° C, and the introduced hydrogen pressure was 9 to 10 MPa for 3 hours. The obtained product was precipitated in a large amount of methanol, and dried under reduced pressure to obtain a ring-opening copolymerized hydride [1]. The hydrogenation rate by ¹ H-NMR analysis was 99.9%. It was determined by DSC to be Tg = 139 °C. After the GPC measurement, the weight average molecular weight (Mw) = 36,000, and the molecular weight distribution (Mw/Mn) = 2.8. Further, the refractive index n _D = 1.532 and the Abbe number is 57. The results are shown in Table 1.

[Embodiment 2]

The same operation as in Example 1 was carried out except that the geometric isomer contained 90% of the compound (2-1) (including the specular isomer) was used as the TCP to obtain a ring-opening copolymerized hydride [2] ]. The hydrogenation rate by ¹ H-NMR analysis was 99.9%. It was determined by DSC to be Tg = 139 °C. After the GPC measurement, the weight average molecular weight (Mw) = 36,000, and the molecular weight distribution (Mw/Mn) = 2.8. Further, the refractive index n _D = 1.533 and the Abbe number is 57. The results are shown in Table 1.

[Example 3]

The same operation as in Example 1 was carried out except that the geometric isomer contained 96% of the compound (2-1) (including the specular isomer) was used as the TCP to obtain a ring-opening copolymerized hydride [3]. ]. The hydrogenation rate by ¹ H-NMR analysis was 99.9%. It was determined by DSC to be Tg = 139 °C. After the GPC measurement, the weight average molecular weight (Mw) = 40,000, and the molecular weight distribution (Mw/Mn) = 2.9. Further, the refractive index n _D = 1.533 and the Abbe number is 56. The results are shown in Table 1.

[Comparative Example 1]

The same operation as in Example 1 was carried out except that 50% of the compound (2-1) (including a specular isomer) was used as the geometric isomer, and a ring-opening copolymerized hydride was obtained [4]. . The hydrogenation rate by ¹ H-NMR analysis was 99.9%. It was determined by DSC to be Tg = 140 °C. After the GPC measurement, the weight average molecular weight (Mw) = 39,000, and the molecular weight distribution (Mw/Mn) = 2.8. Further, the refractive index n _D = 1.530 and the Abbe number is 57. The results are shown in Table 1.

[Example 4]

0.4 parts by mass of a rubbery polymer (DYNARON 8903P manufactured by JSR; styrene ‧ ethylene butylene styrene block copolymer) was added to 99.6 parts by mass of the ring-opening copolymerized hydride [1] obtained in Example 1, Anti-aging agent (IRGANOX 1010 manufactured by BASF) 0.03 parts by mass, using a twin-axis kneading machine (TEM-37BS manufactured by Toshiba Machine Co., Ltd., temperature 280 ° C, screw rotation number 100 rpm, feeder rotation number 10 rpm, discharge amount 18 kg/hour) Mix and extrude to become granule 1. Using this pellet 1, a test piece of 60 mm × 80 mm × 1.0 mm was produced by injection molding (S2000i100B manufactured by FANUC, mold binding pressure of 100 tons, resin temperature of 280 ° C, and mold temperature of 120 ° C). The plate was sliced to a thickness of about 0.1 μm, and the polystyrene portion was dyed with ruthenium tetroxide. After observation by a transmission electron microscope, the rubbery polymer became a slightly spherical micro-block structure having a diameter of about 0.2 μm in the hydride matrix. .

Next, autoclave sterilization treatment was carried out using a test plate. The test plate was hung in a dedicated metal cage, fixed in an autoclave (HV-240MIV manufactured by Hirayama Seisakusho Co., Ltd.), and treated at 123 ° C for 70 minutes. After 70 minutes, after cooling to 60 degrees, the apparatus was turned on and the metal cage was taken out and aged in the atmosphere for 30 minutes. The appearance of the test plate after aging was good, and no white turbidity, cracks, and deformation due to heat were observed by visual observation, and no crack was observed by the microscope.

[Comparative Example 2]

0.03 parts by mass of an anti-aging agent (IRGANOX 1010 manufactured by BASF) was added to 100 parts by mass of the ring-opening copolymerized hydride [1] obtained in Example 1, and a twin-axis kneading machine (TEM-37BS manufactured by Toshiba Machine Co., Ltd., and The same conditions as in Example 4 were kneaded and extruded to prepare pellets 2. Using this pellet 2, a test piece of 60 mm × 80 mm × 1.0 mm was produced by injection molding (manufactured by FANUC S2000i100S under the same conditions as in Example 4).

After the autoclave treatment of the test plate was carried out in the same manner as in Example 4, the visual white turbidity was severely opaque, and cracking was confirmed by microscopic observation.

[Example 5]

The same operation as in Example 1 was carried out except that 71% of the compound (2-1) (including a mirror isomer) was used as the geometric isomer, and a ring-opening copolymerized hydride was obtained [5]. . The hydrogenation rate by ¹ H-NMR analysis was 99.9%. It was determined by DSC to be Tg = 141 °C. After the GPC measurement, the weight average molecular weight (Mw) = 37,000, and the molecular weight distribution (Mw/Mn) = 2.7. Further, the refractive index n _D = 1.532 and the Abbe number is 56. The results are shown in Table 1.

[Embodiment 6]

A ring-opening copolymerized hydride was obtained in the same manner as in Example 1 except that 57% of the compound (2-1) (including a mirror isomer) was used as the geometric isomer. . The hydrogenation rate by ¹ H-NMR analysis was 99.9%. It was determined by DSC to be Tg = 141 °C. After the GPC measurement, the weight average molecular weight (Mw) = 34,000, and the molecular weight distribution (Mw/Mn) = 2.5. Further, the refractive index n _D = 1.532 and the Abbe number is 56. The results are shown together in Table 1.

[Comparative Example 3]

The same operation as in Example 1 was carried out except that the compound (2-1) (including the mirror isomer) contained in the geometrical isomer was used as the TCP to obtain a ring-opening copolymerized hydride [7]. . The hydrogenation rate by ¹ H-NMR analysis was 99.9%. It was determined by DSC to be Tg = 140 °C. After the GPC measurement, the weight average molecular weight (Mw) = 38,000, and the molecular weight distribution (Mw/Mn) = 2.8. Further, the refractive index n _D = 1.532 and the Abbe number is 57. The results are shown together in Table 1.

The manufacture of TCP is described below as a monomer embodiment. Further, an example of a polymer using the monomer will be described as a polymer example. Further, both the molecular weight and the Tg were measured by the above method, and the intrinsic viscosity, the gel evaluation, and the ratio of the structural unit in the polymer other than the evaluation items were measured or evaluated by the following methods.

(1) Intrinsic viscosity [η _inh ]

The intrinsic viscosity was measured using a Ubbelohde type viscometer in chlorobenzene at a sample concentration of 0.5 g/dL and a temperature of 30 °C.

(2) Gel evaluation

A T-die having a width of 600 mm was installed at the front end of a single-axis extruder having a diameter of 50 mm to extrude a sufficiently dried cyclic olefin polymerization hydride, and a sheet-like molded article having a thickness of 0.8 mm was obtained by cooling on a roll and a conveyor belt. . The obtained molded article was sampled in an area of 12 × 10 cm and dissolved in toluene, and subjected to pressure filtration using a membrane filter made of Teflon (registered trademark) having a pore size of 0.1 μm. The number of transparent gels seen on the filter was counted to determine the gelation inhibition performance. When the number of gels in the criterion is determined to be small, the gel production inhibition performance is good. The number of gels is 0 to 2, which is marked as "○", 3 to 9 are marked as "△", and 10 or more are recorded as "×". "." In addition, when the number of the gels was 10 or more, it was confirmed that the defects at the time of product formation were remarkable, which was an unacceptable level.

(3) Composition of each component in the TCP content

It was measured by gas chromatography (GC). The capillary column was TC-WAX from GL Sciences.

Monomer Example 1

DCP (purity 98%, bridge/hanging = 99/1) was placed in a nitrogen-substituted autoclave, and stirred at 180 ° C for 3 hours while the reaction was carried out until the DCP conversion rate was 40%, and the TCP content was obtained. . The obtained TCP-containing material (I) was simply distilled, and the light-boiling portion of the unreacted DCP or the like and the reboiled portion of the CPD tetramer or more were removed to obtain a TCP-containing material (II). Further, the obtained TCP content (II) was subjected to rectification by a distillation column (filler: HELI PACK) at a column top pressure of 0.5 kPa and a reflux ratio of 30, and the compound represented by the formula (5) in the distillate/ When the mass ratio of the compound represented by the formula (6) was 99.0/1.0, the recovery of the TCP-containing material (III) was started. To the recovered TCP content (III), 200 ppm of an antioxidant was added to obtain TCP (A). The composition of TCP(A) is that the 6,5,6-TCP represented by (6) is 0.3% by mass, the DCP is 0.3% by mass, and the bridge/hanging in the 6,6,5-TCP is 84/16, and The specific oxide content was 30 ppm. Its gas chromatogram is shown in Figure 2.

Monomer Examples 2 to 5 and Monomer Comparative Examples 1 to 5

Except that the conditions described in Table 1 were changed, TCP (J) was obtained from TCP (B) in the same manner as in the first embodiment. The characteristics of TCP (J) obtained from TCP (B) are shown in Table 2.

Polymer Example 1

100 parts by mass of TCP (A) obtained in the monomer example 1 and 9 parts by mass of 1-hexene as a molecular weight modifier were added to 280 parts by mass of cyclohexane, and the mixture was heated and stirred at 105 °C. Further, 0.005 parts by mass of triisobutylaluminum and 0.003 parts by mass of methanol were added, and further 0.005 parts by mass of WCl _{6 was} added, and a polymer was obtained by a reaction for 1 hour. The yield of the polymer was 99% by mass and was good. The solution of the obtained polymer was poured into an autoclave, and 200 parts by mass of cyclohexane was further added. Next, 0.006 parts by mass of a hydrogenation catalyst of RuHCl(CO)[P(C ₆ H ₅ )] _{3 was added} , and after heating to 90 ° C, hydrogen gas was injected into the reactor to bring the pressure to 10 MPa. Subsequently, the pressure was maintained at 10 MPa, and the reaction was carried out at 165 ° C for 3 hours to obtain a hydrogenated cyclic olefin polymerization hydride.

The cyclic olefin polymerization hydride was a weight average molecular weight (Mw) = 3.8 × 10 ⁴ , a molecular weight distribution (Mw / Mn) = 2.3, an intrinsic viscosity (η _inh ) = 0.48, and a glass transition temperature (Tg) = 139 °C. Further, after the hydrogenation rate of the cyclic olefin polymerization hydride was determined by ¹ H-NMR measurement, the olefinic unsaturated bond was 99.9% or more and hydrogenated.

The obtained cyclic olefin polymerization hydride solution was solidified using a large amount of methanol, and dried to obtain a cyclic olefin polymerization hydride. As a result of the evaluation of the gel, the number of gels was one, and it was judged as "○".

In addition, the comprehensive evaluation of each of the examples and the comparative examples was performed as "○" when the polymerization conversion ratio was 92% or more, the molecular weight distribution (Mw/Mn) was 2.9 or less, and the gel evaluation was Δ or more. When satisfied, it is marked as "X". The results are shown in Table 3.

Polymer Examples 2-8 and Polymer Comparative Examples 1-9

The cyclic olefin polymerization hydride was obtained in the same manner as in Polymer Example 1, except that the TCP (A) used in Polymer Example 1 was changed to the monomer shown in Table 3. The evaluation results of the obtained cyclic olefin polymerization hydride are shown in Table 3.

[Industry possible use]

The cyclic olefin ring-opening polymer of the present invention, in particular, the cyclic olefin ring-opening polymer of a hydride, can be suitably used as an optical component as a thermoplastic transparent resin excellent in light transmittance or heat resistance. Examples of the optical component include an optical lens, a film, and a sheet. Examples of the specific examples include an image pickup lens, a light guide plate, a retardation film, a protective film, a film, a touch panel, a transparent electrode substrate, and a substrate for a TFT. A color filter substrate, a medical container such as a pre-filled syringe, or the like. In particular, the cyclic olefin ring-opening polymer of the present invention, particularly the cyclic olefin ring-opening copolymerized hydride of the hydride, can be preferably used in various forms because of its high refractive index and high Abbe number. The use of the body is particularly applicable to the production of molded articles used in various optical applications such as lenses and films, and is particularly applicable to optical lens applications.

Figure 1 is a Diels-Alder reaction diagram of DCP and CPD.

2 is a gas chromatogram of the compound obtained in Monomer Example 1.

Claims (11)

A cyclic olefin ring-opening polymer obtained by polymerizing a cyclic olefin monomer containing a compound (1) represented by the following formula (1), which is characterized by the above formula ( 1), n is 1, 2 or 3, and each geometric isomer of the above compound (1) contains 55 mol% or more as the geometric isomer (2), n = 1 to 3, each of the following cases. When the compound is n=2, the compound represented by the following formula (2-1) is a compound represented by the following formula (2-2), and the compound represented by the following formula (2-3) is represented by the following formula (2-3). In the case of a compound, the specular isomer is also included in the presence of a specular isomer. The cyclic olefin ring-opening polymer of claim 1, wherein the cyclic olefin ring-opening polymer has a polystyrene-equivalent weight average molecular weight of 20,000 to 150,000 as measured by gel permeation chromatography. The cyclic olefin ring-opening polymer according to claim 1 or 2, wherein the compound (1) contains 10 to 90 mol% based on the total monomers of the copolymerization. The cyclic olefin ring-opening polymer according to claim 1 or 2, wherein the ring-opening polymer has a refractive index of 1.531 or more at 589 nm, and is bent. The flexural modulus is 2600 MPa or more. The cyclic olefin ring-opening polymer according to claim 1 or 2, wherein the compound (1) is represented by the above formula (2-1). The cyclic olefin ring-opening polymer according to claim 1 or 2, wherein the cyclic olefin monomer comprises the compound (3) represented by the following formula (3), [In the formula (3), m is an integer of 0 to 3, and each of A ¹ to A ⁴ independently represents any one of the following (i) to (iv), and at least one of the above represents (iii), (i) a hydrogen atom (ii) a halogen atom (iii) a polar group selected from the group consisting of an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amine group, and a thiol group, and (iv) may pass through a halogen atom or a The aliphatic group (iii) is substituted with an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. The cyclic olefin ring-opening polymer according to claim 1 or 2, wherein the cyclic olefin monomer comprises a compound (4) represented by the following formula (4), [In the formula (4), B ¹ to B ⁴ each independently represent any of the following (i) to (iii), or represent (iv) or (v), (i) a hydrogen atom (ii) a halogen atom ( Iii) an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group or an aromatic hydrocarbon group which may be substituted by a halogen atom, (iv) B ¹ and B ² or B ³ and B ⁴ represent a bond to each other to form an alkylene group And B ¹ to B ⁴ independently of the above-mentioned bonding are independent of each other and represent (i) to (iii), (v) B ¹ and B ³ , B ¹ and B ⁴ , B ² and B ³ , Or B ² and B ⁴ are bonded to each other to form a cyclic structure together with the carbon atoms bonded to the respective bonds, and B ¹ to B ⁴ independent of the aforementioned bonding are independent of each other to indicate that they are selected by the above (i) to (iii) ]. A cyclic olefin ring-opening polymerization hydride characterized in that the hydride is obtained by hydrogenating a cyclic olefin ring-opening polymer according to claim 1 or 2. A cyclic olefin ring-opening polymerization hydride composition characterized in that 90 to 99.99% by mass of the above cyclic olefin ring-opening polymerization hydride, and 10 to 0.01 are formulated with respect to all the compositions. a mass% of a formulation which is incompatible with the hydride, and the aforementioned formulation is an oak Glial polymer. A tricyclopentadiene represented by the following formula (5), characterized in that the tricyclopentadiene has the following characteristics of at least one of (a), (b) and (c), and (a) The above formula (6) represents 1,4,4a,4b,5,8,8a,9a-octahydro-1,4;5,8-dimethylene-1H-indole relative to tricyclopentadiene The amount is 1% by mass or less, and (b) the tricyclopentadiene represented by the following formula (5) is 3a, 4, 4a, 5, 8, 8a, 9, 9a- represented by the following formula (2-1). An endo body of octahydro-4,9;5,8-dimethylene-1H-benzo[f]indole with respect to the bridge body and 3a, 4, 4a represented by the following formula (2-1a) , 5,8,8a,9,9a-octahydro-4,9; 5,8-dimethylidene-1H-benzo[f]pyrene (exo) body total amount of 50% or more (c) The content of the oxide contained in the entire formula (5) and the following formula (6) is 100 ppm or less, The tricyclopentadiene of claim 10, which has the characteristics indicated by the above (a), (b) and (c).