WO2002072652A1 - Addition copolymers, hydrogenated addition copolymers and processes for producing both - Google Patents

Abstract

An addition copolymer which comprises at least repeating units derived from a conjugated diene and repeating units derived from a cyclic olefin with the contents of the former and latter repeating units being 10 to 99 mole % and 90 to 1 mole % respectively based on the whole of the repeating units of the copolymer and has a weight-average molecular weight of 5,000 to 1,000,000 in terms of polystyrene as determined by gel permeation chromatography and a glass transition temperature of 100 to 200 °C. This copolymer can be designed not only as elastomers but also as plastics.

Description

 AKITODA Sho Addition copolymers, hydrides of addition copolymers, and processes for their production

 The present invention relates to an addition copolymer or a hydride of an addition copolymer, and a method for producing the same. More specifically, the present invention relates to an addition copolymer and a hydride of an addition copolymer having a repeating structural unit derived from a conjugated gen-based monomer and a repeating structural unit derived from a cyclic olefin-based monomer, and methods for producing the same. Background art

 Conjugated gen-based polymers such as polyptadene-polyisoprene have been known for a long time. In recent years, techniques have been developed to control the ratio of 1,4-bonds and 1,2-bonds in polymers by various polymerization catalysts, and to control the ratio of cis and trans structures. As a result, the use of conjugated gen-based polymers as rubber materials for tires, resin modifiers, automotive parts, shoe soles, and the like has expanded dramatically. However, conjugated polymers generally require vulcanization and carbon blending in order to exhibit elasticity and mechanical strength. For this reason, there is a problem not only in terms of processing equipment but also in terms of quality, regarding transparency and odor.

 Also, random copolymers and block copolymers with styrene, hydrides of copolymers with styrene, and the like have been produced as conjugated polymers having enhanced rigidity and elasticity. However, even with these, rigidity, elasticity, and even mechanical strength were still insufficient.

 On the other hand, a bull addition copolymer of ethylene and a cyclic olefin such as norpolenenes has been reported as a hydrocarbon-based polymer having both the flexibility of a linear polymer and the rigidity of a cyclic polymer. However, this cyclic olefin-buil addition copolymer has problems that the ethylene portion has crystallinity, so that it has insufficient transparency, lacks low-temperature stability, and has insufficient mechanical strength. there were.

Thus, the ethylene of this cyclic-olefin-buil addition copolymer is converted to a conjugated gen. There are several possible improvements. As a method for producing a copolymer of a conjugated gen and a cyclic olefin, a thermal polymerization method based on a Diels-Alder reaction and a cationic polymerization method based on a Friedel-Crafts reaction have been known for a long time. In thermal polymerization, the ring structure is continuous, it is a rigid and brittle, so-called petroleum resin.In the case of cationic polymerization, the resulting polymer is a low-molecular-weight substance similar to an oligomer, and it also inhibits side reactions such as crosslinking reaction and cyclization reaction. As a result, only rigid and brittle materials were obtained.

 The polymerization mechanism of conjugated gens using transition metal compounds as polymerization catalysts and the polymerization of cyclic olefins have been studied in detail. However, since the polymerization reaction mechanism of the conjugated diene and the cyclic olefin is different, it has been generally accepted that it is impossible to produce a copolymer having a sufficient molecular weight with a weight average molecular weight of 500 or more. Thus, the emergence of a conjugated gen-monocyclic olefin copolymer that is highly elastic, has excellent mechanical strength, and has excellent transparency as an elastomer or plastic material has been strongly desired. No successful cases have been reported. Disclosure of the invention

 It is an object of the present invention to provide a hydrogenated conjugated monocyclic olefin addition copolymer and a conjugated conjugated monocyclic olefin addition copolymer, which can be designed as an elastomer or a plastic, and a method for producing the same. It is in.

 The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that when a specific polymerization catalyst is used, a high-molecular-weight conjugated gen-monocyclic olefin addition copolymer can be obtained. Furthermore, they have found that the copolymer and its hydride have high elasticity, excellent mechanical strength, and excellent transparency, and have completed the present invention based on these findings.

 That is, according to the present invention, an addition copolymer having at least a repeating structural unit derived from a conjugated gen-based monomer and a repeating structural unit derived from a cyclic olefin-based monomer,

The content of each of the repeating structural units with respect to the entire polymer repeating structural unit is as follows: a repeating structural unit derived from a conjugated gen-based monomer: 10 to 99 mol%; a repeating structural unit derived from a cyclic olefin-based monomer: 9 0-1 mol%, The weight average molecular weight in terms of polystyrene determined by gel permeation chromatography is 5,000 to 1,000, 0000,

 An addition copolymer having a glass transition temperature of 100 to 200 ° C. is provided.

 According to the present invention, there is provided an addition copolymer hydride having at least a repeating structural unit derived from a conjugated diene monomer and a repeating structural unit derived from a cyclic olefinic monomer,

 The content of each of the repeating structural units with respect to the total polymer repeating structural units is: a repeating structural unit derived from a conjugated gen-based monomer: 10 to 99 mol%;

 Recurring structural unit derived from a cyclic olefin monomer: 90 to 1 mol. /. And the weight average molecular weight in terms of polystyrene by gel permeation chromatography is 5, 000 to: I, 000, 000,

 A glass transition temperature of 100 to 200 ° C.,

 An addition copolymer hydride having a ratio of the number of double bonds (excluding the double bond of the aromatic ring) to the total number of carbon-carbon bonds of 0.2% or less is provided.

 According to the present invention, at least a conjugated gen-based monomer and a cyclic olefin are present in the presence of a polymerization catalyst containing a transition metal compound belonging to Groups 4 to 10 of the periodic table in which a ligand is coordinated with π electrons. The present invention provides a method for producing an addition copolymer, which comprises polymerizing a monomer containing a base monomer.

 According to the present invention, at least a conjugated gen-based monomer and a cyclic olefin are present in the presence of a polymerization catalyst containing a transition metal compound belonging to Groups 4 to 10 of the periodic table in which a ligand is coordinated with π electrons. An addition copolymer obtained by polymerizing a monomer containing a base monomer to obtain an addition copolymer, and then hydrogenating a carbon-carbon double bond in the addition copolymer. A method for producing a hydride is provided.

When the addition copolymer of the present invention or its hydride is used as a plastic, the ratio of the repeating structural unit derived from the conjugated monomer to the total repeating structural units of the copolymer or its hydride is used. Is preferably from 10 to 50 mol%. When the addition copolymer of the present invention or its hydride is used as the elastomer, the copolymer or the hydride of the hydride may have a repeating structural unit derived from a conjugated gen monomer with respect to all the repeating structural units of the hydride. Preferably, the proportion is between 50 and 99 mol%. In the addition copolymers and their hydrides of the present invention, and their production methods, it is preferable that the cyclic olefin-based monomer is a norportene-based monomer.

 In the method for producing an addition copolymer and the method for producing a hydride thereof according to the present invention, the polymerization catalyst is preferably an aryl complex of a transition metal of Group 10 of the periodic table.

 In the method for producing an addition copolymer and the method for producing a hydride thereof according to the present invention, it is preferable that the polymerization catalyst is a cyclopentagenenyl complex of a transition metal of Group 4 or 5 of the periodic table.

 According to the present invention, there is provided a hydrogenated copolymer of an addition copolymer and an addition copolymer, which can be designed as an elastomer or a plastic, and a method for producing the same. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, embodiments of the present invention will be described. These embodiments are described to facilitate understanding of the present invention, and are described to limit the present invention. Not something.

 The addition copolymer of the present invention is an addition copolymer having at least a repeating structural unit derived from a conjugated gen-based monomer and a repeating structural unit derived from a cyclic olefin-based monomer. The ratio of each monomer repeating structural unit to the unit is 10 to 99 mol% of the conjugated gen-based monomer-derived repeating structural unit, and 90 to 1 of the cyclic olefin-based monomer-derived repeating structural unit. Mol% of the addition copolymer. The proportion of each monomer repeating structural unit in the present addition polymer is preferably arbitrarily selected depending on the purpose of use of the present addition polymer. For example, when used as an elastomer having a Tg of 40 ° C or less, the ratio of the repeating structural unit derived from the co-gen monomer to the total repeating structural units of the addition copolymer is 50 to 9%. 9 mol% is preferred,

60-99 mol% is more preferable. On the other hand, when used as a plastic, the proportion of the repeating structural unit derived from the conjugated diene monomer is preferably 1 0-5 0 mole _^0/0 to the total repeating structural units in addition copolymer, 1 0-4 0 mole _^0/0 is more preferable Les,. The repeating structural unit derived from the third monomer capable of addition copolymerization with the above two monomers is preferably 50 mol% or less based on all repeating structural units of the addition copolymer. Or less than 40 mol%, more preferably 30 mol% or less.

 The copolymer according to the present invention has a weight average molecular weight (hereinafter sometimes referred to as “Mw”) of 5,000 to 1,000,000 in terms of polystyrene by genole permeation chromatography. 000, preferably 7,000—500,0

00, more preferably 10,000 to 400,000, and a glass transition temperature (hereinafter sometimes referred to as “Tg”) of from 100 to 200 ° C, preferably from 90 to 190 ° C, Preferably it is one of 80-180 ° C.

 The addition copolymer of the present invention has a sufficiently high weight-average molecular weight and an appropriate glass transition temperature, so that it has excellent mechanical strength, and has no crystallinity, and thus has excellent transparency.

 Further, the hydride of the addition copolymer of the present invention has the same composition of the repeating structural unit, the same range of the weight average molecular weight and the glass transition point as the above addition copolymer, The ratio of the number of double bonds (excluding the double bond of the aromatic ring) to the number of bonds is 0.2% or less, preferably 0.1% or less, more preferably 0.05% or less. The hydride of the addition copolymer of the present invention has advantages of excellent mechanical strength, elasticity and transparency, as well as good heat resistance and weather resistance, since it has few double bonds.

 In order to produce the addition copolymer of the present invention, a conjugated gen-based monomer, a cyclic olefin-based monomer and, if desired, a third monomer are addition-copolymerized. If a catalyst containing a transition metal compound of Groups 4 to 10 of the periodic table as a main component is used as a polymerization catalyst, a copolymer having a sufficiently high molecular weight in the above range can be obtained.

 The hydride of the addition copolymer of the present invention can be produced, for example, by dissolving the addition copolymer obtained by the above method in an organic solvent and performing a hydrogenation reaction in the presence of a hydrogenation catalyst. .

The conjugated diene monomer used in the present invention includes a linear or branched conjugated diene monomer represented by the following general formula [1], wherein R ¹ , R ² , R ³ and R ⁴ are not bonded to each other. And a cyclic conjugated diene monomer in which R ¹ and R ⁴ are bonded to each other. 1

(Wherein R ¹ , R ² , R ³ and R ⁴ may independently have a hydrogen atom or a halogen atom, or a substituent containing a halogen atom, a nitrogen atom, an oxygen atom or a silicon atom, A hydrocarbon group which may be branched and has 1 to 20 carbon atoms, and R ¹ and R ⁴ may be bonded to each other to form a cyclic structure.)

 The conjugated diene monomer represented by the above general formula [1] may be a compound in which two olefinic double bonds are conjugated to each other, and specific examples include butadiene, isoprene, piperylene, 2, 3 Linear or branched conjugated monomers such as dimethyl-1,3-butadiene, 1,3-hexadiene, 2-methyl-1,1,1-pentadiene, 3-methynole-1,1,1-pentadiene; Examples include cyclic conjugated monomers such as cyclopentadiene, methylcyclopentadiene, 1,3-cyclohexadiene, and 1,3-cyclooctadiene.

The repeating structural unit derived from the conjugated gen-based monomer is a structural unit in the polymer when the conjugated gen-based monomer is subjected to addition polymerization. There are two types of addition polymerization of conjugated diene monomers, 1,4-addition type and bullet addition type. In addition, 1,4-additions include cis- and trans-types, and bullet additions include 1,2-additional and 3,4-additional types. Therefore, the repeating structural units of the conjugated diene monomer include 1,4-cis-type (the following general formula [2]), 1,4-trans-type (the following general formula [3]), 1,2-vinyl There are four types: the following (general formula [4]) and the 3,4-Bull type (general formula [4-1]). Conjugated diene circularly Orefin addition copolymer of the present invention, 1 0-99 moles of recurring structural units derived from these four inclusive conjugated diene-based monomer based on all repeating structural units of in ⁰ /. Occupy. -

H

 , Y

 [S] H

 [2]

TJP02/01534 本発明で使用する環状ォレフィン系単量体は、 環内にォレフィン性二重結合を 有する環状炭化水素化合物で、 具体的には、 下記一般式 [5] で示されるモノ環 状ォレフイン系単量体と、 下記一般式 [6] で示されるノルポルネン系単量体を 挙げることができる。

TJP02 / 01534 The cyclic olefin monomer used in the present invention is a cyclic hydrocarbon compound having an olefinic double bond in the ring, and specifically, a monocyclic olefin represented by the following general formula [5]: And a norponene-based monomer represented by the following general formula [6].

 Chemical 5

(In the formula, a plurality of R ^s , R ^e, and R ⁷ each independently represent a hydrogen atom or a halogen atom, or an optionally branched hydrocarbon group having 1 to 20 carbon atoms. it may also form a ring with two R ⁶ attached to a carbon atom is bonded to each other les. 1 is an integer 0-7.)

 Chemical 6

(Wherein, R ⁸ to R ¹⁵ each independently represent a hydrogen atom, a halogen atom or an optionally branched hydrocarbon group having 1 to 20 carbon atoms. R ^{ie to} R ¹⁹ each independently represent a chromium atom or a halogen atom, Kei atom, an oxygen atom or a nitrogen atom which may have a including substituent, a branched or may be a hydrocarbon group having 1 to 20 carbon atoms. R ¹⁶ and R ¹⁹ may combine with each other to form a ring, and m is 0, 1 or ^2. ) The structural unit derived from the cyclic olefin monomer is a structural unit in a polymer obtained by subjecting the above cyclic olefin monomer to beul addition polymerization. Specifically, a 1,2_ addition structural unit represented by the following general formula [7] when a monocyclic olefin monomer is subjected to addition polymerization, and a 1,2_ addition structural unit when a norbornene monomer is subjected to addition polymerization. The structural unit represented by the general formula [8] can be mentioned. The structural unit derived from the monocyclic olefin monomer includes not only the 1,2-additional structure represented by the general formula [7], but also the 1,3-additional structure represented by the general formula [9]. The conjugated diene-cyclic olefin addition copolymer of the present invention contains a cyclic structural unit derived from the cyclic olefin monomer represented by the general formula [7], the general formula [9] and the general formula [8]. 1 to 90 mole ⁰ / in the total repeatedly structural units. Occupy.

 化 —Ί

化 —8

-8

化 9

Chemical 9

Specific examples of the monocyclic olefin monomer include cyclopropene, cyclobutene, cyclopentene, methinolecyclopentene, cyclohexene, methinolecyclohexene, cycloheptene, cyclooctene and the like. Further, as an example in which two R ⁶ bonded to adjacent carbon atoms are bonded to each other to form a ring outside the cyclic olefin, for example, bicyclo [3., 3.0] octene (general formula [ 10]), tricyclo [5.2.1.02, 6] decal 3-ene (general formula [1 1]), bicyclo [4.3.0] noner 3,7-gen (general formula [12] ).

 Chemical 10

化

Conversion

ノルボルネン系単量体の具体例としては、 ノノレポルネン、 5—メチルノルボル ネン、 5一ェチルノルボルネン、 5—プチルノルポルネン、 5—へキシルノルボ ルネン、 5—デシルノルボルネン、 5—シクロへキシルノルポルネン、 5—シク 口ペンチノレノルポルネンなどの無置換またはアルキル基を有するノルポルネン類

Specific examples of norbornene-based monomers include nonolepolene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorpolene, 5-hexylnorbornene, 5-decylnorbornene, and 5-cyclohexylnorbornene. Or unsubstituted or alkyl group-containing norponenes, such as pentolinolenorpolene

Norbornenes having alkenyl groups such as 5-ethylidene norbornene, 5-vinylnonolebornene, 5-propenylnonole ponolenene, 5-cyclohexenylnorbornene and 5-cyclopentenylnorbornene;

 Norbornenes having an aromatic ring, such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonyl norbornene, 5-methinole-5-methoxycarbonylnorbornene, 5-methyl-1-ethoxycarbel Nonorebornene, norbornenyl_2-methylpropionate, norpolnenyl-2-methyloctanoate, norpolpolene-5,6-dicarboxylic anhydride, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene, 5,5 Polar groups containing oxygen atoms, such as di- (hydroxymethyl) norbornene, 5-hydroxyisoprovirnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarboxyl 6 Norbornenes having;

5 Xia Bruno norbornene, norbornene one 5, norbornenes having polar group containing nitrogen atom such as 6-dicarboxylic acid I Mi de; Jishiku port Pentajen, Torishi black ^{[. 4. 3. I 2 '5} 0] deca one 3-ene, tricyclo [4. 4. I ² ' ⁵ .

0] Principle 3-ene. In addition, tetracyclo [6.

^{5. I 2 '5. 0 1} ' 6. 0 8 '13] trideca one 3, 8, 10, 12 Tetoraen (1, 4 Metano one 1, 4, 4 a, 9 a- also referred tetrahydrofluorene), tetracyclo ^{[6. 6. 1 2 's.} 0 1' 6 · 0 8 '13] Tetoradeka 3, 8, 10, 1 2 — Norbornenes having an aromatic ring such as tetraene (1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene);

 Tetracyclododecenes having unsubstituted or alkyl groups such as tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene ;

 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-biertetracyclododecene, 8-propeninoletetracyclododecene, 8-cyclohexeninoletetracyclododecene, 8- Tetracyclododecenes having an exocyclic double bond such as cyclopentenyltetracyclododecene;

 Tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene;

 8-Methoxycarbonyltetracyclododecene, 8-methyl-18-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene _ 8, 9 Tetracyclododecenes having a substituent containing an oxygen atom, such as dicarboxylic acid and tetracyclododecene-1,8-dicarboxylic anhydride;

 Tetracyclododecenes having a substituent containing a nitrogen atom, such as 8-cyanotetracyclododecene and tetracyclododecene-18,9-dicarbonate imide;

 Tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene;

 Tetracyclododecenes having a substituent containing a silicon atom, such as 8-trimethoxysilyltetracyclododecene;

Unsubstituted or alkenyl such as hexahexaheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexynolehexacycloheptadecene, 12-cyclopentylhexacycloheptadecene, etc. Hexacyclic mouth heptadecenes having a kill group; 12-Methylidenehexacycloheptadecene, 12-ethylidenehexaheptaheptacene, 12-Bulbhexacycloheptadecene, 12-Propenylhexacycloheptaheptacene, 12-Cyclohexaenohexacycloheptadecene 1-hexahexene heptadecenes having an exocyclic double bond, such as a pentohexahexene heptadecene;

 Hexacyclic heptadecenes having an aromatic ring such as 12-phenylhexacycloheptadecene;

 12-Methoxycarboelhexacycloheptadecene, 12-methyl_12-Methoxycarbonylhexacycloheptadecene, 12-Hydroxymethylhexacycloheptadecene, 12-Methoxylcyclohexacycloheptadecene, to Hexacycloheptadecenes having a substituent containing an oxygen atom, such as mouth heptadecene-l, 2,13-dicarboxylic acid and hexacyclohepta-decene-l, 2,13-dicarboxylic anhydride;

 Hexacycloheptadecenes having a substituent containing a nitrogen atom, such as 12-cyanohexaheptaheptadecene and hexacyclohexaheptadecene;

 Hexacycloheptadecenes having a substituent containing a halogen atom, such as 12-cyclohexahexaheptadecene;

 Hexacycloheptadecenes having a substituent containing a silicon atom, such as 12-trimethoxysilinolehexacycloheptadecene, and the like.

 Among these norpolene-based monomers, those of general formula [6], in which m is 0 and composed of relatively few rings, are preferred because they are easy to polymerize. Among them, norbornene, methylnorbornene, and ethylnorpocene are particularly preferable. Runnene, ethylidene norporene, dicyclopentapentane and the like are preferred.

The third monomer that can be addition-copolymerized with a conjugated diene monomer or a cyclic olefin monomer is styrene, o-methylstyrene, p-methynolestyrene, m-methynolestyrene, or o. , p-Dimethinolestyrene, ethynolestyrene,: — tert-butylinolestyrene, α-methynolestyrene, o-chlorostyrene, p-chlorostyrene, _m -chlorostyrene, p-bromostyrene, burnaphthalene, etc. - Olefin compounds such as ethylene, propylene and 1-butene;

(Meth) acrylic acid alkyl esters such as (meth) methyl acrylate, (meth) acrylic acid 2-ethylhexyl, (meth) lauryl acrylate, etc .; nitrile group-containing monomer such as (meth) acrylonitrile Body; (meth) acrylamide, (meth) acrylamide, の -methylol (meth) ataliamide, (meth) acrylamide monomer such as Ν-butoxymethyl (meth) acrylamide, and the like.

 The charge ratio of the conjugated gen monomer and the cyclic olefin monomer during the polymerization reaction is such that all the repeating structural units of the conjugated gen-cyclic olefin added copolymer are conjugated gen monomer. It is necessary to determine such that the repeating structural unit derived from the cyclic olefin monomer is 90 to 1 mol% with the repeating structural unit derived from a cyclic olefin monomer being 10 to 99 mol%. The relationship between the charged ratio of both monomers and the ratio of the repeating structural units derived from both monomers can be understood by conducting preliminary experiments.

 In the present invention, as a polymerization catalyst for addition-copolymerizing a conjugated diene monomer and a cyclic olefin monomer, a transition metal compound belonging to Groups 4 to 10 of the periodic table, In addition, a polymerization catalyst whose main component is a compound having a ligand coordinated with π electrons is used.

Any of transition metals of Groups 4 to 10 of the periodic table can be used, but specific examples include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, and rhenium. , Iron, rubidium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum and the like. Of these, titanium, zirconium, hafium, vanadium, chromium, manganese, iron, cobalt, nickel and palladium are preferred. The ligand coordinated by π electrons is a ligand in which an unsaturated compound or an unsaturated group coordinates to the above-mentioned transition metal using its π molecular orbital. Specific examples of ligands coordinated by π electrons include ethylene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, 1,4-cyclohexadiene, 1,5-cyclohexadiene, 1,5,9— Linear or cyclic olefins or non-conjugated polyolefins such as cyclododecatriene, norbornadiene, and dicyclopentapentane; 2-norbornolenyl, 6-methoxy-12-norbornenyl, cyclootate Olefinyl groups such as butadiene, isoprene, 1,3-hexadiene and 1,3-octadiene;

 Aryl group, crotinolene group, pentagenenyl group, 2,4-dimethynolepentageninole group, 2,7-dimethyl-1,2,6-octacten-1,1,8-diyl group, 2,6,10-dodecatriene-11 , 12-diyl group, cyclopentagenenyl group, methylcyclopentagenenyl group, dimethylcyclopentagenenyl group, trimethylcyclopentenyl group, tetramethylcyclopentagenenyl group, pentamethylcyclopentenyl group, n- Linear, branched or cyclic genenyl groups such as butynolecyclopentageninole group, indeninole group, tetrahydroindul group, cyclooctagenyl group;

 Aromatic compounds such as tetraphenylenolecyclobutadiene, benzene, toluene, p-cymene, 1,3,5,7-cyclooctatetraene; phenylenoacetylene, diphenylacetylene, di (ethoxycarbonyl) Acetylenes such as acetylene can be mentioned. Further, a polydentate ligand in which a plurality of these ligands are crosslinked is also included. Among these, a linear, branched or cyclic genenyl group is particularly preferred.

 In the present invention, the above transition metal compound having a ligand coordinated with π electrons may be used alone, or may be used in combination with a cocatalyst as needed.

 Further, a supported catalyst in which the above catalyst is supported on an inorganic carrier such as magnesium chloride, silica, alumina or the like or an organic carrier such as polystyrene may be used.

 Particularly preferred examples of the polymerization catalyst used in the present invention include an aryl complex of a transition metal belonging to Group 10 of the periodic table and a cyclopentadenyl complex of a transition metal belonging to Group 4 or 5 of the periodic table (a so-called meta-opening catalyst). Catalyst).

The aryl group complex of a transition metal of Group 10 of the periodic table is a transition metal compound of Group 10 of the periodic table having an aryl group, and specifically includes a compound represented by the following general formula [13]. Can be. Chemical 3

R ²¹ ~ ((M ¹ () ( ¹ ) (Y ¹ ) _n [1 3]

R 22

(Where M is a transition metal of Group 10 of the periodic table, and R ² °, R ²¹ and R ²² are each independently a water atom or a halogen atom, or a halogen atom, a nitrogen atom, an oxygen atom or a silicon atom. An optionally branched hydrocarbon having 1 to 20 carbon atoms, which may have a substituent containing an atom, and R ² ° and R ²² are bonded to each other to form a cyclic structure. X ¹ represents any anionic ligand, Y ¹ represents any neutral ligand, n is 0, 1 or 2, and p is 1 or 2.) Specific examples of aryl complexes of transition metals of Group 10 of the periodic table include bis (arylnickenolebromide), bis (arylnickel acetate), bis (arylnickel trifluoroacetate), and aryl (hexafluoroacetone). Nickel trifluoroacetate, Aryl (Hexaclo acetone) Nickel trifluoroacetate, [crotyl (1,5-cyclooctadiene) nickel] hexafnorolophophosphate, [crotyl (1,5-cyclooctadiene) echkel] tetrakis [3, 5-bis (trifluoromethylinole) -phenyl] borate, 2,6,10-dodecatriene 1-yleckenolehexafluorophosphate, methallylnickel (tricyclohexylphosphine) .aryl nickel such as trifluorophosphate Compound ;

Bis (aryl palladium chloride), aryl palladium (tricyclohexynolephosphine) chloride, bis (aryl palladium acetate), bis (aryl palladium trifluoroacetate), aryl palladium (tricyclohexylphosphine) Trifluoroacetate, aryl palladium (tree o-tolyl phosphine) chloride, aryl palladium (tri-o-tolyl phosphine) triflate-aryl palladium (tri-o-tolyl phosphine) ditorate, bis ( A Aryl palladium compounds such as aryl palladium iodide; aryl platinum (tricyclohexyl phosphine) chloride, aryl platinum (tricyclohexyl phosphine) triflate, bis (aryl platinum acetate), bis (aryl platinum trifluoroacetate) (1) and the like.

 Of these, halogen-containing aryl complexes, specifically, bis (arylnickel bromide), bis (aryluckel trifluoroacetate), aryl (hexanol acetonate acetone) Nickelene trifnoreoacetate acetate, arinole (Hexachloroacetone) Nickel trifluoroacetate, [crotyl (1,5-cyclooctadiene) eckenole] hexafluorophosphate, [crotinole (1,5-cyclootatagene) nickel] tetrakis [3,5— Bis (trifluoromethyl) -phenyl] borate, 2,6,10-dodecatriene-1 —ylnickelhexafluorophosphate, methallylnickel (tricyclohexylphosphine) triflate, bis (arylpalladium chloride) ), Aryl palladium (tricyclo (Xylphosphine) chloride, bis (arylpalladium trifluoroacetate), arylenepalladium (tricyclohexynolephosphine) trifluoroacetate, arylpalladium (tri_-tolylphosphine) chloride , Aryl palladium (tri-o-tolyl phosphine) triflate, bis (aryl palladium iodide), aryl palladium (trisyl hexyl phosphine) chloride, aryl platinum (trisyl hexyl phosphine) triflate, bis (Arinole platinum trifluoroacetate) and the like.

A cycle pentagenenyl complex of a transition metal of Group 4 or 5 of the Periodic Table is a compound of Group 4 or 5 of the Periodic Table that has a cycle pentajeel group or a substituted cycle pentajenyl group as a ligand. The compound is not particularly limited, and examples thereof include a compound represented by the following general formula [14]. Chemical 1 4

(T is a cyclopentagenenyl group or a substituted cyclopentagenyl group, and L is a cyclopentagenenyl group, a substituted cyclopentagenenyl group, an alkyl group having 1 to 8 carbon atoms or a halogen atom when q is 0. the, m is consequent opening Pentaje two Le group when 1,. M ² is the periodic table illustrating the ligand having a hetero atom of the first group V or group 1 6-substituted cyclopentadienyl group or the periodic table X ² represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, and Y ² represents an alkyl group having 1 to 8 carbon atoms, a halogen atom or a hydrogen atom. Represents a methylene group, a silylene group or a dimethylene group, q represents 0 or 1. T and L, X ² and Y ² may be the same, and when q is 0, L, X ² and Y ² May be the same.)

 The cyclopentagenenyl group or substituted cyclopentenyl group of T and L includes cyclopentagenenyl group, indul group, fluorenyl group, and one or more of these hydrogen atoms are substituted with an organic group. It is a thing. Organic groups include not only hydrocarbon groups such as methyl group, ethyl group or phenyl group, but also ether groups, thioatenole groups, carbonyl groups, sulfoninole groups, ester groups, thioester groups, amino groups, amide groups. And an organic group having at least one atomic group having a hetero atom such as a phosphino group or a phosphinyl group. Examples of the ligand having a hetero atom of Group 15 or Group 16 of the periodic table of L include ligands having nitrogen, phosphorus, oxygen or sulfur. Of these, nitrogen or phosphorus belonging to Group 15 of the periodic table is preferable, and nitrogen is particularly preferable.

Examples of the metal of Group 4 or Group 5 of the periodic table of M ² include titanium, zirconium, hafdium, and vanadium. Above all, titanium or zircon Dummy is particularly preferred. Examples of the alkyl group having 1 to 8 carbon atoms of L, X ² and Y ² include methyl, ethyl, propyl, isopropyl, butyl, isoptyl, tert-butyl, pentyl, isopentyl, hexyl, isohexyl, and octynole. , 2-ethylhexyl and the like, and the halogen atom include chlorine, bromine, iodine and fluorine atoms. Among them, methyl, ethyl, propyl or butyl having 1 to 4 carbon atoms, or chlorine or bromine is preferable.

 Specific examples of the cyclopentenyl complex of a transition metal belonging to Group 4 or Group 5 of the periodic table represented by the above general formula [14] include: q is 0, L is a cyclopentagenenyl group, and substituted cyclopentagenenyl. Examples of the compound which is a group include bis (cyclopentagen) titanium dimethyl, bis (1,2-dimethylcyclopentagenenyl) zirconium dichloride, bis (cyclopentageninole) dinoreconidium dipheninole, bis (Pentamethylcyclopentagenenyl) Hafnium dichloride, Bis (η-butynolecyclopentagenenyl) dinoreconidum dichloride, Bis (indenyl) dinorecone dichloride, Bis (cyclopentagenenyl) Vanadium dichloride.

 Compounds in which q is 0 and L is an alkyl group having 1 to 8 carbon atoms or a halogen atom include cyclopentagenenyltitanium trichloride, pentamethylcyclopentagenoretitanium trimethyl, and pentamethyi. Noresic mouth pentagenenyl zirconium trichloride, (2-methoxetinole) cyclopentageninoletitanium trichloride, methoxycarboninole methylcyclopentagenenyl titanium trichloride, 2- (N, N-Jetylamino) Tylcyclopentagenenyltitanium trichloride and the like.

Compounds in which q is 1 and L is a cyclopentagenenyl group or a substituted cyclopentagenenyl group include rac-dimethylsilylbis (1-indul) zirconium dichloride, dimethylsilyl (cyclopentagenenyl) (9 —Fluorenyl) zirconium dichloride, dimethylmethylidene (cyclopentagenenyl) (9-fluorenyl) zirconium dichloride, diphenyl-methylidene (cyclopentageninole) (9-fluoreninole) disresiconidum dichloride, rac—ethylenebis (11 indul) dinoreconidum dichloride, rac-ethylenebis (4, 5, 6,7-tetrahydro-11 indul) zirconium dichloride and the like.

Examples of the compound in which q is 1 and L is a ligand having a hetero atom belonging to Group 15 or 16 of the periodic table include dimethylsilyltetramethylcyclopentagenenyl (t-butylamide) titanium dimethyl Dimethylsilyltetramethylcyclopentadienyl ( _t- butylamide) zirconium dichloride; dimethylsilylcyclopentenyl (phenylamide) zirconium dichloride;

Among them, when q is 0, L is an alkyl group having 1 to 8 carbon atoms or a halogen atom, such as cyclopentageninoletitanium trichloride, Pentamethylcyclyl pentadienyl zirconium trichloride, (2-methoxethyl) cyclopentageninoletitanium trichloride, methoxycarbonylmethylcyclopentagenenyl titanium trichloride, 2- (N, N-jetinoleamino) Preferred is ethylcyclopentadienyltitanium trichloride. as q is 1, L is cyclopentadienyl group or a substituted cyclopentadienyl group _ra c- di methyl bis (1-Indeniru) zirconium two Umujikurori de, dimethylsilyl (consequent opening Pentajeniru) ( 9-Fluorenyl) Zirconium dichloride, dimethyl methylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylenomethylidene (cyclopentapentaenyl) (9-funolelenyl) Zirconium dichloride, rac-ethylene bis (1-indur) Zirco umium dichloride, rac-ethylene bis (4,5,6,7-tetrahydro-11-indenyl) zirconium dichloride, etc., and dimethylsilyltetramethylcyclide pentagenenyl where L is an amide group (t-butylamide) titanium dimethyl, Dimethylsilyltetramethylcyclopentagenenyl (t-butylamide) di / reconium dichloride, pentagenenyl (pheninoleamide) zirconium dichloride, etc. are preferred.

In the present invention, the cocatalyst used as necessary may react with a transition metal compound as a main component to develop catalytic activity, activate the catalyst, or use a polymerization catalyst. It has the function of stabilizing. Therefore, as an example of a co-catalyst,

(1) Alkylating agents, (2) those which react with a transition metal compound to form an ionic complex, and (3) Lewis bases, but are not limited thereto.

 Examples of the alkylating agent of the above (1) include organic lithiums such as η-butyl lithium, methyl lithium, and phenyl lithium; butyl ethyl magnesium, butyl octinole magnesium, dihexyl magnesium, ethyl magnesium chloride, η Organic magnesium such as butylmagnesium chloride and arylmagnesium bromide; Organic magnesium such as dimethyl sub-sharp, getyl sub-bell, and diphenyl sub-bell; Trimethylaluminum, triethylaluminum, triisobutylaluminum, and diethyleneol Organic aluminum such as minichloride, ethylaluminum sesquichloride, ethylaluminum dichloride, methylaluminoxane, ethylaluminoxane, i-butylaluminoxane, and chloroaluminoxane It can be.

Examples of the compound that reacts with the transition metal compound of the above (2) to form an ionic complex include the organoaluminums mentioned in the above (1); triethylammonium tetraphenylborate, and dimethylanilinium tetrakis (pentafluorophenyl) borate. Pam, Tetrakis (pentaphnoleolopheninole) Trityl borate, Tetrakis (pantaphneololophenylinole) Lithium borate, Tetrakis (pentaphnoleolophenylene) Ferrousenium borate, Tris (pentafluorophenyl) Boron e ©-containing compounds such _{as; Mg (C 1 θ4) 2} , AgC 10 4, Mg (I θ4) 2, Ag IO 4, (NH 4) C 1 θ4, (P h 3 C) C 1 θ4, (C _{1 3 C) C 10 4,} (NBU 4) C 10 4, (NE) _{I_rei_4, (P h 3 C) I} 0 4, (C 1 3 C) IO 4, such as (NB U4) I θ4 Perchlorate or periodate; such as hexafluoro silver phosphate Compounds; Furuorosuruhon acid Anmoniumu, sulfur compounds such as chlorosulfonic silver; to hexa full O b antimony compounds such as antimony acid Anmoniumu; bentonite bets, and the like clay compounds such Monmori opening night.

The Lewis base of the above (3) is an electron donating compound and generally has a hetero atom. Compound. Examples include nitrogen compounds such as N-heterocarbene ring compounds, amines, amides and pyridines; oxygen compounds such as ethers, ketones and esters; sulfur compounds such as thioethers, thioesters and sulfones; phosphorus compounds such as phosphines. Can be Among them, a highly basic N-heterocarbene cyclized compound, pyridine, phosphine and the like are preferable.

 In the present invention, the polymerization reaction may be performed in a solvent or without a solvent.However, when a hydrogenation reaction is subsequently performed after the polymerization reaction, polymerization in a solvent is more quickly performed in the next step. This is preferable because it can be shifted. The polymerization solvent is not particularly limited as long as it dissolves the polymer and does not inhibit the polymerization.

 Specific examples of the polymerization solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methinolecyclohexane, dimethylcyclohexane, trimethinolecyclohexane, ethynolecyclohexane, and getylcyclohexane. Alicyclic hydrocarbons such as hexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexanehydrindene, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; nitromethane, nitrobenzene, and acetonitrile Nitrogen-containing hydrocarbons; ethers such as Jethyl ether and tetrahydrofuran; and halogen-containing hydrocarbons such as chlorophonolem, dichloromethane, chlorobenzene, and dichlorobenzene; this Among these solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and ethers that are widely used industrially are preferable.

 When the polymerization is performed in a solvent, the total concentration of the monomers is 1 to 60% by weight. /. Is preferable, 2 to 55% by weight is more preferable, and 5 to 50% by weight is particularly preferable. If the concentration of the monomer is too low, the productivity will be poor, and if it is too high, the viscosity after polymerization will be too high to make handling difficult.

In the production method of the present invention, the ratio of the transition metal compound as the polymerization catalyst to the total amount of the monomers is (transition metal: monomer) as follows: 1: 100 to 1: 2,000,000 (monolith: Mol), preferably from 1: 500 to 1: 1,000,000 (mol: monole), more preferably from 1: 1,000 to 1: 500,000 (mol: mol). If the amount of the catalyst is too large, it becomes difficult to remove the catalyst.If the amount is too small, sufficient polymerization activity is obtained. I can not get the nature. The ratio between the transition metal compound and the cocatalyst varies depending on the cocatalyst to be added. In general, (transition metal: cocatalyst) is 1: 0.1 to 1: 20,000 (mol: mol). And preferably 1: 0.5 to 1: 10,000 (mole: mol), more preferably 1: 0.8 to: 1: 5,000 (mole: mol).

 The polymerization reaction is started by mixing the above-mentioned monomer and a polymerization catalyst. The polymerization temperature is not particularly limited, but is usually -30 ° C to 200 ° C, preferably 0 ° C to 180 ° C. The polymerization time is usually from 1 minute to 100 hours.

 In order to produce the hydride of the addition copolymer of the present invention, 80% or more of all carbon-carbon double bonds in the conjugated gen-cyclic olefin addition copolymer are hydrogenated. In order to achieve a significant effect of improving heat resistance and weather resistance, hydrogenation is preferably performed on 90% or more, more preferably 95% or more, of all carbon-carbon double bonds. As a result, the ratio of double bonds (excluding aromatic bond double bonds) to the total number of carbon-carbon bonds in the polymer is 0.2% or less, preferably 0.1% or less, more preferably 0.05%. It can be:

 The hydrogenation reaction is carried out in a hydrogen atmosphere by adding a hydrogenation catalyst to the addition copolymer, preferably to a solution of the addition copolymer organic solvent.

 The hydrogenation catalyst used in the present invention can be used without any particular limitation as long as it is generally used for the hydrogenation reaction of olefins and aromatic compounds. Specific examples of the hydrogenation catalyst include (a) a supported metal catalyst in which a transition metal such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, alumina, silica, or diatomaceous earth; Mouth) Homogeneous catalysts consisting of organic transition metal compounds such as titanium, cobalt or nickel and organometallic compounds such as lithium, magnesium, aluminum or tin; (c) Metal complex catalysts such as rhodium and ruthenium Can be.

Specific examples of the supported metal catalyst of the above (a) include nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, Examples include catalysts such as diatomaceous earth, palladium Z alumina, platinum / silica, platinum / alumina, rhodium / silica, rhodium / alumina, ruthenium / nosilica, ruthenium / noalumina. As the homogeneous catalyst of the above (Port), (organic transition metal compound / organic metal compound) is described in terms of cobalt triethyl aluminum acetate, nickel acetyl acetonate / trisoptinole aluminum, titanocene aluminum oxide Π —Butyllithium, zirconocene dichloride / sec—A combination of butyllithium, tetrabutoxytitanate / dimethylmagnesium and the like.

 Examples of the metal complex catalyst (c) include dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, dihydridotetra (triphenylphosphine) ) Ruthenium, dihydrido (acetonitrile) tris (triphenylphosphine) ruthenium, dihydrido (tetrahydrofuran) tris (triphenylphosphine) ruthenium, and the like.

The organic solvent used for the hydrogenation reaction is usually an inert organic solvent. The inert organic solvent is preferably a hydrocarbon-based solvent or an ether-based solvent which is excellent in the solubility of the conjugated gen-cyclic olefin addition copolymer hydride to be produced. Examples of such a solvent include aromatic hydrocarbon solvents such as benzene and toluene; aliphatic hydrocarbon solvents such as _n- pentane and _n- hexane; and alicyclic hydrocarbon solvents such as cyclohexane and decalin. Solvents include ethers such as tetrahydrofuran and ethylene glycol dimethyl ether.

 When the same solvent as that used in the polymerization reaction is used, a hydrogenation reaction can be performed by adding a hydrogenation catalyst to the solution as it is after the polymerization reaction.

The optimal reaction conditions for the hydrogenation reaction vary depending on the type of hydrogenation catalyst used, but the temperature is usually from 120 ° C to 250 ° C, preferably from 110 ° C to 220 ° C. , More preferably from 0 to 200 ° C; the hydrogen pressure is usually from 0.01 to 1 OMPa, preferably from 0.05 to 7.5 MPa, more preferably from 0.1 to 5 MPa. a: The reaction time is usually 0.1 to 100 hours, preferably 0.2 to 10 hours. If the hydrogenation temperature is too low, the reaction rate will be slow, and if it is too high, side reactions may occur. If the hydrogen pressure is too low, the reaction rate will be slow, and if it is too high, a high pressure reactor will be required. If the reaction time is too short, the degree of hydrogenation is insufficient, and if it is too long, side reactions may occur. After the hydrogenation reaction, the length of the hydrogenation catalyst is removed by filtration with a filter when the supported metal catalyst described in (a) above is used. The homogeneous catalyst of the above (mouth), and

If a metal complex catalyst such as rhodium or ruthenium in (c) is used, it can be separated by adsorption to an adsorbent, or by washing with water or a lower alcohol in the presence of an organic acid and / or inorganic acid. to recover. Also, depending on the application of the hydrogenated polymer, it is not necessary to remove the hydrogenation catalyst.

 The addition copolymer and the hydride of the addition copolymer of the present invention (hereinafter, both may be referred to as “cyclic olefin addition copolymer” in some cases) are an antioxidant, an ultraviolet absorber, a weathering stabilizer, and cloudiness. As a polymer composition prepared by appropriately blending various compounding agents such as antistatic agents, antistatic agents, organic or inorganic fillers, fillers, crosslinking agents, vulcanizing agents, as an elastomer material or as a plastic material. Provided.

 Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and zeolite-based antioxidants. Of these, phenol-based antioxidants, particularly alkyl-substituted phenol-based antioxidants, are preferred. . By adding these antioxidants to the cyclic olefin addition copolymer, it is possible to prevent coloring and strength reduction of molded products due to oxidative deterioration during molding without reducing transparency and low water absorption. Therefore, it is particularly important as a compounding agent.

Examples of phenolic antioxidants include octadecyl-3- (3,5-di-t-butynoleic 4-hydrodroxypheny ^ /) propionate, 2,2, -methylene-bis (4-methylinole 6-t-butynolephenol) ), 1,1,3-Tris (2-methyl-4-hydroxy-5-t-butylpheninole) butane, 1,3,5-trimethylenolae 2,4,6-Tris (3,5-di 1-t-butynole 4-hydroxyhydroxybenzole) Benzene, tetrakismethylene 1- (3-, 3,5, di-t-butynolee 4, —hydroxyphenylepropionate) methane [ie pentaerythritinole tetrakis 3- (3,5-di-t-butyl-4-hydroxyphenylpropionate)], triethylene glycol bis {3- (3-t-butyl-4-hydroxy-5-methylphen) Alkyl-substituted phenolic compounds such as nyl) propionate}; 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methyl — 4-Methylphenyl acrylate, 2,4-di-t-amyl-6- {1- (3,5-di-t-amyl-1-2-hydroxyphenyl) ethyl} phenyl acrylate Patent No. 179953-Atallylate compounds described in JP-A-1-16863; 6- (4-Hydroxy-3,5-di-t-butylanilino) -1,2,4-bisoctylthio-1,3,5 Triazine, 4-bisoctylthio-1,3,5-triazine, 2-octylthio-1,4,6-bis (3,5-di-t-butyl-4-oxyanilino) -1,3,5-triazine, etc. Group-containing phenolic compounds can be used.

 The phosphorus-based antioxidant is not particularly limited as long as it is a substance generally used in the general resin industry. Examples thereof include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, and the like. Tris (noyurphenyl) phosphite, tris (dinoyurphenyl) phosphite, tris (2,4-di-t-p-inolephene), phosphite, 10— (3,5-g-butynoley 4-hydroxy benzyl) ) —9,10-Dihydro 9-oxa 10-phosphophenanthrene 10-oxide and other monophosphite compounds; 4,4, butylidene-bis (3-methino-l- 6-t-butyl-phenylene-triethyl) Decyl phosphite), 4,4, isopropylidene-bis [phenyldialkyl (C12-C15) phosphite] Any diphosphite compound can be used.

 Examples of the zwitterion-based antioxidants include dilauryl-1,3-thiodipropionate, dimyristyl 3,3,1-thiodipropionate, distearyl-3,3-thiodipropionate, and radiaryl stearinole 1-3. , 3-thiodipropionate, pentaerythri tonole-tetrakisou-laurinole-thio-propionate,

3,9-bis (2-dodecylthioethyl) —2,4,8,10-tetraoxaspiro [5,5] pentane.

 Each of these antioxidants can be used alone or in combination of two or more.The amount of the antioxidants is appropriately selected, but is usually 0.1 to 100 parts by weight of the cyclic olefin addition copolymer. It is 001 to 5 parts by weight, preferably 0.01 to 1 part by weight.

Examples of ultraviolet absorbers and weather stabilizers include, for example, 2,2,6,6-tetramethyl 4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-14-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-14-piperidyl) _2— ( 3,5-di-t-butyl-4-hydroxybenzyl) — 2-n-butylmalonate, 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] — 1— {2-—3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl}-2,2,6,6-hindered amine compounds such as tetramethylpiperidine; 2 — (2-Hydroxy-1-5—Methynolefenore) Benzotriazonole, 2- (3-T-Ptinole1-2-Hide Moutine-1-5—Methinolefenole) 1-5—Clozen Benzotriazonole, 2— (3, 5—di-t—butynole 1—hydroxyv Benzotriazole-based compounds such as 1-5-benzo-benzo-l-azo- 1-, 2- (3,5-di-t-amino-l- 2-hydroxyphenyl) benzotriazol; 2,4-di-t-l Bezohate compounds such as 3,5-di-t-butynole 4-hydroxybenzoate and hexadecinole 3,5-di-t-butyl-4-hydroxybenzoate are exemplified. '

 These ultraviolet absorbers and weathering stabilizers can be used alone or in combination of two or more. The amount of the ultraviolet absorber and the weather stabilizer is usually 0.001 to 5 parts by weight, preferably 0.01 to 2 parts by weight, per 100 parts by weight of the cyclic olefin addition copolymer. Range.

 In addition, by adding an alcoholic compound to the cyclic olefin addition copolymer of the present invention, it is possible to reduce the properties such as transparency, low water absorption and mechanical strength in a long-time high-temperature and high-humidity environment. The product can be made into a molded product that does not easily become cloudy even when used in The alcoholic compound is a compound having at least one non-phenolic hydroxyl group in the molecule, and preferably has at least one hydroxyl group and at least one ether bond or ester bond.

Specific examples of such compounds include, for example, dihydric or higher polyhydric alcohols, more preferably trihydric or higher polyhydric alcohols, and even more preferably one of the hydroxyl groups of a polyhydric alcohol having 3 to 8 hydroxyl groups. Etherified or esterified alcoholic ester compounds include alcoholic ester compounds. Examples of the dihydric or higher polyhydric alcohol include, for example, polyethylene glycol, dali cellonole, trimethylonolepropane, pentaerythritol, diglycerolone, triglycerol, dipentaerythritol, and sorbitol. Is preferably a polyhydric alcohol having 3 to 8 hydroxyl groups. When an alcoholic ester aldehyde compound is obtained, glycerol, diglycerol, triglycerol, and the like, from which an alcohol 1 "raw ester compound containing α, β-diol can be synthesized, are preferable.

 Such alcoholic compounds include, for example, glycerin monostearate, glycerin monolaurate, glycerin dilaurate, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol monoberate and dipentaerythritol distearate Polyester of polyhydric alcohol; 3- (octynoleoxy) — 1,2-propanediol, 1, 6 —dihydroxy-1,2,2-di (hydroxymethyl) -17 — (4-nourpheny2oxy) 1-4 — Alcoholic ether compounds obtained by the reaction of oxoheptane, ρ-noylphenyl ether and formaldehyde with glycidol, —by the reaction of glycidol with the condensate of octylphenyl ether and formaldehyde Alcoholic Eterui 匕合 product to be, .rho. Okuchirufue two ether and alcohol one Le ether compound obtained by reaction of a condensate and glycidol dicyclopentadiene, and the like. These polyhydric alcoholic compounds are used alone or in combination of two or more.

 Although the molecular weight of these polyhydric alcoholic compounds is not particularly limited, those having a molecular weight of usually 500 to 200, preferably 800 to 150 are preferable because the transparency is hardly reduced.

 The compounding amount of the alcoholic compound is usually 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight, particularly preferably 0 to 10 parts by weight, based on 100 parts by weight of the cyclic olefin addition copolymer. 0.5 to 2 parts by weight.

Examples of the antistatic agent include long-chain alkyl alcohols such as stearyl alcohol and behenyl alcohol; sodium alkyl sulfonate, phosphonium anoalkyl sulfonate; fatty acid esters such as glyceryl stearate; Xyamine compounds; alkyl phosphamines; polyoxyethylene alkylamines; alkyl jetanoyl ureamides; polyoxyethylene-polyoxypropylene block copolymers; organoboron-based surfactants; cationic surfactants; , Tin oxide powder, antimony-containing tin oxide powder, and the like. The amount of the antistatic agent is usually in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the cyclic olefin addition copolymer.

 As the organic filler, ordinary organic polymer particles or cross-linked organic polymer particles can be used. Examples thereof include polyolefins such as polyethylene and polypropylene; and halogen-containing bulb weights such as polychlorinated vinyl and polychlorinated vinylidene. Polymers derived from polyunsaturated acids such as polyarylate and polymethacrylate; polymers derived from unsaturated alcohols such as polybier alcohol and polyacetate; polyethylene oxide or bisglycidyl Polymers derived from ethers; Aromatic condensation polymers such as polyphenylene oxide, polycarbonate, and polysulfone; Polyurethanes; Polyamides; Polyesters; Aldehyde phenolic resins; Particles or crosslinked natural polymer compounds To name the particles Kill.

 Examples of inorganic fillers include Group 1 element compounds such as lithium fluoride and borax (hydrated sodium borate); Group 2 element compounds such as magnesium carbonate, magnesium phosphate, calcium carbonate, strontium titanate, and barium carbonate; Group 4 element compounds such as titanium dioxide (titayua) and titanium monoxide; Group 6 element compounds such as molybdenum dioxide and molybdenum trioxide; Group 7 element compounds such as manganese chloride and manganese acetate; Group 8 to 10 element compounds; Group 11 element compounds such as cuprous iodide; Group 12 element compounds such as zinc oxide and zinc acetate; aluminum oxide (anoremina), aluminum fluoride, and anoleminosilicate (silicate) Group 13 element compounds such as lumina, kaolin, kaolinite; silicon oxide (silica, silicon) Gel), graphite, carbon, graph eye DOO, 1 4 group element compound such as glass; kernal stones, pronation Doo, mica (My force, Kinunmo) include particles of natural minerals, such as Pairosu ore.

Further, other polymers are arranged in the cyclic olefin addition copolymer of the present invention. Can be used in combination. Other polymers include thermoplastic resins or elastomers.

 Examples of the thermoplastic resin include an amorphous or crystalline norbornene-based ring-opening polymer, an amorphous or crystalline norbornene-based ring-opened polymer hydride, an amorphous norbornene-based addition polymer; a low-density polyethylene, Α-olefin resin such as high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, ethylene-ethyl acrylate copolymer, ethylene mono-butyl acetate copolymer, polypropylene, etc .; polystyrene, hydrogenated Polystyrene, syndiotactic polystyrene, impact-resistant polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-acrylonitrile-butadiene copolymer (ABS), styrene-methyl methacrylate-butadiene copolymer (MBS) Aromatic vinyl resin such as polymethyl Methacrylate, polyvinyl chloride, polyvinyl chloride, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, polycarbonate, cellulose triacetate, polyester terimide, polyimide, polyarylate, polysulfone, polyether sulfone. And the like. Of these, amorphous norbornene-based polymers, α-olefin-based resins, and aromatic vinyl-based resins are preferred. These thermoplastic resins can be used alone or in combination of two or more.

Elastomer is a polymer having a Tg of 40 ° C. or less. When the block copolymer has two or more glass transition temperatures, if the lowest glass transition temperature is 40 ° C. or lower, it can be used as an elastomer in the present invention. The viscosity of the elastomer (ML _{1 +4} , 100 ° C) is appropriately selected depending on the purpose of use, and is usually 5 to 300.

Examples of the elastomer include: ethylene-α-olefin rubber such as ethylene-propylene rubber; ethylene-α-olefin-polyene copolymer rubber; ethylene-methyl methacrylate, ethylene-butyltin acrylate, etc. Unsaturated carboxylic acid ester copolymers; alkyl acrylate polymers such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and radiuryl acrylate; polybutadiene, low-crystalline polybutadiene Styrene, polyisoprene, random copolymer of styrene and butadiene or isoprene, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) alkyl acrylate copolymer, butadiene-(meth) Conjugated gen-based rubbers such as alkyl acrylate-acrylonitrile copolymer, phthalene-1 (meth) alkyl acrylate-atari-mouth ethryl-styrene copolymer, butylene-isoprene copolymer; styrene-butadiene block copolymer Aromatic vinyl conjugated diene such as hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-butadiene random copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer Block copolymer; styrene-grafted ethylene-propylene elastomer; polyethylene terephthalate · poly (tetramethylene oxide) glycol copolymer; polyethylene terephthalate / isophthalate · poly (tetramethylene oxide) 'glycol Nore block copolymer, polybutylene terephthalate z isophthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate nodecane dicarboxylate 'Poly (tetramethylene oxide) Polyester such as dalicol block copolymer Thermoplastic elastomer; Ethylene ionomer resin and the like. Among these elastomers, ethylene-α-olefin-based rubber, conjugated-gen-based rubber, aromatic butyl-conjugated-gen-based block copolymer, and polyester-based thermoplastic elastomer are preferred. These elastomers can be used alone or in combination of two or more.

 In the polymer composition using the cyclic olefin addition copolymer of the present invention, if necessary, other compounding agents such as light stabilizers, near-infrared absorbing agents, coloring agents such as dyes and pigments, lubricants, A plasticizer, an anti-blocking agent, an optical brightener, a deodorant, and the like can be blended, and these can be used alone or in combination of two or more, and the blending amount does not impair the object of the present invention. It is appropriately selected within the range.

The molded article of the cyclic olefin addition copolymer of the present invention, in addition to having excellent transparency, has properties as an elastomer having a high elastic recovery rate due to the composition of the repeating structural unit constituting the polymer. Plus with large tensile strength It can exhibit the characteristics as tics. Also, the conjugated gen monocyclic olefin addition copolymer hydride has an advantage of further excellent heat resistance and weather resistance, and is therefore suitable for use outdoors.

 The cyclic olefin addition copolymer of the present invention can be molded by various molding methods such as a force render molding method, an extrusion molding method, an inflation molding method, a vacuum molding method, a cast molding method, an injection molding method, and a press molding method. Molded into a product.

 The cyclic olefin addition copolymer of the present invention includes optical products such as a lens for a camera, a lens for an overhead projector, a prism, a light diffusion plate, an optical fiber, a light guide plate, an optical fiber, a polarizing film, and a retardation film; Liquid containers such as liquid medicine containers, samples, infusion bags and eye drops containers; medical equipment such as syringes and medical infusion tubes; packaging materials such as tapes and buffer sheets; trays, pliers, stationery and storage boxes Consumer materials such as storage boxes, closet boxes, etc .; Transparent cases for storing goods, packaging materials such as blister packages; Pharmaceutical packaging materials such as powdered drug capsule containers, press-through packages for tablets; food wrap films, shrink Film, sealant film, knurl stretch film, agricultural film, etc. Norem; Vibration damping material; Pipe, tube, foam tube; Wire coating material; Automobile parts such as tires, side moulds, mudguards, bumpers, lamps, reflectors, etc .; Lighting parts, household appliances parts; Shoe soles; It can be used for civil engineering materials such as water sheets and drain materials; building materials; furniture materials; Among these uses, it is possible to provide a flexible and tough olefin-based resin molded article which cannot be realized by conventional conjugated gen-based polymers, olefin-based polymers, α-olefin-cycloolefin-added copolymers, and the like.

 Example

 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. Parts and percentages are by weight unless otherwise specified. The measuring method was as follows.

 (1) Weight average molecular weight (Mw) and number average molecular weight (Mn)

 Gel permeation using chloroform as a solvent. Chromatography (G

It was measured as a polystyrene equivalent value by PC).

(2) Composition and hydrogenation rate of cyclic olefin addition copolymer resin Measured by iH-NMR spectrum. Composition unit mole _^0/0. Hydrogenation rate units _^0/0. Ratio of number of double bonds to total carbon one-carbon bond number (excluding double bonds of the aromatic ring) is - was determined by NMR spectrum, the unit ^_0/0.

 (3) Glass transition temperature (T g)

 It was measured by a differential scanning calorimeter (DSC). In units.

 (4) Total light transmittance

 According to AS TM-D 1003, the total light transmittance (unit:%) was measured.

 (Example 1)

 To a pressure-resistant glass reactor equipped with a stirrer, 34.4 parts of toluene, 3.7 parts of butadiene (BD), and 2.6 parts of dicyclopentadiene (DCPD) dissolved in 1 part of cyclohexane were added. Next, diphenylmethylidene (cycopene pentageninole) dissolved in 2.5 parts of toluene (9-phenolic) dinorecone dichloride 0.05 parts and toluene 1.7 parts 0.34 parts of the dissolved methylaluminoxane was mixed in another glass reactor and added to the reactor to initiate polymerization. After polymerization at room temperature for 70 hours, the polymerization reaction solution was poured into a large amount of hydrochloric acid-acidic methanol to completely precipitate the polymer. The polymer was separated by filtration, washed, and dried under reduced pressure at 40 ° C for 18 hours. The yield of the obtained polymer was 1.8 parts (weight-based yield: 29%), the weight ratio of the BD / DCPD repeating unit was 40Z60, Mw was 5,800, and Mn was 3,6. 00. T g was 151 ° C.

 (Example 2)

 To a pressure-resistant glass reactor equipped with a stirrer, 60 parts of toluene, 3.5 parts of BD, and 23.5 parts of norpolpolene (NB) dissolved in 20 parts of toluene were added. Next, 0.14 parts of aryl (hexacrocetone acetone) nickel trifluoroacetate dissolved in 10 parts of toluene was added, and polymerization was carried out at 50 ° C for 20 hours. After pouring into a large amount of methanol to completely precipitate the polymer, the polymer was separated by filtration, washed, and dried under reduced pressure at room temperature for 40 hours. The yield of the obtained polymer was 10.5 parts, and the weight ratio of the polymer to the BDZ NB repeating unit was 43Z57. ] ^ 1 was 48,200 and Mn was 24,100. T g was 128 ° C.

Subsequently, 10 parts of the obtained polymer and cyclohexane were placed in an autoclave equipped with a stirrer. The hydrogenated catalyst solution obtained by adding 90 parts of nickel acetylacetonate, and then adding 0.097 parts of nickel acetyl acetate 0.30 parts of triisobutylaluminum to 4.7 parts of cyclohexane was added. Autoclave, hydrogen pressure 9.8MPa, 140. The hydrogenation reaction was carried out for 8 hours. The reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer, washed by filtration, and dried under reduced pressure at room temperature for 40 hours. The obtained polymer hydride was in a yield of 9.8 parts, and the weight ratio of the BDZNB repeating unit was 43Z57, Mw was 52,200, and Mn was 26,100. The hydrogenation rate was 99.4%, the ratio of the number of double bonds to the total number of carbon-carbon bonds in the polymer was 0.04%, and the Tg was 141 ° C.

 The obtained polymer hydride was formed into a large rigid disc having a diameter of 3.5 cm and a thickness of lmm by hot pressing. The total light transmittance of this disk was 92%, indicating high transparency.

 (Comparative Example 1)

 Example 1 was the same as Example 1 except that diphenylmethylidene (cyclopentapentaenyl) (9-fluorenyl) zirconium dichloride was changed to nickel acetylacetonate, which is known as a polymerization catalyst for BD. Copolymerization of BD and DCPD was attempted in the same manner as in 1. However, it did not polymerize.

 (Comparative Example 2)

 In Comparative Example 1, instead of 3.7 parts of BD and 2.6 parts of DCPD, the monomers were changed to 13.5 parts of BD and 23.5 parts of DCPD, and the reaction temperature was 70 hours at room temperature. The procedure was performed in the same manner as in Comparative Example 1 except that the temperature was changed to 260 ° C for 2.5 hours. Since a polymer was obtained, a hydrogenation reaction was carried out in the same manner as in Example 2. After cooling, the reaction solution was poured into a large amount of methanol to precipitate a polymer, which was separated by filtration, washed, and dried under reduced pressure at room temperature for 40 hours. The yield of the polymer was 26.0 parts, the weight ratio of the repeating unit of 80 to 60% was 36/64, Mw was 1600, Mn was 1350, and the hydrogenation ratio was 99.5%. The ratio of the number of double bonds to the total number of carbon-carbon bonds in the polymer was 0.03%, and T g was 113 ° C.

When this polymer hydride was hot pressed, a number of cracks were formed and a disk could not be formed. (Example 3)

 Example 2 was repeated, except that 23.5 parts of NB was changed to 3.5 parts. The polymer was obtained in a yield of 13.0 parts, the weight ratio of BD / NB repeating units was 87-13, Mw was 223,000, 1 ^ 11 was 84,000, and Tg was 120 ° C. I got it.

 This polymer was dissolved in toluene, and a disk having a diameter of 3.5 cm and a thickness of lmm was prepared by a casting method. This disc was highly elastic.

 (Comparative Example 3)

 Comparative Example 2 was performed in the same manner as Comparative Example 2 except that DCPD was changed from 23.5 parts to 3.5 parts. The yield of the polymer was 15.0 parts (yield: 88.2%), the weight ratio of the BD / D CPD repeating unit was 79/21, Mw was 1000, Mn was 900, and Tg was 60 ° C. . Using this polymer, a hydrogenation reaction was carried out in the same manner as in Example 2. After cooling, the reaction solution was poured into a large amount of methanol to precipitate a polymer, which was separated by filtration, washed, and dried under reduced pressure at room temperature for 40 hours. The yield was 98%, Mw was 1100, Mn was 950, and the hydrogenation rate was 97%. The ratio of the number of double bonds to the total number of carbon-carbon bonds in the polymer is 0.1 ° /. And the T g was 75 ° C. The polymer after hydrogenation was dissolved in toluene, and an attempt was made to produce a disc with a diameter of 3.5 cm and a thickness of lmm by the casting method. However, many cracks occurred and the disc could not be produced.

(Hereinafter, margin)

table 1

Car facility 1 饰 nS fiT5 "lJl

 1 2 1 2 3 3

BD 3.7 13.5 3.7 13.5 13.5 13.5 Preparation composition DCPD 2.6 ― 2.6 23.5 ― 3.5

 (Parts) B ― 23.5 ― ― 3.5 ―

BD 40 43 36 87 79 Composition DCPD 60 ― 64 1 21

(Molar ratio) NB 1 57 ― 13 ― Unit yield (Weight 29 28.4 S 70.3 76.5 88.2

Mw 5800 48200 without 1500 223000 1000 after Mn 3600 24100 1200 84000 900

Tg (° C) 151 128 105-20 60 Yield (% by weight) 98 95 98 Water Mw 52 200 1600 1 100 element Mn 26 100 1350 Θ50 Hydrogenation rate (%) 99.4 99.5 97 After double bond ratio (%) 0.04 0.03 0.1

Tg (° C) 141 113 75 Hot-pressed plate is hot-pressed plate Cast sheet Cast sheet High transparency and cracks are highly elastic Cracks

High rigidity

As shown in Table 1, each of the addition copolymers of the present invention is a sufficiently large polymer having an Mw of 50,000 or more (Examples 1 to 3). (Example 2). The addition copolymer of the present invention exhibits a plastic-like property with high rigidity and an elastic elastomer-like property depending on whether the number of repeating structural units derived from the conjugated diene monomer is small or large. (Examples 2 and 3).

 According to the method for producing an addition polymer of the present invention, an addition polymer can be obtained even at a reaction temperature of room temperature (Example 1). None (Comparative Example 1). In addition, although the polymerization occurs when the reaction is carried out at 260 ° C using this catalyst, the polymer has a small Mw of 200 or less, regardless of the number of repeating structural units derived from conjugated gen-based monomers. Cracks occurred in the molded product (Comparative Example 2, Comparative Example 3).

Claims

Claim aspects 1. An addition copolymer having at least a repeating structural unit derived from a conjugated gen-based monomer and a repeating structural unit derived from a cyclic olefin-based monomer, wherein each of the repeating structural units is based on the entire polymer repeating structural unit. Of the repeating structural unit derived from the conjugated diene monomer: 10 mol% to 99 mol%, and the repeating structural unit derived from the cyclic olefin type monomer: 90 mol ⁰ /. ~ 1 mol%,  The weight average molecular weight in terms of polystyrene determined by gel permeation chromatography is 5, 000 to: 1, 000, 000,  An addition copolymer having a glass transition temperature of —100 ° C. to 200 ° C.  2. The addition copolymer according to claim 1, wherein the content of the repeating structural unit derived from the conjugated diene monomer is from 10 mol% to 50 mol%.  3. The addition copolymer according to claim 1, wherein the content of the repeating structural unit derived from the conjugated diene monomer is 50 mol% to 99 mol%.  4. The addition copolymer according to claim 1, wherein the cyclic olefin monomer is a norpoleneene monomer.  5. An addition copolymer hydride having at least a repeating structural unit derived from a conjugated gen-based monomer and a repeating structural unit derived from a cyclic olefin-based monomer, The content of each of the repeating structural units with respect to the total polymer repeating structural units is: a repeating structural unit derived from a conjugated gen-based monomer: 10 mol% to 99 mol%; a repeating structural unit derived from a cyclic olefinic monomer : 90 mol ⁰ /. ~ 1 mol%,  The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography is 5, 000 to: 1, 000, 000,  A glass transition temperature of 100 to 200 ° C., An addition copolymer hydride in which the ratio of the number of double bonds (excluding the double bond of the aromatic ring) to the total number of carbon-carbon bonds is 0.2% or less. 6. The hydride of the addition copolymer according to claim 5, wherein the content of the repeating structural unit derived from the conjugated diene monomer is from 10 mol% to 50 mol%.  7. The hydride of an addition copolymer according to claim 5, wherein the repeating structural unit derived from the conjugated diene monomer is 50 mol% to 99 mol%.  8. The hydride of an addition copolymer according to claim 5, wherein the cyclic olefin monomer is a norpoleneene monomer.  9. In the presence of a polymerization catalyst containing a transition metal compound belonging to Groups 4 to 10 of the periodic table in which the ligand is coordinated by π electrons, at least a conjugated gen-based monomer and a cyclic olefin-based monomer are used. A method for producing an addition copolymer, comprising polymerizing a monomer containing:  10. The method for producing an addition copolymer according to claim 9, wherein the polymerization catalyst is an aryl complex of a transition metal belonging to Group 10 of the periodic table.  11. The method for producing an addition copolymer according to claim 9, wherein the polymerization catalyst is a cyclic pentagenyl complex of a transition metal of Group 4 or 5 of the periodic table.  12. In the presence of a polymerization catalyst containing a transition metal compound belonging to Groups 4 to 10 of the periodic table in which the ligand is coordinated by π electrons, at least a conjugated gen-based monomer and a cyclic olefin-based monomer are Producing a hydrogenated addition copolymer, which comprises polymerizing a monomer containing the compound to obtain an addition copolymer, and then hydrogenating a carbon-carbon double bond in the addition copolymer. Method.  13. The method for producing a hydride of an addition copolymer according to claim 12, wherein the polymerization catalyst is an aryl complex of a transition metal belonging to Group 10 of the periodic table.  14. The method for producing a hydride of an addition copolymer according to claim 2, wherein the polymerization catalyst is a cyclopentagenyl complex of a transition metal of Group 4 or 5 of the periodic table.