JP5569147B2 - Method for producing cyclic olefin ring-opening polymer - Google Patents

Description

  The present invention relates to a method for producing a cyclic olefin-based ring-opening polymer using a ruthenium catalyst having high polymerization activity, and a cyclic olefin-based polymer.

  Polymers obtained by polymerizing cyclic olefin compounds by ring-opening metathesis reaction are thermoplastic transparent resins that have both high light transmittance and heat resistance. Optical lenses, optical fibers, optical films, etc. that require these functions Applications are expanding in the field of optical materials. Resins for optical materials are required to be less colored, and it is therefore necessary to reduce the amount of metal remaining in the resin to a level of ppm relative to the resin weight. If the product is a low molecular weight compound, this can be achieved by a low-cost separation process such as distillation, but if it is a medium or high molecular weight compound, a solvent extraction method or column adsorption can be used. A costly process that requires a large amount of solvent, adsorbent, etc. must be used. Therefore, when mass-producing low-priced general-purpose resins, it is necessary to reduce the burden on this process. As one of the improvement measures, there is a method of reducing the amount of catalyst to be used by increasing the activity of the catalyst.

However, with the tungsten and molybdenum catalyst systems that have been employed in the production of conventional general-purpose resins, the catalyst amount that allows the polymerization reaction to proceed quantitatively is at the level of catalyst / monomer = 1 / tens of thousands (molar ratio). The performance was far from the ppm level (= 1 / 1,000,000). On the other hand, ruthenium carbene complexes such as Grubbs complex, which are widely studied as highly active metathesis reaction catalysts, have a limit of 1 / 100,000 to 1 / 500,000, and further improvement is required. It had been.

The present invention has been made in view of such problems of the prior art, and the object is to use a ruthenium catalyst having a high polymerization activity, to reduce the number of polymerization processes, and to achieve a high monomer pass-through rate. Another object of the present invention is to provide a method for producing a cyclic olefin-based ring-opening polymer capable of reducing the metal content in the polymer and the like, and a cyclic olefin-based ring-opening polymer.

The present inventors can proceed the reaction quantitatively with a target amount of catalyst by using a complex species having a specific structure (Special Table 2010-503713) to solve the above problem. As a result, the present invention has been completed.

That is, according to the present invention, the following is provided.

  [1] A method for producing a cyclic olefin-based ring-opening polymer, comprising a step of subjecting a cyclic olefin-based compound to a ring-opening polymerization reaction in the presence of a catalyst represented by the following formula (1).

式（１）中、Ｘ^１、Ｘ^２、およびＬは配位子を表す。ａ、ｂ、ｃ、ｄは、相互に独立に、水素原子、ニトロ基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、またはフェニルを表し、前記フェニル基は、炭素数１〜６のアルキル基および炭素数１〜６のアルコキシ基で置換されていてもよい。Ｒ^１は、炭素数１〜１２のアルキル基、炭素数５〜６のシクロアルキル基、炭素数７〜１８のアラルキル基、またはアリール基を表し、Ｒ^２は、水素原子、炭素数１〜１２のアルキル基、炭素数５〜６のシクロアルキル基、炭素数７〜１８のアラルキル基、アリールを表し、Ｒ^３は、水素原子、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、炭素数２〜１２のアルキニル基、アリールを表す。

In formula (1), X ¹ , X ² , and L represent a ligand. a, b, c, and d each independently represent a hydrogen atom, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or phenyl, It may be substituted with a 1-6 alkyl group and a C1-C6 alkoxy group. R ¹ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, or an aryl group, and R ² represents a hydrogen atom or 1 to 12 carbon atoms. Represents an alkyl group, a cycloalkyl group having 5 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and aryl, and R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Group, a C2-C12 alkynyl group and aryl are represented.

[2] The cyclic olefin compound according to [1], wherein the cyclic olefin compound is at least one selected from compounds represented by the following formula (X ₀ ) and the following formula (Y ₀ ). A method for producing a ring-opening polymer.

（式（Ｘ_０）中、Ｒ^ｘ１〜Ｒ^ｘ４は、それぞれ独立に下記（ｉ）〜（ｉｘ）で示される基を表し、ｋ^ｘ、ｍ^ｘおよびｐ^ｘは、それぞれ独立に０または正の整数を表す。
（ｉ）水素原子
（ｉｉ）ハロゲン原子
（ｉｉｉ）トリアルキルシリル基
（ｉｖ）酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基を含む置換または非置換の炭素原子数１〜３０の炭化水素基
（ｖ）置換または非置換の炭素原子数１〜３０の炭化水素基
（ｖｉ）極性基（但し（ｉｖ）を除く）
（ｖｉｉ）Ｒ^ｘ１とＲ^ｘ２、またはＲ^ｘ３とＲ^ｘ４が、相互に結合して形成されたアルキリデン基で、該結合に関与しないＲ^ｘ１〜Ｒ^ｘ４は、相互に独立に上記（ｉ）〜（ｖｉ）より選ばれる基
（ｖｉｉｉ）Ｒ^ｘ１とＲ^ｘ２、またはＲ^ｘ３とＲ^ｘ４が、相互に結合して形成された単環もしくは多環の炭化水素環または複素環で、該結合に関与しないＲ^ｘ１〜Ｒ^ｘ４は、相互に独立に上記（ｉ）〜（ｖ）より選ばれる基、もしくはＲ^ｘ１とＲ^ｘ２が、相互に結合して形成された単環の飽和炭化水素環または複素環で、該結合に関与しないＲ^ｘ１〜Ｒ^ｘ４は、相互に独立に上記（ｉ）〜（ｖ）より選ばれる基

(Wherein _{^{(X 0), R x1 ~R}} x4 each independently represent a group represented by the following ^{(i) ~ (ix),} k x, m x and ^{p x} are each independently 0 or a positive Represents an integer.
(I) a hydrogen atom (ii) a halogen atom (iii) a trialkylsilyl group (iv) a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms containing a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom Hydrogen group (v) substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi) polar group (excluding (iv))
(Vii) R ^x1 and R ^x2 , or R ^x3 and R ^x4 are alkylidene groups formed by bonding to each other, and R ^{x1 to} R ^{x4 that} are not involved in the bonding are independently selected from the above (i) to ( ^x ) A group selected from (vi) (viii) R ^x1 and R ^x2 , or R ^x3 and R ^x4 are monocyclic or polycyclic hydrocarbon rings or heterocycles formed by bonding to each other, and are involved in the bond R ^{x1 to} R ^x4 are groups independently selected from the above (i) to (v), or a monocyclic saturated hydrocarbon ring or a heterocycle formed by bonding R ^x1 and R ^x2 to each other. R ^{x1 to} R ^{x4 which} are not involved in the bond in the ring are groups independently selected from the above (i) to (v)

（式（Ｙ_０）中、Ｒ^ｙ１、Ｒ^ｙ２は上記（ｉ）から（ｖｉ）で示される基を表すか、下記（ｉｘ）、（ｘ）で示される基を表し、ｋ^ｙ、ｍ^ｙおよびｐ^ｙは、それぞれ独立に、０または正の整数を表す。
（ｉｘ）Ｒ^ｙ１とＲ^ｙ２が、相互に結合して形成された単環もしくは多環の炭化水素環または複素環
（ｘ）Ｒ^ｙ１とＲ^ｙ２が相互に結合して形成された芳香環

(In the formula _{(Y ^0),} or R ^{y1, R y2} is a group represented by the above (i) (vi), represents a group represented by the following ^{(ix), (x),} k y, m y And ^py each independently represents 0 or a positive integer.
(Ix) R ^y1 and R ^y2 are monocyclic or polycyclic ring formed coupled to one another hydrocarbon ring or a heterocyclic ring (x) R ^y1 and aromatic ring R ^y2 is formed by bonding to each other

  [3] The a, b and c represent a hydrogen atom, and d is a phenyl group substituted with a hydrogen atom, a group selected from a C 1-6 alkyl group and a C 1-6 alkoxy group. The method for producing a cyclic olefin-based ring-opening copolymer according to the above [1] to [2], wherein

  [4] The method for producing a cyclic olefin-based ring-opening copolymer according to the above [1] to [3], wherein a, b, c and d represent a hydrogen atom.

[5] A ligand represented by the formula P (R ^L0 ) ₃ (referred to as formula (L ⁰ )), the following formulas (L ¹ ), (L ² ), (L ³ ) and (L ⁴ ) The method for producing a cyclic olefin-based ring-opening copolymer according to any one of the above [1] to [4], which is a kind selected from the ligands represented by

式（Ｌ^０）中、Ｒ^Ｌ０は、炭素数１〜６のアルキル基、炭素数３〜６の環状炭化水素基またはアリール基を表す。式（Ｌ^１）〜（Ｌ^４）中Ｒ^Ｌ１およびＲ^Ｌ２は、相互に独立に、水素原子、炭素数１〜６のアルキル基、またはアリール基を表わす。Ｒ^Ｌ３およびＲ^Ｌ３は、相互に独立に、水素原子、炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基、またはアリール基を表すか、あるいはＲ^Ｌ３およびＲ^Ｌ４は互いに結合し、５員または６員の環状炭化水素基を表わす。Ｒ^Ｌ５およびＲ^Ｌ６はハロゲン原子を表す。

In the formula (L ⁰ ), R ^L0 represents an alkyl group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, or an aryl group. In the formulas (L ¹ ) to (L ⁴ ), R ^L1 and R ^L2 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group. R ^L3 and R ^L3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group, or R ^L3 and R ^L4 are bonded to each other. Represents a 5-membered or 6-membered cyclic hydrocarbon group. R ^L5 and R ^L6 represent a halogen atom.

  [6] The amount of the catalyst represented by the formula (1) used is such that the molar ratio with the cyclic olefin compound (catalyst / cyclic olefin compound) is 1 / 10,000,000 to 1 / 500,000. The method for producing a cyclic olefin-based ring-opening polymer according to the above [1] to [5].

  According to the present invention, it is possible to quantitatively advance a ring-opening metathesis polymerization reaction of a cyclic olefin with a small catalyst amount, and a method for producing a cyclic olefin-based ring-opening copolymer having a low metal content at low cost. Can be provided.

Hereinafter, the present invention will be specifically described.

<Catalyst>
The catalyst used in the present invention is a catalyst represented by the following formula (1). (Hereinafter also referred to as catalyst (1))

式（１）中、式（１）中、Ｘ^１〜Ｘ^２はアニオン性配位子を表し、Ｌは中性配位子を表す。ａ、ｂ、ｃ、ｄは、相互に独立に、水素原子、ニトロ基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、またはフェニルを表し、前記フェニル基は、炭素数１〜６のアルキル基および炭素数１〜６のアルコキシ基で置換されていてもよい。Ｒ¹は、炭素数１〜１２のアルキル基、炭素数５〜６のシクロアルキル基、炭素数７〜１８のアラルキル基、またはアリール基を表し、Ｒ²は、水素原子、炭素数１〜１２のアルキル基、炭素数５〜６のシクロアルキル基、炭素数７〜１８のアラルキル基、アリールを表し、Ｒ³は、水素原子、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、炭素数２〜１２のアルキニル基、アリールを表す。

In the formula (1) wherein ^(1), X 1 to X ² represents an anionic ligand, L is representative of the neutral ligand. a, b, c, and d each independently represent a hydrogen atom, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or phenyl, It may be substituted with a 1-6 alkyl group and a C1-C6 alkoxy group. R ¹ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, or an aryl group, and R ² represents a hydrogen atom or 1 to 12 carbon atoms. Represents an alkyl group, a cycloalkyl group having 5 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and aryl, and R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Group, a C2-C12 alkynyl group and aryl are represented.

X ¹ and X ² are preferably halogen atoms, particularly Cl and Br.

A, b, c and d each independently represent a hydrogen atom, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or phenyl, and the phenyl group has 1 carbon atom. It may be substituted with an alkyl group of ˜6 and an alkoxy group of 1 to 6 carbon atoms. R ¹ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and an aryl group, and R ² represents hydrogen, 1 to 12 carbon atoms Represents an alkyl group, a cycloalkyl group having 5 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and aryl, and R ³ represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, An alkynyl group having 2 to 12 carbon atoms and aryl are represented.

  A, b, c and d are preferably a hydrogen atom, a nitro group, a methyl group, an ethyl group, an isopropyl group, a methoxy group or a phenyl group, and the phenyl group may be substituted with a methyl group or a methoxy group, Particularly preferred is a hydrogen atom.

R ¹ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and an aryl group.

R ¹ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-heptyl group, a cyclopentyl group, a cyclohexyl group, or a 2-methylcyclohexyl group. 2,4-dimethylcyclohexyl group, benzyl group, 1-phenylethyl group, 2-phenylethyl group, phenyl group, o-, m-, p-tolyl group, and 3,5-dimethylphenyl group are preferable.

R ² represents hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, or aryl.

R ² represents a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-heptyl group, cyclopentyl group, cyclohexyl group, 2- A methylcyclohexyl group, 2,4-dimethylcyclohexyl group, benzyl group, 1-phenylethyl group, 2-phenylethyl group, phenyl group, o-, m-, p-tolyl group, and 3,5-dimethylphenyl group; preferable.

R ³ represents hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or aryl.

R ³ is preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group. Further, R ¹ , R ² , and R ³ are each particularly preferably a hydrogen atom.

L is a ligand represented by the formula P (R ^L0 ) ₃ (hereinafter referred to as formula (L ⁰ )), the following formulas (L ¹ ), (L ² ), (L ³ ) and (L ⁴ ). It is a kind selected from the ligands represented.

In the formula (L ⁰ ), R ^L0 represents an alkyl group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms, or an aryl group, and is preferably a phenyl group, a cyclopentyl group, or a cyclohexyl group.

In the formulas (L ¹ ) to (L ⁴ ), R ^L1 and R ^L2 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group. R ^L3 and R ^L4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group, or R ^L3 and R ^L4 are bonded to each other. Represents a 5-membered or 6-membered cyclic hydrocarbon group. R ^L5 and R ^L6 represent a halogen atom.

L is preferably the formula (L ¹ ), R ^L1 and R ^L2 are preferably mesityl groups, and R ^L3 and R ^L4 are preferably hydrogen atoms.

<Cyclic olefin compound>
The cyclic olefin compound used in the present invention is a compound represented by the formula (X ₀ ) (hereinafter also referred to as the compound (X ₀ )) and a compound represented by the formula (Y ₀ ) (hereinafter referred to as the compound (Y _0). It is also preferable that it is at least one kind selected from.

When R ^{x1 to} R ^x4 in the formula (X ₀ ) or R ^y1 and R ^{y2 in} the formula (Y ₀ ) are halogen atoms, examples thereof include a fluorine atom, a chlorine atom, and a bromine atom, and substituted or unsubstituted carbon In the case of a hydrocarbon group having 1 to 30 atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-heptyl group, cyclopentyl group, cyclohexyl Group, benzyl group, 1-phenylethyl group, substituted or unsubstituted alkyl group such as 2-phenylethyl group, phenyl group, o-, m-, p-tolyl group, and 3,5-dimethylphenyl group, naphthyl And a substituted or unsubstituted aryl group such as a group, a biphenyl group, an indenyl group, a fluorenyl group, and an anthracenyl group. Examples of the polar group include an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group, or a hydroxyl group.

Specific examples of the compound (X ₀ ) include bicyclo [2.2.1] hept-2-ene (also referred to as “norbornene”), 5-methyl-bicyclo [2.2.1] hept-2-ene. 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene 8-methyl-tetracyclo [4.4.0.1 ^{2 , 5} . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 5-phenyl - bicyclo [2.2.1] hept-2-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^4,9 ] tetradeca-4,6,8,12-tetraene (1,4,4a, 9a-tetrahydro-1,4-methanofluorene), 5-methoxy-bicyclo [2.2.1] hept-2 -Ene, 5-hydroxymethyl-bicyclo [2.2.1] hept-2-ene, 5-amino-bicyclo [2.2.1] hept-2-ene, 5-methoxycarbonyl-bicyclo [2.2 .1] Hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyl-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 ] dodec-3-ene. .

Specific examples of the compound formula (Y ₀ ) include tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (also referred to as “dicyclopentadiene”), pentacyclo [6.5.1. 0.0 ^2,7 . 1 ^3,6 . 0 ^9,13] pentadeca-4,10-diene (also referred to as "bird cyclopentadiene".), Heptacyclo [8.7.0.1 ^2,9. 0 ^3,8 . 1 ^4,7 . 1 ^{11, 17} . 0 ^{12, 16]} eicosa-5,13-diene (also referred to as "tetra cyclopentadiene."), And Nonashikuro [10.9.1.0 ^2,11. 1 ^3,10 . 0 ^4,9 . 1 ^5,8 . 0 ^13,21 . 1 ^14,20 . 0 ^15,19 ] pentacosa-6,16-diene (also referred to as “pentacyclopentadiene”). Among these, dicyclopentadiene and tricyclopentadiene are preferable.

Compound formula (X ₀ ) or compound (Y ₀ ) may be used alone or in combination of two or more, and the composition ratio is not particularly limited and may be mixed at an arbitrary ratio. it can.

<Ring-opening copolymerization>
In the cyclic olefin ring-opening polymerization of the present invention, the amount of the catalyst (1) used is such that the molar ratio with the cyclic olefin compound (catalyst (1) / cyclic olefin compound) is 1 / 10,000,000 to 1. / 500,000 is preferable, and 1 / 10,000,000 to 1 / 1,000,000 is more preferable. When the ratio is larger than 1 / 500,000, the hue of the polymer is greatly affected. When the amount is less than 1 / 10,000,000, there is a problem that the polymerization reaction does not proceed.

As the polymerization solvent, a solvent that can dissolve or disperse the catalyst (1), the compound (X ₀ ), the compound (Y ₀ ), and the produced ring-opening polymer can be used. Specific examples of the polymerization solvent include alkanes such as pentane, hexane, heptane, octane, nonane, decane, cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, benzene, toluene, xylene, ethylbenzene, cumene. Aromatic hydrocarbons such as, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, halogenated alkanes such as chlorobenzene, chloroform, tetrachloroethylene, ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, etc. And saturated ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane. Among these, the polymerization solvent used in the present invention preferably contains an aromatic hydrocarbon having good solubility. Moreover, these polymerization solvents can be used alone or in combination of two or more.

  In the method for producing a cyclic olefin-based ring-opening copolymer of the present invention, the ring-opening copolymerization reaction conditions may be appropriately adjusted so that the obtained cyclic olefin-based copolymer has a desired molecular weight depending on the application. In addition, a molecular weight regulator can be used in the ring-opening copolymerization reaction.

  Specific examples of molecular weight regulators that can be suitably used include α- such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. Examples thereof include olefins and styrene. Among these, 1-butene and 1-hexene are particularly preferable.

  These compounds can be used as molecular weight regulators alone or in combination of two or more.

  The amount of the molecular weight regulator used is not particularly limited, but is preferably 0.001 to 0.6 mol, more preferably 1 mol per 1 mol of the cyclic olefin monomer used for the ring-opening copolymerization reaction. Is preferably in the range of 0.002 to 0.1 mol. When the amount is less than 0.001, an ultrahigh molecular weight component is generated and a gel is easily formed. When the amount is more than 0.6 mol, the polymerization reaction is often inhibited.

  The reaction time for carrying out the ring-opening copolymerization reaction is not particularly limited, but is desirably 0.1 to 10 hours, preferably 0.1 to 5 hours, and more preferably 0.1 to 3 hours in production. . The reaction temperature is preferably in the range of about 30 to 180 ° C, preferably about 70 to 160 ° C.

  The molecular weight of the cyclic olefin-based ring-opened polymer of the present invention can be appropriately adjusted and produced according to the use and the like, and is not particularly limited, but is measured by gel permeation chromatography (GPC). The number average molecular weight (Mw) in terms of polystyrene needs to be 20,000 to 150,000. When the molecular weight is less than 20,000, the strength of the molded product may be low. On the other hand, when the molecular weight exceeds 150,000, the solution viscosity becomes too high, and the productivity, moldability, and processability of the cyclic olefin copolymer of the present invention may be deteriorated.

  In addition, the molecular weight distribution (Mw / Mn) of the cyclic olefin polymer according to the present invention is not particularly limited. However, for example, when used for a film application, it is usually 1.5 to 10, preferably 1. It is desirable to be 5 to 8, more preferably 1.5 to 5.

<Additives>
The cyclic olefin copolymer of the present invention may be used for molding as it is, but it is used by adding additives such as known antioxidants and ultraviolet absorbers for improving heat resistance and light resistance. Can do. As the additive, for example, known phenol compounds, thiol compounds, sulfide compounds, disulfide compounds, phosphorus compounds and the like can be used as additives to the resin, and at least one of these compounds is used as an additive. By adding 0.01 to 10 parts by weight with respect to 100 parts by weight of the cyclic olefin-based ring-opening polymer of the present invention, characteristics such as heat deterioration resistance and light resistance can be improved.

  Moreover, you may add and use another additive for the cyclic olefin type ring-opening copolymer of this invention as needed. For example, for the purpose of obtaining a colored film, colorants such as dyes and pigments may be added, and a leveling agent may be added to improve the smoothness of the resulting film. Examples of the leveling agent include a fluorine-based nonionic surfactant, a special acrylic resin leveling agent, and a silicone leveling agent.

<Application>
The cyclic olefin ring-opening copolymer according to the present invention, particularly the cyclic olefin ring-opening copolymer that is a hydride, is formed into a desired shape such as a lens shape, a film shape, or a sheet shape by a known method. And can be suitably used for various optical parts such as an optical film.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following Examples and Comparative Examples, each step such as polymerization reaction and catalyst preparation was performed under a nitrogen atmosphere.

<Catalyst>
The catalysts used in this example or comparative example are shown below.

  In Examples and Comparative Examples described later, each measurement and evaluation was performed by the following methods.

Glass transition temperature (Tg)
Using a differential scanning calorimeter (trade name: DSC6200, manufactured by Seiko Instruments Inc.), an extrapolated glass transition start temperature (hereinafter simply referred to as glass transition temperature (Tg)) was determined according to Japanese Industrial Standard K7121.

Weight average molecular weight and molecular weight distribution Gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020), tetrahydrofuran (THF) as a solvent, polystyrene equivalent weight average molecular weight (Mw) and molecular weight Distribution (Mw / Mn) was measured.

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

Analysis of the amount of metal ruthenium in the polymer For the quantitative analysis of the metal ruthenium present in the polymer, an atomic absorption analyzer: Model Z2700 manufactured by Hitachi, Ltd. was used. A standard ruthenium metal aqueous solution was diluted, a calibration curve was prepared by atomic absorption analysis, and the sample was measured with a toluene solution having a polymer solid content of 10% by weight.

[Example 1]
As the cyclic olefin compound (monomer), 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (120 g, 517 mmol) and 1-hexene (0.37 g, 4.4 mmol) as a molecular weight regulator were added to toluene (180 g), and the mixture was heated and stirred at 80 ° C. To this monomer toluene solution, the catalyst (1-1) (96.6 μg, 0.15 μmol) was added as a toluene solution (0.98 mL) to initiate the polymerization reaction. Sampling was performed over time, and ethyl vinyl ether (0.15 μmol) was added as a reaction terminator 1 hour after the start of polymerization to obtain a toluene solution of the ring-opening copolymer (1). Table 1 shows changes with time in the monomer conversion rate. The final monomer conversion was 99%. 1 g of this solution was collected, precipitated in a large amount of methanol, and dried under reduced pressure to obtain a sample for evaluation of the ring-opening copolymer (1). The Tg of this polymer was 210 ° C. The amount of metal ruthenium in this polymer was 0.1 ppm. As a result of GPC measurement, the weight average molecular weight (Mw) was 50,000, and the molecular weight distribution (Mw / Mn) was 2.0.

[Comparative Example 1]
The same operation as in Example 1 was carried out except that the catalyst (2) (849 μg, 1.0 μmol) was used instead of the catalyst (1-1), and a toluene solution of the ring-opening copolymer (2) was prepared. Obtained. Table 1 shows changes with time in the monomer conversion rate. The final monomer conversion was 85%. 1 g of this solution was collected, precipitated in a large amount of methanol, and dried under reduced pressure to obtain a sample for evaluation of the ring-opening copolymer (2). The Tg of this polymer was 211 ° C. The amount of metal ruthenium in this polymer was 0.9 ppm. As a result of GPC measurement, the weight average molecular weight (Mw) was 56,000, and the molecular weight distribution (Mw / Mn) was 1.8.

[Comparative Example 2]
The same operation as in Example 1 was performed except that catalyst (3) (627 μg, 1.0 μmol) was used instead of catalyst (1-1), and a toluene solution of ring-opening copolymer (3) was prepared. Obtained. Table 1 shows changes with time in the monomer conversion rate. The final monomer conversion was 52%. 1 g of this solution was collected, precipitated in a large amount of methanol, and dried under reduced pressure to obtain a sample for evaluation of the ring-opening copolymer (3). The Tg of this polymer was 212 ° C. The amount of metal ruthenium in this polymer was 0.9 ppm. As a result of GPC measurement, the weight average molecular weight (Mw) was 62,000 and the molecular weight distribution (Mw / Mn) was 1.8.

[Example 2]
As the cyclic olefin monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (37.6 g, 162 mmol), tricyclopentadiene (71.5 g, 361 mmol), bicyclo [2.2.1] hept-2-ene (21.9 g, 232 mmol), molecular weight 1-butene (0.66 g, 11.8 mmol) was added to toluene (275 g) as a regulator, and the mixture was heated to 100 ° C. with stirring. To this monomer toluene solution, a toluene solution (1.01 mL) of catalyst (1-1) (377 μg, 0.58 μmol) was added to initiate the polymerization reaction. After 1 hour of polymerization, ethyl vinyl ether (0.58 μmol) was added as a reaction terminator to obtain a toluene solution of the ring-opening copolymer (4). The final monomer conversion was 99%. 1 g of this solution was collected, precipitated in a large amount of methanol, and dried under reduced pressure to obtain a sample for evaluation of the ring-opening copolymer (4). The Tg of this polymer was 165 ° C. The amount of metal ruthenium in this polymer was 0.4 ppm. ^{According to 1} H-NMR analysis, the monomer composition in the polymer was found to be 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene was 14.3 mol%, tricyclopentadiene was 57.3 mol%, and bicyclo [2.2.1] hept-2-ene was 28.4 mol%. As a result of GPC measurement, the weight average molecular weight (Mw) was 33,000, and the molecular weight distribution (Mw / Mn) was 2.3.

[Example 3]
As the cyclic olefin monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . Other than using tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (dicyclopentadiene) (68.2 g, 517 mmol) instead of 1 ^7,10 ] -3-dodecene Performed the same operation as Example 1, and obtained the toluene solution of the ring-opening copolymer (5). The final monomer conversion was 99%. 1 g of this solution was collected, precipitated in a large amount of methanol, and dried under reduced pressure to obtain a sample for evaluation of the ring-opening copolymer (5). The Tg of this polymer was 135 ° C. The amount of metal ruthenium in this polymer was 0.2 ppm. As a result of GPC measurement, the weight average molecular weight (Mw) was 45,000 and the molecular weight distribution (Mw / Mn) was 1.9.

  The cyclic olefin-based ring-opening copolymer according to the present invention can quantitatively advance the ring-opening metathesis polymerization reaction of the cyclic olefin-based compound with a small amount of catalyst by using a specific catalyst. , High monomer pass-through rate, and metal content in polymer can be reduced. In the future, it can be expected to be suitably used for optical lenses, films, and sheets for thermoplastic transparent resins excellent in light transmittance and heat resistance, particularly for optical parts. Specific examples thereof include an imaging lens, a light guide plate, a retardation film, a protective film, an adhesive film, a touch panel, a transparent electrode substrate, a TFT substrate, and a color filter substrate.

Claims (6)

A method for producing a cyclic olefin-based ring-opening polymer, comprising a step of subjecting a cyclic olefin-based compound to a ring-opening polymerization reaction in the presence of a catalyst represented by the following formula (1).

(In Formula (1), X < ¹ >, X < ² > and L represent a ligand. A, b, c, and d are mutually independently a hydrogen atom, a nitro group, a C1-C12 alkyl group, Represents an alkoxy group having 1 to 12 carbon atoms or phenyl, and the phenyl group may be substituted with an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, wherein R ¹ represents the number of carbon atoms; 1-12 alkyl group, a cycloalkyl group having 5 to 6 carbon atoms, an aralkyl group or an aryl group, having 7 to 18 carbon atoms, ^{R 2} represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, carbon atoms Represents a cycloalkyl group having 5 to 6 carbon atoms, an aralkyl group having 7 to 18 carbon atoms and aryl, and R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms 12 represents an alkynyl group, aryl.) The cyclic olefin ring-opening polymer according to claim 1, wherein the cyclic olefin compound is at least one selected from compounds represented by the following formula (X ₀ ) and the following formula (Y ₀ ). Manufacturing method.

(Wherein _{^{(X 0), R x1 ~R}} x4 each independently represent a group represented by the following ^{(i) ~ (ix),} k x, m x and ^{p x} are each independently 0 or a positive Represents an integer.
(I) a hydrogen atom (ii) a halogen atom (iii) a trialkylsilyl group (iv) a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms containing a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom Hydrogen group (v) substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi) polar group (excluding (iv))
(Vii) R ^x1 and R ^x2 , or R ^x3 and R ^x4 are alkylidene groups formed by bonding to each other, and R ^{x1 to} R ^{x4 that} are not involved in the bonding are independently selected from the above (i) to ( ^x ) A group selected from (vi) (viii) R ^x1 and R ^x2 , or R ^x3 and R ^x4 are monocyclic or polycyclic hydrocarbon rings or heterocycles formed by bonding to each other, and are involved in the bond R ^{x1 to} R ^x4 are groups independently selected from the above (i) to (v), or a monocyclic saturated hydrocarbon ring or a heterocycle formed by bonding R ^x1 and R ^x2 to each other. R ^{x1 to} R ^{x4 which} are not involved in the bond in the ring are groups independently selected from the above (i) to (v))

(In the formula _{(Y ^0),} or R ^{y1, R y2} is a group represented by the above (i) (vi), represents a group represented by the following (ix), (x), k y, m y And ^py each independently represents 0 or a positive integer.
(Ix) R ^y1 and R ^y2 are monocyclic or polycyclic ring formed coupled to one another hydrocarbon ring or a heterocyclic ring (x) an aromatic ring R ^y1 and R ^y2 are formed by bonding to each other)   A, b, and c represent a hydrogen atom, and d is a phenyl group substituted with one group selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The manufacturing method of the cyclic olefin type | system | group ring-opening copolymer of Claim 1-2 characterized by the above-mentioned.   The said a, b, c, and d represent a hydrogen atom, The manufacturing method of the cyclic olefin type ring-opening copolymer of Claims 1-3 characterized by the above-mentioned. The L is represented by a ligand represented by the formula P (R ^L0 ) ₃ (referred to as the formula (L ⁰ )), the following formulas (L ¹ ), (L ² ), (L ³ ) and (L ⁴ ). The method for producing a cyclic olefin-based ring-opening copolymer according to any one of claims 1 to 4, which is a kind selected from the following ligands.

(In the formula (L ⁰ ), R ^L0 represents an alkyl group having 1 to 6 carbon atoms, a cyclic hydrocarbon group having 3 to 6 carbon atoms or an aryl group. In the formulas (L ¹ ) to (L ⁴ ), R ^L1 and R ^L2 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, and R ^L3 and R ^L4 each independently represent a hydrogen atom, having 1 to 6 carbon atoms. Represents an alkyl group, an alkenyl group having 2 to 6 carbon atoms, or an aryl group, or R ^L3 and R ^L4 are bonded to each other to represent a 5- or 6-membered cyclic hydrocarbon group, and R ^L5 and R ^L6 represent a halogen atom. Represents an atom.) The amount of the catalyst represented by the formula (1) is such that the molar ratio with the cyclic olefin compound (catalyst / cyclic olefin compound) is 1 / 10,000,000 to 1 / 500,000. method of manufacturing a ring-shaped olefin ring-opening polymer according to claims 1-5.