JP2008248171A - Production method of cyclic olefin-based polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a resin composition which exhibits improved transferability in the molding, is hardly colored even during the detention at a high temperature, and can be easily molded. <P>SOLUTION: The above favorable characteristics are achieved when norbornene or tetracyclododecene, which has been prepared by thermally reacting (a) ethylene, (b) high-purity cyclopentadiene or dicyclopentadiene having a purity higher than 95 wt.%, and optionally (c) norbornene, is used within 7 days after the generation of norbornene or tetracyclododecene. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a cyclic olefin polymer.

  In recent years, optical lenses such as pickup lenses for optical disk optical systems, collimator lenses, and various lenses for small imaging have been replaced with transparent plastic injection-molded lenses instead of conventional glass-ground lenses in order to improve productivity and reduce weight. Investigation continues.

  However, plastics generally have poorer transferability at the time of molding as a high-performance amorphous resin, and the difficulty of molding, such as coloring at the time of residence at high temperatures, is a problem.

For the improvement, for example, improvement in molding conditions as disclosed in Japanese Patent Laid-Open No. 2003-311773, or material handling measures as disclosed in Japanese Patent Laid-Open No. 2003-31737, etc. Although it has been made, it has not yet been sufficiently improved, and there is a need for a material that can be easily molded in every situation.
JP 2003-31773 A JP 2003-31737 A

  It is an object of the present invention to provide a method for producing a resin composition that improves transferability at the time of molding, is less likely to be colored when staying at a high temperature, and is easy to mold.

The present invention is characterized in that, in the method for producing a cyclic olefin polymer, a cyclic olefin as a raw material thereof is used in at least one method selected from the following methods.
1) (a) ethylene, (b) high-purity cyclopentadiene or dicyclopentadiene having a purity of more than 95% by weight, and (c) norbornene or tetracyclododecene obtained by, if necessary, heat-reacting with norbornene, Use within 7 days of formation of norbornene or tetracyclododecene.
2) (a) ethylene, (b) high-purity cyclopentadiene or dicyclopentadiene having a purity of more than 95% by weight, and (c) norbornene or tetracyclododecene obtained by subjecting norbornene to heat reaction as necessary. After storage in the presence of a stabilizer, the stabilizer is used after being reduced to 10 ppm or less by distillation.

  A resin composition that is easy to mold and is easily and efficiently provided that has poor transferability during molding and is less likely to be colored when retained at high temperatures.

As a result of intensive studies to solve this problem, the present inventors have used a cyclic olefin as a raw material in a method for producing a cyclic olefin polymer in at least one method selected from the following methods. The inventors have found that this problem can be solved and completed the present invention.
1) (a) ethylene, (b) high-purity cyclopentadiene or dicyclopentadiene having a purity of more than 95% by weight, and (c) norbornene or tetracyclododecene obtained by, if necessary, heat-reacting with norbornene, Use within 7 days of formation of norbornene or tetracyclododecene.
2) (a) ethylene, (b) high-purity cyclopentadiene or dicyclopentadiene having a purity of more than 95% by weight, and (c) norbornene or tetracyclododecene obtained by subjecting norbornene to heat reaction as necessary. After storage in the presence of a stabilizer, the stabilizer is used after being reduced to 10 ppm or less by distillation.
That is, the present invention has the general chemical formula (1);

(However, in the formula, x and y represent copolymerization ratios and are real numbers satisfying 0/100 ≦ y / x ≦ 95/5, n represents the number of substitutions of the substituent Q, and 0 ≦ n ≦ 2. R ¹ is one or more 2 + n-valent groups selected from a group of hydrocarbon groups having 2 to 20 carbon atoms, and R ² is a hydrogen atom or a carbon number composed of carbon / hydrogen. 1 to 2 or more monovalent groups selected from 1 to 10 structural groups, and R ³ represents 1 to 2 or more tetravalent groups selected from a hydrocarbon group having 2 to 10 carbon atoms. Q is COOR ⁴ (R ⁴ is a hydrogen atom and one or two or more monovalent groups selected from the group consisting of carbon and hydrogen and having 1 to 10 carbon atoms). 1 type or 2 types or more of monovalent groups selected from a structural group of Method for producing a cyclic olefin polymer, characterized by use in at least one way in the manufacturing method of the cyclic olefin polymer composed of granulated selected cyclic olefins which is a raw material of the following methods.

1) (a) ethylene, (b) high-purity cyclopentadiene or dicyclopentadiene having a purity of more than 95% by weight, and (c) norbornene or tetracyclododecene obtained by, if necessary, heat-reacting with norbornene, Use within 7 days of formation of norbornene or tetracyclododecene.
2) (a) ethylene, (b) high-purity cyclopentadiene or dicyclopentadiene having a purity of more than 95% by weight, and (c) norbornene or tetracyclododecene obtained by subjecting norbornene to heat reaction as necessary. After storage in the presence of a stabilizer, the stabilizer is used after being reduced to 10 ppm or less by distillation.

(Cyclic olefin polymer)
It consists of one or more structures represented by the general chemical formula (1).
For each symbol in the general formulas (1) and (2), the following preferable conditions can be given, and these conditions are used in combination as necessary.
[1] The R ¹ group is a group having at least one ring structure in the structure.
[2] R ³ is an exemplary structure (a), (b), (c) as an example of a structural unit containing this group (when n = 0);

（但し、式中、Ｒ^１は前述の通り）
である。

(However, in the formula, R ¹ is as described above.)
It is.

[3] n is 0.
[4] y / x is a real number that satisfies 20/80 ≦ y / x ≦ 65/35.
[5] R ² is a hydrogen atom and / or —CH ₃ .
[6] Q is —COOH or —COOCH ₃ group.
More preferably, it consists of one or more structures represented by the general chemical formula (2).
Most preferably, for each symbol in the general formula (2), the following most preferable conditions can be listed, and these conditions are used in combination as necessary.
[1] R ¹ group is represented by the general chemical formula (3);

(Wherein p is an integer of 0 to 2).
Furthermore, it is preferably a divalent group in which p is 1 in the general formula (2).
[2] R ² is a hydrogen atom. Among these, as an embodiment in which these are combined, the cyclic olefin-based resin is ethylene and tetracyclo [4.4.0.1 ^2,5 . Most preferred among all is a polymer obtained by random addition polymerization of 1 ^7,10 ] -3-dodecene.

(Copolymerization type)
In addition, the type of copolymerization is not limited at all in the present invention, and various known copolymerization types such as random copolymer, block copolymer, alternating copolymerization and the like can be applied, but random copolymer is preferable. .

(Other structures that can be used as part of the main chain)
Further, the polymer used in the present invention has a repeating structural unit derived from another copolymerizable monomer as required, as long as the good physical properties of the product obtained by the molding method of the present invention are not impaired. May be. The copolymerization ratio is not limited, but it is preferably 20 mol% or less, more preferably 10 mol% or less. If the copolymerization is further performed, there is a possibility that optical properties will be impaired and high-precision optical parts may not be obtained. is there. The type of copolymerization is not limited, but a random copolymer is preferred.

(Molecular weight of polymer)
The molecular weight of the polymer used in the optical component of the present invention is not limited, but the intrinsic viscosity [η] measured in decalin at 135 ° C. is preferably 0.03 to 10 dl / g, more preferably 0. 0.05 to 5 dl / g, most preferably 0.10 to 2 dl / g.

  When the molecular weight is higher than this range, the moldability is deteriorated, and when the molecular weight is lower than this range, the molded product becomes brittle.

(Glass-transition temperature)
The glass transition temperature is not particularly limited, but is preferably 50 ° C. or higher and 240 ° C. or lower. More preferably, it is 50 degreeC or more and 160 degrees C or less. Among these, the temperature is most preferably 100 ° C. or higher and 150 ° C. or lower. If the temperature is out of this range, the operation cannot be guaranteed under conditions where the product is used at a high temperature. If it is higher than this range, melt molding may be difficult.

(Measuring method)
Known methods can be applied. A measuring apparatus etc. are not limited.
The glass transition temperature of the thermoplastic amorphous resin is measured using a differential scanning calorimeter (DSC). For example, measurement is performed at a temperature rising rate of 10 ° C./min using DSC-20 manufactured by SEIKO Electronics Industry Co., Ltd.

(Total light transmittance / spectral light transmittance)
The total light transmittance and spectral light transmittance are not particularly limited.

  However, since it is essential to transmit light when used in optical applications, it is preferable that the light transmittance is some degree. The light transmittance is defined by the spectral light transmittance or the total light transmittance depending on the application.

  When it is assumed that all light rays or a plurality of wavelength regions are used, it is necessary that the total light transmittance is good, preferably 85% or more, more preferably 88% or more. The amount of light cannot be secured. Measurement methods Known methods can be applied. A measuring apparatus etc. are not limited. In accordance with ASTM D1003, a thermoplastic amorphous resin is molded into a sheet having a thickness of 3 mm, and the total light transmittance of the molded sheet is measured using a haze meter.

  In the case of an optical system (for example, a laser optical system) used only in a specific wavelength region, even if the total light transmittance is not high, it can be used if the spectral light transmittance in the wavelength region is good. In this case, the spectral light transmittance at the wavelength used is preferably 85% or more, more preferably 88% or more. Measurement methods Known methods can be applied. A measuring apparatus etc. are not limited.

  In addition to the above-described components, the resin composition used in the present invention is a known weather stabilizer, heat stabilizer, antistatic agent, flame retardant, and the like within a range that does not impair the good characteristics of the optical component of the present invention. Slip agents, antiblocking agents, antifogging agents, lubricants, natural oils, synthetic oils, waxes, organic or inorganic fillers, and the like may be blended.

  For example, the weathering stabilizer blended as an optional component includes, for example, known light-resistant stabilizers, UV absorbers such as benzophenone compounds, benzotriazole compounds, nickel compounds, hindered amine compounds, in addition to known hindered amine additives. It is done. The hindered amine light-resistant stabilizer usually has a 3,5-di-tert-butyl-4-hydroxyphenyl group and a 2,2,6,6-tetramethylpiperidyl group or 1,2,2,6,6 in the structure. A compound having a -pentamethyl-4-piperidyl group, specifically, 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl ] -4- [3-3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine (for example, SANOL LS-2626, manufactured by Sankyo Corporation) ) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid-bis- (1,2,2,6,6-pentamethyl-4-piperidyl) (eg , Tinuvin 144, manufactured by Nippon Ciba-Geigy Co., Ltd.) . Specific examples of the benzotriazole ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2,2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl, 2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butyl-phenyl) benzotriazole, 2- (2′-hydroxy) -3'-tert-butyl-5'-methyl-phenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, etc., commercially available Tinuvin 328, Tinuvin PS (both manufactured by Ciba Geigy), SEESORB 709 (2 Examples include benzotriazole derivatives such as-(2'-hydroxy-5'-t-octylphenyl) benzotriazole, manufactured by Shiraishi Calcium Co.). Specific examples of benzophenone ultraviolet absorbers include 2,4-dihydroxy benzophenone, 2-hydroxy-4-methoxy benzophenone, 2,2'-dihydroxy-4-methoxy benzophenone, and 2,2'-dihydroxy. -4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone, 2-hydroxy-4 -Methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxy benzophenone, 2-hydroxy-4-octadecyloxy benzophenone, 2-hydroxy-4-n-dodecyloxy benzophenone, 2-hydroxy -4-Benzyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxy benzopheno 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, Uvinul 490 (2,2'-dihydroxy-4,4'-dimethoxy benzophenone) And other tetra-substituted benzophenone mixtures (manufactured by GAF), Permyl B-100 (benzophenone compound, manufactured by Ferro), and the like.

  In addition, as a heat stabilizer to be blended as an optional component, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t Phenol-type antioxidants such as 2-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamide bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearin Fatty acid metal salts such as zinc acid, calcium stearate, calcium 1,2-hydroxystearate, multivalents such as glycerol monostearate, glycerol distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate Examples include alcohol fatty acid esters, Stearyl pentaerythritol diphosphite, phenyl-4,4′-isopropylidenediphenol-pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris ( Phosphorus stabilizers such as 2,4-di-t-butylphenyl) phosphite may be used. These may be blended alone or in combination. For example, a combination of tetrakis [methylene-3- (3.5-di-t-butyl-4-hydroxyphenyl) propionate] methane, zinc stearate and glycerin monostearate can be exemplified. These stabilizers can be used alone or in combination of two or more.

  The mixing method of the cyclic olefin polymer used in the present invention and other resin components and additives is not limited, and known methods can be applied. For example, a method of mixing each component simultaneously.

  The cyclic olefin used in the present invention is preferably a cyclic olefin represented by the formula [I] or [II].

The cyclic olefin represented by the formula [I] or [II] will be described.
In the above formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, Ra and Rb are each independently the following atoms or hydrocarbon groups. When q is 0, each bond is bonded to form a 5-membered ring. .

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C3-C15 cycloalkyl group, and an aromatic hydrocarbon group are mentioned each independently independently. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. As the cycloalkyl group, Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. These hydrocarbon groups may be substituted with a halogen atom.

Furthermore, in the above formula [I], R ^{15 to} R ¹⁸ may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed May have a double bond. Specific examples of the monocyclic or polycyclic ring formed here are shown below.

In the above example, the carbon atom numbered 1 or 2 represents a carbon atom to which R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is bonded in the formula [I]. R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group, and an isopropylidene group.

In the above formula [II], p and q are 0 or a positive integer, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

  The halogen atom has the same meaning as the halogen atom in the above formula [I]. Examples of the hydrocarbon group include independently an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group. It is done. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. As the cycloalkyl group, Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. Specific examples include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. These hydrocarbon groups and alkoxy groups may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. It may be connected via. That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ or the groups represented by R ¹⁰ and R ¹¹ are combined with each other to form a methylene group. An alkylene group of any one of (—CH ₂ —), an ethylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ₂ CH ₂ CH ₂ —) is formed. Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Examples of the monocyclic or polycyclic aromatic ring in this case include the following groups in which R ¹⁵ and R ¹² further form an aromatic ring when n = m = 0.

  Here, q has the same meaning as q in formula [II]. Specific examples of the cyclic olefin represented by the formula [I] or [II] as described above are shown below.

(In the above formula, the numbers 1 to 7 represent carbon position numbers.) And derivatives in which a hydrocarbon group is substituted for this bicyclo [2.2.1] -2-heptene. Examples of the hydrocarbon group include 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5. -Phenyl, 5-benzyl, 5-tolyl, 5- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- ( Anthracenyl), 5,6-diphenyl and the like.

  Further derivatives include cyclopentadiene-acenaphthylene adducts, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a-hexahydro. And bicyclo [2.2.1] -2-heptene derivatives such as anthracene.

Tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene, 5-methyltricyclo [4.3. Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives such as 0.1 ^2,5 ] -3-decene, tricyclo [4.4.0.1 ^2,5 ] -3-undecene, Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivatives such as 10-methyltricyclo [4.4.0.1 ^2,5 ] -3-undecene.

(In the above formula, the numbers 1 to 12 indicate the position number of carbon.) And derivatives in which a hydrocarbon group is substituted. As this hydrocarbon group, for example, 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2,10 -Dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 9-isobutyl-2,7-dimethyl 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8-ethylidene-9- Methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene-9-methyl, 8-n-propylidene-9- Ethyl, 8-n-propylidene-9-isopropyl, 8-n -Propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8-isopropylidene-9-isopropyl, 8-isopropylidene-9-butyl, 8- Chloro, 8-bromo, 8-fluoro, 8,9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl, 8-tolyl, 8- (ethylphenyl), 8- (isopropylphenyl), Examples include 8,9-diphenyl, 8- (biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8- (anthracenyl), and 5,6-diphenyl.

Still other derivatives include adducts of (cyclopentadiene-acenaphthylene adduct) and cyclopentadiene. Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene and its derivatives. Pentacyclo [7.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13 ] -3-pentadecene and its derivatives. Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] 4,10 penta octadecadienoic Penta cyclopentadiene octadecadienoic compound such. Pentacyclo [8.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13 ] -3-hexadecene and its derivatives. Pentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene and its derivatives. Hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene and derivatives thereof. Heptacyclo [8.7.0.1 ^2,9 . 1 ^4,7 . 11 ^1,17 . 0 ^3,8 . 0 ^12,16 ] -5-eicosene and its derivatives. Heptacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^{11, 18} . 0 ^3,8 . 0 ^12,17 ] -5- ^henecocene and its derivatives. Octacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^{11, 18} . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene and its derivatives. Nonacyclo [10.9.1.1 ^4,7 . 1 ^13,20 . 1 ^{15, 18} . 0 ^2,10 . 0 ^3,8 . 0 ^{12, 21} . 0 ^14,19] -5-pentacosene and derivatives thereof. Nonacyclo [10.10.1 ^{5, 8} ,. 1 14, ²¹ . 1 ^{16, 19} . 0 ^2,11 . 0 ^4,9 . 0 ^13,22 . 0 ^15,20] -6-hexacosenoic, and the like derivatives thereof.

  Specific examples of the cyclic olefin represented by the general formula [I] or [II] are shown above, but as a more specific structure example of these compounds, paragraph number of the original specification of Japanese Patent Application No. 5-196475. Examples of the structure of the cyclic olefin shown in [0032] to [0054] can be given. The cyclic olefin resin used in the present invention may contain two or more units derived from the cyclic olefin.

  The cyclic olefin represented by the general formula [I] or [II] as described above can be produced by subjecting cyclopentadiene and an olefin having a corresponding structure to Diels-Alder reaction.

(Cyclic olefin)
Although the kind of cyclic olefin used by this invention is not specifically limited as mentioned above, Preferably it is norbornene or tetracyclododecene.

The cyclic olefin used in the present invention is characterized by using a cyclic olefin as a raw material in at least one method selected from the following methods.
1) (a) ethylene, (b) high-purity cyclopentadiene or dicyclopentadiene having a purity exceeding 95% by weight, and (c) norbornene or tetracyclododecene obtained by heating reaction with norbornene if necessary Cyclic olefins are used within 7 days after norbornene or tetracyclododecene is formed.
2) (a) ethylene, (b) high-purity cyclopentadiene or dicyclopentadiene having a purity of more than 95% by weight, and (c) norbornene or tetracyclododecene obtained by heating reaction with norbornene if necessary The cyclic olefin is stored in the presence of a stabilizer and then used after reducing the stabilizer to 10 ppm or less by distillation.

  Here, when the cyclic olefin such as norbornene or tetracyclododecene of 1) above is used within 7 days after the production, it is preferably produced and then added after the production without adding an additive such as a stabilizer. It is supplied to the polymerization reaction within -5 days for use. The oxygen concentration in the cyclic olefin supplied to the polymerization reaction is preferably 10 ppm or less, and preferably 0.1 to 5 ppm for the purpose of stabilizing the polymerization. The time until it is supplied to the polymerization reaction after being produced here is the polymerization after the cyclic olefin obtained by heating reaction of cyclopentadiene or dicyclopentadiene and, if necessary, (c) norbornene, comes out of the production reactor. It means the average time to be fed into the reactor.

  Here, after the cyclic olefin such as norbornene or tetracyclododecene of 2) above is stored in the presence of a stabilizer, the stabilizer is reduced to 10 ppm or less by distillation, and then supplied to the polymerization reaction and used. Details will be described. Preservation means a period of about 8 days to 5 years, preferably about 8 days to 1 year. During storage, cyclic olefins such as norbornene or tetracyclododecene are kept at 50 ° C. or lower, preferably 30 ° C. or lower. During storage, cyclic olefins such as norbornene or tetracyclododecene contain 10-10000 ppm, preferably 50-5000 ppm of stabilizer. The stabilizer is not particularly limited, but hydroquinone, 2,6-di-tert-butylphenol, 2,6-di-tert-butylcresol, 4-methoxyphenol, 3,5-di-tert-butyl-4-hydroxytoluene Phenol compounds such as 4-tert-butylcatechol, amine compounds such as N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine, N-nitroso-N-phenylbenzoamine, and phenothiazine are preferably added. The 4-tert-butylcatechol is preferably used. During storage, the oxygen concentration in the cyclic olefin such as norbornene or tetracyclododecene is preferably 10 ppm or less, and preferably 0.1 to 5 ppm for stabilizing the polymerization. The stored cyclic olefin is preferably continuously distilled in a distiller to reduce the concentration of the stabilizer contained in the cyclic olefin to 10 ppm or less, preferably 0.1 to 8 ppm. The distillation of the cyclic olefin is usually performed at 100 to 200 ° C, preferably 120 to 150 ° C. During the distillation of the cyclic olefin, the oxygen concentration in the system is 10 ppm or less, preferably 0.1 to 5 ppm.

(Method for producing cyclic olefin polymer)
The cyclic olefin polymer of the present invention can be produced by the following method. When the cyclic olefin polymer of the present invention is an ethylene / cyclic olefin random copolymer (a1), it is disclosed in the above publication using ethylene and the cyclic olefin represented by the above formula [I] or [II]. It can manufacture with the manufactured manufacturing method. Among these, this copolymerization is carried out in a hydrocarbon solvent, and an ethylene / cyclic olefin random copolymer (a1) using a catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent as a catalyst. It is preferable to manufacture.

  In this copolymerization reaction, a solid group IVB metallocene catalyst can also be used. Here, the solid group IVB metallocene catalyst is a catalyst comprising a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organoaluminum oxy compound, and an organoaluminum compound blended as necessary. Here, the transition metal of group VI is zirconium, titanium or hafnium, and these transition metals have a ligand containing at least one cyclopentadienyl skeleton. Here, examples of the ligand containing a cyclopentadienyl skeleton include a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and a fluorenyl group, which may be substituted with an alkyl group. These groups may be bonded via other groups such as an alkylene group. The ligand other than the ligand containing a cyclopentadienyl skeleton is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or the like.

  Furthermore, what is normally used for manufacture of an olefin resin can be used for an organoaluminum oxy compound and an organoaluminum compound. Such solid IVB metallocene catalysts are described in, for example, JP-A-61-221206, JP-A-64-106 and JP-A-2-173112.

  When the cyclic olefin polymer of the present invention is a ring-opening polymer or a ring-opening copolymer, for example, the cyclic olefin represented by the above formula [I] is polymerized or copolymerized in the presence of a ring-opening polymerization catalyst. Can be manufactured.

  As such a ring-opening polymerization catalyst, a catalyst comprising a metal halide, nitrate or acetylacetone compound selected from ruthenium, rhodium, palladium, osmium, indium or platinum and a reducing agent, or titanium, palladium, zirconium Alternatively, a catalyst comprising a metal halide selected from molybdenum or the like or an acetylacetone compound and an organoaluminum compound can be used.

  When the cyclic olefin polymer of the present invention is a ring-opening polymer or a ring-opening copolymer, the ring-opening polymer or the ring-opening copolymer is generally used by hydrogenation. A conventionally known hydrogenated resin composition comprising 100 parts by weight of the ring-opening polymer or ring-opening copolymer (a2) obtained and 0.01 to 10 parts by weight of an unreacted cyclic olefin monomer (unsaturated hydrocarbon) It can be obtained by hydrogenation in the presence of a catalyst. At this time, since the unreacted cyclic olefin monomer (unsaturated hydrocarbon) and the ring-opening polymer or ring-opening copolymer are hydrogenated simultaneously, the reaction is simple and preferable.

(Method of treating polymer solution with adsorbent)
The resin composition solution is preferably passed through an adsorption device to remove by-products such as the polymerization catalyst and oxide used in the production of the resin before and after being fed into the reactor for hydrogenation. The adsorber is filled with an adsorbent such as activated clay, activated carbon, diatomaceous earth, pearlite, alumina, nickel, silica, silica alumina and the like. Filtration can be used in combination with the adsorption. The treatment with the adsorbent may be performed before the hydrogenation reactor or after the hydrogenation reactor or in the presence of the hydrogenation catalyst and the adsorbent in the hydrogenation reactor.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not restrict | limited at all by these Examples.

The physical property measuring methods in the examples are as follows.
(1) Glass transition temperature (Tg)
Using DSC-20 manufactured by SEIKO Electronics Industry Co., Ltd. in nitrogen at 10 ° C./min. After raising the temperature to 250 ° C. under the temperature raising conditions, the sample was once cooled rapidly, and then measured at a temperature raising rate of 10 ° C./min.
(2) Number average molecular weight (Mn)
Using GPC Alliance 2000 (Waters), column: TSKgel GMH6-HT × 2 + TSKgel GMH6-HTL × 2 (total 30 cm × 4, Tosoh Corp.) Detector: differential refractometer Measurement solvent: o-dichlorobenzene Measurement flow rate: 1 mL / min Measurement temperature: 140 ° C. Sample injection amount: 500 μL Standard sample: Monodispersed polystyrene × 16 (Tosoh Corporation) was used for analysis.

[Example 1]
Tetracyclododecene was synthesized by the method described in Example 1 of JP-A-6-9437. Thereafter, the following polymerization reaction was carried out within one day after the synthesis of tetracyclododecene.

Ethylene tetracyclo [4.4.0.1 ^2,5 ... By a known method in a cyclohexane solvent using a vanadium catalyst (VOCl ₃ ). An addition copolymer of 1 ^7,10 ] -3-dodecene (hereinafter referred to as TD) was polymerized. After completion of the polymerization, the reaction product was added to a mixed solvent of concentrated hydrochloric acid (50 ml / L) in acetone / methanol (volume ratio 1/1) to precipitate the entire amount of polymer, stirred, filtered through a glass filter, and dried under reduced pressure. An ethylene / TD copolymer was obtained. The physical properties of the obtained copolymer were Tg = 135 ° C., Mn = 80,000, and b value = 5.

[Example 2]
Tetracyclododecene was synthesized by the method described in Example 1 of JP-A-6-9437. Thereafter, 4-tert-butylcatechol as a stabilizer was added to tetracyclododecene to 100 ppm, and the mixture was stored at 30 ° C. for 1 month. At this time, the oxygen concentration in the storage container was 4 ppm. 30 days after synthesis, the stabilizer was reduced to 1 ppm by distillation, and the polymerization reaction was carried out in the same manner as in Example 1. The physical properties of the obtained copolymer were Tg = 135 ° C., Mn = 80,000, and b value = 6.

[Comparative Example 1]
In Example 2, the cyclic olefin was stored in the same manner as in Example 2 except that no stabilizer was added to tetracyclododecene, and then the polymerization reaction was performed. The physical properties of the obtained copolymer were Tg = 135 ° C., Mn = 80,000, and b value = 18.

Claims (3)

General chemical formula (1);

(However, in the formula, x and y represent copolymerization ratios and are real numbers satisfying 0/100 ≦ y / x ≦ 95/5, n represents the number of substitutions of the substituent Q, and 0 ≦ n ≦ 2. R ¹ is one or more 2 + n-valent groups selected from the group of hydrocarbon groups having 2 to 20 carbon atoms, and R ² is a hydrogen atom or carbon / hydrogen. 1 to 2 or more monovalent groups selected from a structural group of 1 to 10 and R ³ is 1 to 2 or more tetravalent groups selected from a hydrocarbon group having 2 to 10 carbon atoms. Q is COOR ⁴ (R ⁴ is a hydrogen atom and one or more monovalent groups selected from the group consisting of carbon and hydrogen and having 1 to 10 carbon atoms) 1 type or 2 types or more of monovalent groups selected from the structural group represented.) The method of manufacturing a cyclic olefin polymer composed of structural, manufacturing method of the cyclic olefin polymer, characterized by using at least one method selected cyclic olefins which is a raw material of the following methods.
1) (a) ethylene, (b) high-purity cyclopentadiene or dicyclopentadiene having a purity of more than 95% by weight, and (c) norbornene or tetracyclododecene obtained by, if necessary, heat-reacting with norbornene, Use within 7 days of formation of norbornene or tetracyclododecene.
2) (a) ethylene, (b) high-purity cyclopentadiene or dicyclopentadiene having a purity of more than 95% by weight, and (c) norbornene or tetracyclododecene obtained by subjecting norbornene to heat reaction as necessary. After storage in the presence of a stabilizer, the stabilizer is used after being reduced to 10 ppm or less by distillation. The cyclic olefin polymer according to claim 1 is represented by the general chemical formula (2).

(In the formula, R ¹ is one or more divalent groups selected from a hydrocarbon group having 2 to 20 carbon atoms, and R ² is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms. 1 or 2 or more types of monovalent groups selected from the group, x and y are copolymerization ratios, and x / y is a real number of 5/95 or more and 95/5 or less. It is a cyclic olefin type copolymer, The manufacturing method of the cyclic olefin type polymer of Claim 1 characterized by the above-mentioned.   A cyclic olefin polymer obtained by the method according to claim 1.