JPH0892357A - Production of modified norbornene resin - Google Patents

Abstract

PURPOSE: To provide a modified norbornene resin having the properties of a block-copolymerized polymer while keeping the characteristic features of a thermoplastic norbornene resin. CONSTITUTION: This resin consisting of a polymer mixture containing a block copolymer composed of polystyrene block and ring-opened norbornene polymer block is produced by the ring-opened polymerization of a norbornene monomer (e.g. 6-methyl-1,4:4,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene) using a metathesis polymerization catalyst in the presence of a polymeric monomer having a vinyl group on at least one of chain terminals (e.g. a polymer produced by carrying out living anionic polymerization of styrene using an alkyllithium catalyst such as n-butyllithium and reacting the resultant polystyrene with allyl chloride, etc., to introduce vinyl group to the chain terminal). The product may be further hydrogenated. A transparent material having excellent thermal degradation resistance and high refractive index can be produced e.g. by block- copolymerizing the norbornene polymer with a polystyrene and hydrogenating the product in such a manner as to saturate the double bond of the main chain while keeping the aromatic ring structure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel modified norbornene-based resin and a method for producing a hydrogenated product thereof, more specifically, a modified norbornene-based resin comprising a heteropolymer block and a norbornene-ring-opening polymer block, and The present invention relates to a method for producing the hydrogenated product.

[0002]

2. Description of the Related Art Norbornene ring-opening polymers and hydrogenated products thereof have heat resistance, transparency, low hygroscopicity, low water absorption, chemical resistance, moisture resistance, water resistance, transparency and low birefringence. It is widely used as a resin in optical materials, medical materials, electrical insulation materials, automobile parts materials, and the like. In particular, norbornene-based ring-opening polymers and hydrogenated products thereof are excellent in low birefringence as compared with other transparent thermoplastic resins, and are attracting attention as optical materials.

However, as the technology advances, it has become necessary to introduce various properties into the norbornene ring-opening polymer and its hydrogenated product depending on the purpose of use. For example, norbornene ring-opening polymers and hydrogenated products thereof had the characteristic of having a large refractive index, but in order to make optical components thinner, those having a higher refractive index have been required. Conventionally, it has been suggested that the introduction of an aromatic ring structure into a polymer structure increases the refractive index (for example, JP-A-61-42602). Therefore, it is conceivable to introduce many aromatic ring structures into the resin structure even in the norbornene-based polymer. However, the monomers that can undergo metathesis copolymerization with norbornene-based monomers are limited. For example, when styrene is used as a comonomer and metathesis-copolymerized with a norbornene-based monomer, it is only introduced at the end of the norbornene-based ring-opening polymer, and since the amount introduced is small, a high refractive index polymer or its hydrogenated product Was not obtained.

As another method, there is known a method of hydrogenating a graft copolymer obtained by ring-opening polymerization of a norbornene-based monomer in the presence of styrene / butadiene rubber or styrene / butadiene / styrene / block copolymer. (For example, Japanese Patent Laid-Open No. 3-54220). However, in this method, the desired modification effect is difficult to obtain due to the low grafting reaction rate during ring-opening polymerization, and the obtained polymer generally has a molecular weight distribution (Mw / M
Since n) is large, there is a problem of poor moldability, and it is not suitable for the purpose of introducing other characteristics into the norbornene-based polymer.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have earnestly studied the method of introducing a different polymer into a norbornene ring-opening polymer, and as a result, have found that the terminal portion of the polymer suitable for the purpose of modification has ethylenic Introducing a saturated bond, by metathesis copolymerizing it with a norbornene-based monomer as a polymer monomer, a block copolymer having a norbornene-based ring-opening polymer block and a heteropolymer block can be efficiently obtained, Further, they have found that the moldability is good, and have completed the present invention.

[0006]

Thus, according to the present invention, ring-opening polymerization of a norbornene-type monomer with a metathesis catalyst in the presence of a polymer monomer having an ethylenically unsaturated bond in at least one terminal portion of the main chain is carried out. And a method for producing a hydrogenated modified norbornene-based resin characterized by hydrogenating the modified norbornene-based resin.

(Heterogeneous Polymer of A Block) In the present invention, first, the heterogeneous polymer which becomes the A block of the block copolymer is polymerized.

The monomer used to obtain the heterogeneous polymer is not particularly limited and includes, for example, ethylene, propylene, 1
Examples include monoolefins such as butene and isobutene; styrenes such as styrene, α-methylstyrene, β-methylstyrene and vinylnaphthalene;
These monomers include alkyl groups, halogens,
It may be substituted with a polar group such as a cyano group or a silyl group. However, since the carboxyl group and the hydroxyl group may interfere with the metathesis ring-opening polymerization reaction described later, it is preferable not to use such a monomer containing no substituent.

Other monomers such as conjugated dienes such as diolefins such as butadiene and isoprene; polar substitutes of diolefins such as chloroprene; and the like may be used in combination within a range that does not impair the object of the present invention. However, when a conjugated diene is used, a vinyl group may be introduced into the side chain, and the vinyl group may be graft-polymerized in the subsequent ring-opening polymerization step to increase the viscosity of the resin and deteriorate the moldability. Therefore, the content of the repeating structural unit having a vinyl group in the A block used in the present invention is preferably 15% by weight or less, more preferably 10% by weight or less, further preferably 5% by weight or less, and particularly preferably 0% by weight. To do.

The method for polymerizing these monomers to obtain a heterogeneous polymer is not particularly limited, and a general method for producing a hydrocarbon-based polymer, for example, a radical polymerization method such as solution polymerization, emulsion polymerization or bulk polymerization; Anionic polymerization method using an alkali metal compound or the like as a catalyst; BF ₃ , AlCl ₃ ,
A cationic polymerization method using TiCl ₄ or the like as a catalyst; Among these, a method in which a vinyl group is easily introduced at a terminal in order to use a different polymer as a polymer monomer is preferable, and specifically, a living anion polymerization method, which is a kind of cationic polymerization method, is preferable.

The solvent used in the living anionic polymerization method is not particularly limited as long as it is a solvent that dissolves a heterogeneous polymer and inhibits the polymerization reaction of the monomer, and a solvent that does not inhibit the metathesis ring-opening polymerization is preferable. Examples of such a solvent include aliphatic hydrocarbons such as hexane, heptane, cyclopentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; methylene dichloride, dichloroethane, dichlorostyrene, tetrachloroethane, and chloro. Halogenated hydrocarbons such as benzene and dichlorobenzene; ethers such as diethyl ether and tetrahydrofuran; and the like. The amount of the solvent used is 100 parts by weight or more, preferably 150 parts by weight or more, more preferably 200 parts by weight or more and 2,000 parts by weight or less, preferably 1,500 parts by weight or less, with respect to 100 parts by weight of the monomer. The range is more preferably 1,000 parts by weight or less.

Examples of the alkyllithium catalyst include monovalent alkyllithium such as n-butyllithium and sec-butyllithium; divalent alkyllithium such as dilithiomethane, 1,4-dilithiobutane and 1,6-dilithiohexane. To be done. Depending on the valence of the alkyllithium catalyst, the number of terminals having the living carbanion of the resulting heterogeneous polymer differs.

When alkyl lithium is used as a catalyst, the amount of catalyst is determined according to the type of alkyl lithium, the monomer, and the weight average molecular weight of the desired heteropolymer. For example, when synthesizing polystyrene having a weight average molecular weight of about 200,000 using n-butyllithium,
Usually, about 5 mmol / kg of monomer is used. When the amount of catalyst is increased, the weight average molecular weight decreases, and when the amount of catalyst is decreased, the weight average molecular weight increases.

In the present invention, the different polymer has a weight average molecular weight of 1,000 or more, preferably 2,000 or more, and particularly preferably 5,000 or more, in terms of polystyrene by gel permeation chromatography.
It is in the range of 10,000 or less, preferably 400,000 or less, more preferably 300,000 or less. If the molecular weight is too small, the impact resistance is low, and if it is too large, the solution viscosity becomes high and it becomes difficult to bond with the B block.
Productivity deteriorates.

(Polymer Monomer) The polymer monomer used in the present invention is one in which an ethylenic unsaturated bond is introduced into at least one terminal portion of the above-mentioned heterogeneous polymer. The introduction method is not particularly limited. For example, if the heterogeneous polymer is radical-polymerized or metathesis-polymerized,
It is also possible to introduce double bonds at the ends by chain transfer. Easy to introduce and easy to control molecular weight,
A method of reacting a heteropolymer polymerized by a living anion polymerization method using an alkyllithium catalyst such as butyllithium with an organic compound having an ethylenically unsaturated bond and a functional group that reacts with a living carbanion present at the terminal is available. preferable.

As the organic compound having a functional group capable of reacting with a living carbanion and a carbon = carbon double bond used in this preferred reaction, allyl chloride, allyl bromide, vinyl chloride, vinyl bromide and 4-chloro-1 are used.
-Butene, 5-bromo-1-pentene, etc.

[Chemical 1] (In the formula, R ^{1 to} R ⁵ are hydrogen or a hydrocarbon group, preferably hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, more preferably hydrogen or a hydrocarbon group having 1 to 2 carbon atoms, particularly preferably hydrogen, X is halogen, n is an integer of 0 or more, preferably 0
Represents an integer of 2 and particularly preferably 1. The organic compound represented by these is illustrated. Usually, the reaction is easily performed by adding these organic compounds to the polymerization reaction liquid.

The amount of the organic compound added is 1.0 times or more the amount of living carbanions, usually the product of the number of moles of the alkyllithium catalyst used and the number of lithium in one molecule of the alkyllithium catalyst (the number of moles). , Preferably 1.1
It is at least twice, more preferably at least 1.2 times and at most 20 times, preferably at most 10 times, more preferably at most 5 times.
If the amount of this organic compound added is too small, the reaction will take time, or the amount of different polymers in which ethylenic unsaturated bonds will not be introduced will increase.If the amount of this organic compound added is too large, it will be wasted and removed. It will be difficult. The ratio of the amount of the high-molecular monomer to be synthesized to the amount of the different polymer used (hereinafter referred to as the ethylenically unsaturated bond introduction rate) is 60% or more, preferably 70% or more, more preferably 75% or more. Before and after the introduction of the ethylenically unsaturated bond, the weight average molecular weight and the solubility in a solvent do not substantially change. Therefore, it is difficult to separate the heterogeneous polymer in which the ethylenically unsaturated bond has not been introduced from the high molecular weight monomer, but the heterogeneous polymer that has not been introduced has almost no effect on the metathesis polymerization. Normal,
In the presence of a mixture of the two, preferably in a reaction system containing a polymer monomer synthesis reaction solution after synthesis,
Metathesis polymerization of a norbornene-based monomer.

The heteropolymer polymerized using polyvalent alkyllithium has terminals corresponding to its valence, and an ethylenically unsaturated bond can be introduced at each terminal.
According to the production method of the present invention, as described below, the type of the resulting block copolymer may be different depending on the number of terminal portions having an ethylenically unsaturated bond of the polymer monomer. , Use high molecular weight monomers according to the purpose.

(B Block) The B block of the block copolymer of the present invention is a block obtained by ring-opening polymerization of a norbornene-based monomer. In the present application, the norbornene-based monomer is subjected to ring-opening polymerization in the presence of the above-mentioned polymer monomer to produce B
Combine blocks.

Norbornene-based monomers are disclosed in JP-A-51-
No. 80400, No. 60-26024, No. 1-168725, No. 1-190726.
Japanese Patent Laid-Open No. 3-14882, Japanese Patent Laid-Open No. 3-12
2137, JP-A-4-63807, JP-A-2-227424, JP-A-2-276842, and the like, and known monomers such as norbornene, its alkyl, alkylidene, and aromatic-substituted derivatives and Halogens of these substituted or unsubstituted olefins,
Polar group substituents such as hydroxyl group, ester group, alkoxy group, cyano group, amide group, imide group and silyl group, for example, 2
-Norbornene, 5-methyl-2-norbornene, 5,
5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-
2-norbornene, 5-cyano-2-norbornene, 5
-Methyl-5-methoxycarbonyl-2-norbornene, 5-hexyl-2-norboernene, 5-octyl-2-norbornene, 5-octadecyl-2-norbornene, etc .; a monomer in which one or more cyclopentadiene is added to norbornene, Derivatives and substitution products similar to the above, for example, 1,4: 5,8-dimethano-1,2,3,
4,4a, 5,8,8a-2,3-cyclopentadienooctahydronaphthalene, 6-methyl-1,4: 5,8
-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-1,2,3,4,4a, 5,5a , 6, 9,
9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene, etc .; a monomer having a polycyclic structure which is polymerized by a Diels-Alder reaction of cyclopentadiene, a derivative or substituent similar to the above, for example, dicyclopentadiene , 2,3-dihydrodicyclopentadiene and the like; Addition products of cyclopentadiene and tetrahydroindene and the like, derivatives and substitution products similar to the above, for example, 1,4-methano-1,4,4a, 4b, 5. 8,
8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a, 5,8,8a-octahydro-2,3-cyclopentadienonaphthalene, and the like.

In the ring-opening polymerization of the norbornene-based monomer, a monomer that can be metathesis copolymerized with the norbornene-based monomer, such as cyclobutene, 1-methylcyclopentene, 3-methylcyclobutene, is used as long as the effect of the present invention is not impaired. , 3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene, cyclooctene, 1-methylcyclooctene,
5-methylcyclooctene, cyclooctatetraene,
Monocyclic cycloolefins such as 1,5-cyclooctazine and cyclododecene; acetylenes and substituted acetylenes such as propyne and 1-butene;
Dienes having double bonds at both ends such as 6-heptadiene; and the like may be used in combination with the norbornene-based monomer. In order not to impair heat resistance, transparency, moldability, and impact resistance, 30 of the repeating structural units constituting the B block is used.
% Or more, preferably 40% or more, more preferably 50%
The above is a repeating structural unit in which the norbornene-based monomer is opened.

These monomers are subjected to ring-opening polymerization using a metathesis polymerization catalyst. The metathesis polymerization catalyst is disclosed in, for example, Japanese Patent No. 41-20111, JP-A-46-14.
910, JP-B-57-17883, JP-B-57-61044, JP-A-54-86600, JP-A-58-127728, and JP-A-1-24.
It is known in Japanese Patent Application No. 0517, etc., and essentially consists of (a) a transition metal compound catalyst component and (b) a metal compound promoter component.

(A) Transition gold used for metathesis polymerization catalyst
The catalyst component of the genus compound is a Deming periodic table IVB, V
B, VIB, VIIB, or VIII transition metal
A compound of these transition metal halides,
Sihalide, alkoxy halide, alkoxy
Decarboxylate, (oxy) acetylacetonate,
Carbonyl complex, acetonitrile complex, hydride complex,
These derivatives, P (C of these or these derivatives
_FiveH₆)_FiveAnd complexing agents such as complexing agents. Concrete
Specifically, TiCl_Four, TiBr_Four, VOBr₃, WBr_Four,
WBr₆, WCl₂ , WCl_Four, WCl_Five, WCl₆, W
F_Four, WI₂, WOCl_Four, MoBr₂, MoBr₃, Mo
Br_Four, MoCl_Four, MoCl_Four, MoF_Four, MoOC
l_Four, WO₂, H₂WO_Four, NaWO_Four, K₂WO_Four, (H
N_Four)₂WO_Four, CaWO_Four, CuWO_Four, MgWO_Four, (C
O)_FiveWC (OC₂H_Five) (CH₃), (CO)_FiveWC (O
C₂H_Five) (C_FourH_Five), Tridecylammonium molybde
Phosphate, tridecyl ammonium tungstate, etc.
Is exemplified. Practically, from the viewpoint of polymerization activity, W, M
Compounds of o, Ti, or V are preferred, especially
Halide, oxyhalide, or alkoxy
Halides are preferred.

The metal compound promoter component (b) used in the metathesis polymerization catalyst is a Deming Periodic Table IA, II.
A compound of group A, IIB, IIIA, or IVA having at least one metal element-carbon bond or metal element-hydrogen bond, such as Al, Sn,
Examples thereof include organic compounds such as Li, Na, Mg, Zn, Cd, and B. Specifically, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, triisobutyl aluminum, triphenyl aluminum, diethyl aluminum monochloride, di-n-propyl aluminum monochloride, diethyl aluminum monobromide, diethyl. Organic aluminum compounds such as aluminum monoiodide, diethyl aluminum monohydride, di-n-propyl aluminum monohydride, diisobutyl aluminum monohydride, methyl aluminum sesquichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride; tetramethyl tin, diethyl dimethyl tin, Organics such as tetraethyltin, dibutyldiethyltin and tetrabutyltin 'S compound;
Organolithium compounds such as n-butyllithium; n-
Organic sodium compounds such as sodium pentyl; Organic magnesium compounds such as methyl magnesium iodide, ethyl magnesium bromide, t-butyl magnesium chloride, allyl magnesium chloride; Organic zinc compounds such as diethyl zinc; Organic cadmium compounds such as diethyl cadmium; Trimethylboron Organic boron compounds such as; and the like.

A metathesis polymerization activity can be enhanced by adding a third component in addition to the components (a) and (b).
Examples of such a third component include aliphatic tertiary amine, aromatic tertiary amine, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, and the like. Examples thereof include nitrogen compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and other Lewis acids. Among them, aliphatic or aromatic tertiary amines are preferable, and specific examples thereof include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, α-picoline and the like. Further, a compound containing an OH group, such as alcohol, functions as an inactivating agent that inhibits the metathesis polymerization activity when added in excess of the stoichiometric amount, so it is necessary to add less than the stoichiometric amount. . The stoichiometric amount here means the product of the number of moles of the component (a) and the oxidation number of the transition metal contained in the component (a), OH per molecule of the chemical compound containing an OH group.
It refers to the number of moles represented by the number divided by the number of groups.

The quantitative relationship of these components is as follows: 1 mol or more, preferably 2 mol or more and 100 mol or less, preferably 50 mol or less of the metal element of component (b), relative to 1 mol of the metal element of component (a), The third component is usually used in an amount of 0.005 mol or more, preferably 0.05 mol or more and 10 mol or less, and preferably 3 mol or less with respect to 1 mol of the component (a). When the amount of the component (b) is too small with respect to the amount of the component (a), sufficient activity cannot be obtained with respect to the amount of the component (a). Becomes higher. If the amount of the third component is too small with respect to the amount of the component (a), the effect of adding the third component is small, and if it is too large, it becomes difficult to remove an excessive amount of the third component or the cost increases.

The metathesis polymerization is usually carried out in an inert organic solvent. The solvent used is not particularly limited. In order to efficiently obtain the block copolymer, as the first step, the polymerization of the heteropolymer constituting the A block is carried out in the above-mentioned preferred solvent, and as the second step, the polymerization reaction after the polymerization of the first step is carried out. An organic compound used for introducing an ethylenically unsaturated bond is added to the solution and reacted to synthesize a polymer monomer, and as a third step, a polymer monomer synthesis reaction solution after the synthesis in the second step is necessary. It is preferable that the concentration is adjusted to an appropriate amount of the polymer monomer, and then the norbornene-based monomer and the metathesis polymerization catalyst are added to the reaction solution.

The norbornene-based monomer is 3 parts by weight or more, preferably 5 parts by weight or more, more preferably 10 parts by weight or more and 50 parts by weight or less, preferably 40 parts by weight or less, more preferably 35 parts by weight with respect to 100 parts by weight of the solvent. In the range of not more than parts by weight, the metathesis polymerization catalyst contains the component (a) in an amount of 0.001 mol or more based on 100 mol of the norbornene-based monomer,
Preferably 0.005 mol or more, more preferably 0.0
The amount added is 1 mol or more and 10 mol or less, preferably 5 mol or less, and more preferably 2 mol or less.

The amount of the polymer monomer used in the ring-opening polymerization should be determined according to the target modified norbornene-based resin in consideration of the molecular weight of the polymer monomer, the polymerization activity, the ring-opening polymerization conditions and the like. is there. In general, the high molecular weight monomer is added to the solid content after ring-opening polymerization (modified norbornene-based resin of the present invention, which is a mixture of various polymers described below) in an amount of 0.
The amount is 001% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more and 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less. When the polymer monomer synthesis reaction solution is used, the monomer content may be set within the above range. If the amount of the polymer monomer is too large, the properties of the modified norbornene resin as the norbornene resin will be impaired, and if it is too small, the properties of the different polymer will not be sufficiently introduced.

(Block Copolymer) When the norbornene-based monomer is subjected to metathesis polymerization in the presence of the above-mentioned polymer monomer, the polymer monomer functions as a chain transfer agent, so that the norbornene ring-opening having the polymer monomer bonded to the terminal is carried out. A polymer, that is, a block copolymer having a heteropolymer block and a norbornene ring-opening polymer block is obtained. When the polymer monomer has an ethylenically unsaturated bond only in one of the terminal parts, an AB type block copolymer is mainly obtained. Also, when the polymer monomer is linear and has an ethylenically unsaturated bond at both terminal portions, an AB type block copolymer is mainly obtained, but BAB type and ABA type copolymers are obtained. Other structures may be used. Further, when the polymer monomer has an ethylenically unsaturated bond in addition to the terminal portion, a block copolymer having a B block in the side chain of the A block is obtained, but the ethylenically unsaturated bond at the terminal portion is obtained. Due to its low reactivity compared to the bonds, it is believed that such block copolymers will not be of substantial concern unless the number of ethylenically unsaturated bonds other than the terminal portion is too high.

To recover the modified norbornene-based resin containing the block copolymer, the solution may be poured into a large amount of a poor solvent to cause precipitation, and the solvent may be removed by filtration. As the poor solvent used, methanol, isopropanol,
Acetone etc. are illustrated. The recovered modified norbornene-based resin is usually a ring-opening polymer of a norbornene-based monomer, a heteropolymer having a vinyl bond only at the terminal which is a polymer monomer, or a terminal copolymer in addition to the block copolymer as described above. It is a mixture of different polymers in which vinyl bonds cannot be introduced.

The modified norbornene-based resin obtained by the production method of the present invention remains as a mixture and has a weight average molecular weight of 10,000 or more, preferably 15, in terms of polystyrene measured by gel permeation chromatography.
000 or more, more preferably 20,000 or more, 50
10,000 or less, preferably 400,000 or less, more preferably 300,000 or less, and a number average molecular weight of 8.0.
00 or more, preferably 10,000 or more, more preferably 15,000 or more and 300,000 or less, preferably 250,000 or less, more preferably 150,000 or less, and the molecular weight distribution is 4.0 or less, preferably 3. 5 or less,
More preferably, it is 3.0 or less. If the molecular weight is too small, the mechanical strength will be insufficient, and if it is too large, the moldability in injection molding will be poor. In addition, if the molecular weight distribution is too large, the moldability will deteriorate.

In the block copolymer, the A block is preferably 1% by weight or more, more preferably 10% by weight or more, particularly preferably 30% by weight or more and 70% by weight or less,
Preferably 65% by weight or less, more preferably 60% by weight
It should be as follows.

To separate the block copolymer, depending on the solubility of the polymer constituting each block in the solvent,
A solvent that is a good solvent for the A block heteropolymer and a poor solvent for the B block ring-opening polymer, and a solvent that is a poor solvent for the A block heteropolymer and a good solvent for the B block ring-opening polymer. By alternately washing, a heteropolymer of block A that does not form a block copolymer (a heterogeneous polymer in which an ethylenically unsaturated bond was not introduced at the end and a high-molecular monomer that has not reacted) and a block copolymer It suffices to remove the ring-opening polymer that does not form a united body. For example, polystyrene having a vinyl bond at the terminal is used as the polymer monomer, and 6-methyl-1,4: 5,8- is used as the norbornene-based monomer.
When a block copolymer is synthesized using dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, it is a good solvent for the ring-opening polymer and a poor solvent for polystyrene. The block copolymer is separated using a combination of n-pentane and methyl acetate, which is a poor solvent for the ring-opening polymer and a good solvent for polystyrene. However, depending on the amount ratio of each block of the block copolymer and the like, it may not be possible to separate them. Usually, the mixture is used as it is as a resin without separation. Either a heteropolymer of A block which does not form a block copolymer or a ring-opening polymer which does not form a block copolymer may be used separately.

(Hydrogenated Resin) The resin produced by the production method of the present invention contains a polymer having an unsaturated bond in its main chain. The presence of unsaturated bonds in the main chain makes the resin easily deteriorated. Therefore, it is preferable to hydrogenate the resin to saturate the unsaturated bond.

Hydrogenation is carried out by contacting the resin with hydrogen in the presence of a hydrogenation catalyst. Usually, hydrogenation is carried out in a solvent, but the solvent used may be that used for the polymerization of the B block. When the solvent of the polymerization reaction solution is used as it is as the solvent for the hydrogenation reaction, it is not always necessary to prepare the hydrogenation reaction solution after the resin is precipitated and solidified, and the hydrogenation catalyst is added to the polymerization reaction solution after the polymerization reaction. Can be used as a hydrogenation reaction solution. In that case, before the addition of the hydrogenation catalyst, a deactivating agent for the polymerization catalyst, for example, alcohols such as methanol, butanol, isopropanol, and OH such as water.
The reaction may be stopped by adding a compound having a group to the polymerization reaction solution. When alcohol is used as the deactivating agent, it is usually 1 mol or more and 3 mol per 1 mol of the alkyl lithium.
Add moles. If it is too small, the polymerization reaction cannot be stopped,
If too much, the efficiency is poor. However, when a homogeneous catalyst described below is used as the hydrogenation catalyst, it may cause a decrease in hydrogenation activity, and it may be more efficient as a step to add the hydrogenation catalyst without adding the deactivator. Yes,
The use of the deactivating agent depends on the efficiency of the process.

The hydrogenation catalyst may be a homogeneous catalyst composed of (c) a transition metal compound and (d) a reducing metal compound, or a heterogeneous catalyst. Homogeneous catalysts are easy to disperse in the hydrogenation reaction solution, so the addition amount may be small, and since they have activity even without applying high temperature and pressure, polymer decomposition and gelation do not occur, low cost and stable quality It has excellent properties. The heterogeneous catalyst becomes highly active when subjected to high temperature and high pressure, can be hydrogenated in a short time, and can be easily removed.

Homogeneous catalysts are disclosed in JP-A-58-43412, JP-A-60-26024 and JP-A 64-2.
It is known in Japanese Patent Laid-Open No. 4826 and Japanese Patent Laid-Open No. 1-138257. Examples of the transition metal compound (c) include groups I or groups IV to VII of the Deming Periodic Table.
Compounds of transition metals belonging to any of the group I, eg C
Specific examples thereof include halides of transition metals such as r, Mo, Fe, Mn, Co, Ni, Pd and Ru, alkoxides, acetylacetonates, sulfanates, carboxylates, naphthenates, trifluoroacetates and stearates. As the compound, chromium (III) acetylacetonate, manganese (III) acetylacetonate, iron (III) acetylacetonate, cobalt (III) acetylacetonate, bis- (triphenylphosphine) -cobalt dichloride, nickel (I
I) Acetylacetonate, bis- (tributylphosphine) -palladium and the like. Further, (d) the reducing metal compound includes Deming's Periodic Table IA and I.
A compound of a Group IA, IIB, IIIA, or IVA metal having at least one metal element-carbon bond or metal element-hydrogen bond, for example, A
1 compounds, Li compounds, Zn compounds, Mg compounds, and the like. Specific examples include trimethylaluminum, triphenylaluminum, diethylaluminum chloride,
Ethyl aluminum sesquichloride, diethyl aluminum hydride, methyl lithium, n-propyl lithium, sec-butyl lithium, p-tolyl lithium, xylyl lithium, diphenyl zinc, bis (cyclopentadienyl) zinc, dimethyl magnesium, methyl magnesium bromide , Lithium aluminum hydride and the like. Specifically, as the combination of the component (c) and the component (d), as the component (c), an organometallic compound of Mn, Fe, Co, or Ni, a halide, an alkoxide, an acetylacetonate, a sulfonate, or a naphthenate, ( d) component Al, Li, Zn, Mg
A catalyst obtained by combining an organic compound such as hydride with a hydride is highly active, and the influence of impurities on reaction inhibition / activity reduction is small, which is preferable.
e, Co, or Ni organometallic compound, halide, alkoxide, or acetylacetonate,
As the component (d), a catalyst obtained by combining alkylaluminum or alkyllithium is particularly highly active,
Moreover, the influence of impurities on reaction inhibition / activity reduction is particularly small, so that it is more preferable. The quantitative relationship of these components depends on the type of each component, but in general, the metallic element 1 of the component (c)
The metal element of the component (d) is 0.5 mol or more, preferably 1 mol or more and 50 mol or less, and preferably 8 mol or less with respect to the mol. If the amount is too large or too small, the activity of the hydrogenation reaction is insufficient. If too much, gelation or side reaction may occur.

Heterogeneous catalysts are also known, and examples thereof include those in which a hydrogenation catalytic metal such as Ni or Pd is supported on a carrier. In particular, when mixing the less preferred of such impurities, as a carrier, it is preferable to use an adsorbent such as alumina or diatomaceous earth, and a pore volume 0.5 cm ³ / g or more, preferably 0.7 cm ³ / It is preferable to use alumina of g or more, preferably 250 cm ² / g or more. When such a carrier is used, transition metal atoms derived from the catalyst used for the polymerization can be adsorbed, and a resin with few impurities can be obtained.

When adding a hydrogenation catalyst to the polymerization reaction liquid of the B block for hydrogenation, the resin concentration may change due to volatilization of the solvent after the polymerization reaction. In that case, it is preferable to adjust the amount of the solvent to the resin solid content in a weight ratio of 1 time or more, preferably 2 times or more and 100 times or less, preferably 20 times or less.

The amount of the hydrogenation catalyst used in the hydrogenation reaction varies depending on the type and combination of each component in the case of a homogeneous catalyst, but usually, the transition metal compound of the component (c) is 0. It is 001 mmol or more, preferably 0.1 mmol or more and 1000 mmol or less, preferably 100 mmol or less. Also in the case of a heterogeneous catalyst, the amount of hydrogenation catalyst used in the hydrogenation reaction is
Although it depends on the type of the catalyst metal and the state of loading on the carrier, the amount of the catalyst metal is usually 0.1 per 100 g of the resin.
It is g or more, preferably 1.0 g or more and 20 g or less, preferably 15 g or less. If the hydrogenation catalyst is excessively added to the hydrogenation reaction solution, it will be costly and post-treatment such as removal of the hydrogenation catalyst will be difficult, and if it is too small, the reaction efficiency will be deteriorated.

The hydrogenation reaction is carried out by introducing hydrogen into the hydrogenation reaction solution, and, for example, a method in which the introduced hydrogen is sufficiently contacted with the resin under stirring is preferable. The hydrogen pressure is usually 0.1 kg / cm ² or more, preferably 2 kg / cm ² or more and 100 kg / cm ² or less, preferably 40 kg / cm ² or less. If the hydrogen pressure is too low, the hydrogenation reaction will not proceed, and if it is too high, it will be difficult to control the reaction, and side reactions or gelation may occur.

The hydrogenation reaction is usually carried out at 0 ° C. or higher and 250
℃ or less, when using a homogeneous catalyst, preferably 20 ℃
As described above, 100 ° C. or lower, when using a heterogeneous catalyst, preferably 200 ° C. or higher, more preferably 210 ° C. or higher,
It is carried out at 240 ° C or lower, more preferably 230 ° C or lower. If the temperature is too low, the reaction rate will be slow, and if it is too high, the resin or hydrogenated resin will be easily decomposed or gelated, and the energy cost will be high.

The hydrogenated resin of the present invention is a resin in which 50% or more, preferably 70% or more, and more preferably 80% or more of the unsaturated bonds in the main chain of each component are saturated.
For example, when a block copolymer having an aromatic ring structure in the side chain is contained, the hydrogenation rate of the aromatic ring structure has a large effect on heat deterioration resistance, light deterioration resistance, weather resistance deterioration, etc. There is no. However, for example, the lower the hydrogenation rate of the aromatic ring structure, the higher the refractive index, the physical properties change. For example, a hydrogenation catalyst comprising a combination of bis (cyclopentadienyl) titanium dichloride as the component (c) and alkyllithium as the component (d) (Japanese Patent Publication No. 63-484).
No. 1), a hydrogenation catalyst in which a dialkyl-bis (cyclopentadienyl) titanium as the component (c) and a reducing magnesium compound as the component (d) are combined (JP-A 61-28507), (c). Unsaturation of the aromatic ring in the resin is achieved by using a hydrogenation catalyst (JP-A-1-275606) in which dialkyl-bis (cyclopentadienyl) titanium as a component and alkoxylithium as the component (d) are combined. It is also possible to hydrogenate only other unsaturated bonds without hydrogenating the bonds, and the hydrogenation rate of the aromatic ring structure may be selected according to the purpose.

The method for recovering the hydrogenated resin from the hydrogenation reaction solution is not particularly limited. As with the recovery of the resin described above, the hydrogenation reaction solution is treated with a large amount of a poor solvent, methanol,
In addition to isopropanol, acetone, etc., a hydrogenated resin may be precipitated and solidified, and the solvent may be removed by filtration. Incidentally, when the norbornene ring-opening polymer or polymer monomer is not removed before hydrogenation, a block copolymer hydrogenated product, a norbornene ring-opened polymer hydrogenated product,
A resin in which a polymer monomer having a saturated vinyl bond at the terminal is mixed is obtained. As before hydrogenation, it may be possible to remove norbornene-based ring-opening polymer hydrogenated products, polymer monomers with saturated vinyl bonds at the terminals, etc., but it may be difficult to remove them. Usually, the mixture as it is is used as a resin.

The hydrogenated resin of the present invention is a gel permeation resin containing the hydrogenated resin of each component of the above-mentioned resin (polymerized but not separated). The polystyrene-equivalent value measured by chromatography has a weight average molecular weight of 10,000 or more, preferably 15,000 or more, more preferably 20,000.
Or more and 500,000 or less, preferably 400,000
Or less, more preferably 300,000 or less, number average molecular weight of 8,000 or more, preferably 10,000 or more, more preferably 15,000 or more, 300,000 or less,
Preferably 250,000 or less, more preferably 15
It has a molecular weight distribution of 50,000 or less, a molecular weight distribution of 4.0 or less, preferably 3.5 or less, and more preferably 3.0 or less.
Further, of these, the content derived from the polymer monomer, which is a combination of the A block of the block copolymer and the polymer monomer as it is, is 0.001% by weight or more, preferably 0.1% by weight or more. , More preferably 1% by weight or more, 5
It is 0% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less.

In the present invention, the type and amount of the polymer monomer are selected according to the desired characteristics. For example, as a polymer monomer, a styrene polymer having a vinyl bond introduced at its terminal (hereinafter referred to as polystyrene monomer)
589 at 25 ° C. of hydrogenated resin (polymerized but not separated into individual components) obtained by using
The refractive index in nm [n _D25 ] is 1.50 or more, preferably 1.52 or more, and more preferably 1.54 or more. By increasing the amount of polystyrene monomer used for metathesis polymerization and selecting a hydrogenation catalyst to allow the aromatic ring structure to remain after hydrogenation, the refractive index of conventionally known norbornene ring-opening polymers and their hydrogenated products Higher than that can also be obtained. The Tg of this resin is 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C.
As described above, the temperature is 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 180 ° C. or lower. Further, the light transmittance using a plate having a thickness of 1.2 mm obtained by press molding the hydrogenated resin is 80% or more, preferably 85% or more, and more preferably at any wavelength in the wavelength range of 400 to 830 nm. Is 90% or more. Further, the hydrogenated resin has little adsorption of chemicals, especially alcohols, amines, esters, amides, ethers, carboxylic acids, amino acids and other compounds having a polar group.

Even when a polymer monomer other than the polystyrene monomer is used, the characteristics of the resin are determined depending on the type. When the amount of polymer monomer is small, the water resistance, moisture resistance, water absorption, hygroscopicity, electrical characteristics of hydrogenated resin,
The heat resistance, light deterioration resistance, weather deterioration resistance, heat deterioration resistance, low elution of impurities, etc. are usually the same as those of norbornene-based ring-opening polymer hydrogenated products, and those of non-hydrogenated polymer compositions Their properties are comparable to those of norbornene ring-opening polymers without hydrogenation.

As with the resin before hydrogenation, only the block copolymer hydrogenated product may be separated from the hydrogenated resin, but it may not be possible depending on the amount ratio of each block. Usually, a mixture of polymers is used as it is. Only the components that can be removed may be removed.

(Molding) The resin of the present invention is formed by a well-known thermoplastic resin molding method such as injection molding, extrusion molding, or the like.
Molding can be performed by a cast molding method, an inflation molding method, a blow molding method, a vacuum molding method, a press molding method, a compression molding method, a rotational molding method, a calender molding method, a rolling molding method, a cutting molding method, or the like.

(Use) The hydrogenated resin obtained by the production method of the present invention has various characteristics depending on the polymer monomer used, and depending on the characteristics, it can be widely used as various molded articles including optical materials. Useful in various fields. For example, optical materials such as optical discs, optical lenses, prisms, light diffusion plates, optical cards, optical fibers, optical mirrors, liquid crystal display element substrates, light guide plates, polarizing films, retardation films; containers for liquids, powders, or solid chemicals. (Liquid medicine container for injection, ampoule, vial, prefilled syringe, infusion bag, sealed medicine bag, press-through,
Sterile containers (female, such as packages, solid drug containers, eye drop containers, etc.), sampling containers (sampling test tubes for blood tests, caps for drug containers, blood collection tubes, sample containers, etc.), medical instruments (syringe, etc.), medical instruments, etc. , Forceps, gauze, contact lenses, etc., experimental / analytical instruments (beakers, petri dishes, flasks, test tubes, centrifuge tubes, etc.), medical optical parts (plastic lenses for medical examinations, etc.), piping materials (medical care) Infusion tube, piping, joint, valve, etc.),
Artificial organs and their parts (tooth beds, artificial hearts, artificial roots, etc.)
Medical equipment such as; processing or transfer containers (tanks,
Tray, carrier, case, etc.), protective material (carrier tape, separation film, etc.), piping (pipe,
Tubes, valves, flow meters, filters, pumps, etc.),
Equipment for processing electronic components such as liquid containers (sampling containers, bottles, ampoule bags, etc.); coating materials (for electric wires, cables, etc.), consumer / industrial electronic device enclosures (copy machines,
Computer, printer, TV, VCR,
Electrical insulating materials such as video cameras), structural members (parabolic antenna structural members, flat antenna structural members, radar dome structural members, etc.); general circuit boards (rigid printed boards, flexible printed boards, multilayer printed wiring boards, etc.), high frequencies Circuit board (circuit board for satellite communication equipment, etc.)
Circuit board such as; substrate of transparent conductive film (liquid crystal substrate, optical memory, surface heating element, etc.); semiconductor encapsulant (transistor encapsulant, IC encapsulant, LSI encapsulant, LED encapsulant, etc.) ), Sealing materials for electric / electronic parts (motor sealing materials, capacitor sealing materials, switch sealing materials, sensor sealing materials, etc.); interior materials for automobiles such as interior mirrors and covers for meters; Exterior materials for automobiles such as door mirrors, fender mirrors, beam lenses, and light covers;

[0052]

EXAMPLES The present invention will be specifically described with reference to the following examples. The number average molecular weight Mn and the weight average molecular weight Mw
Is the polystyrene conversion value by gel permeation chromatography, the introduction rate of the ethylenically unsaturated bond at the end of the different polymer is ¹ H-NMR, the retardation value is the double pass method with a wavelength of 830 nm, and the light transmittance is the absorptivity. It was measured using a meter. Also, the drying is 7
It was carried out by holding at 0 ° C. and about 10 torr for 24 hours.

Reference Example 1 200 parts by weight of cyclohexane, 30 parts by weight of styrene, n
-Butyl ether 0.81 parts by weight and n-butyllithium 0.20 parts by weight were mixed and polymerized at 50 ° C for 1 hour while stirring. Subsequently, 0.48 part by weight of allyl chloride was added, and the mixture was reacted at 50 ° C. for 1 hour with stirring.
The reaction liquid was poured into 0 part by weight of isopropanol to precipitate a polymer, which was collected, filtered and dried to obtain 30 parts by weight of the polymer. The obtained polymer has a weight average molecular weight of about 10,
200, number average molecular weight 9,600, molecular weight distribution Mw /
Mn was 1.06 polystyrene, and about 96% of the polymer monomers used in the present invention had a vinyl bond at the polymer terminal introduced therein.

Example 1 Under a nitrogen atmosphere, 15 parts by weight of the polymer obtained in Reference Example 1 was dissolved in 240 parts by weight of cyclohexane to give 6-methyl-1,
4: 4,8-Dimethano-1,4,4a, 5,6,7,
45 parts by weight of 8,8a-octahydronaphthalene, 0.09 parts by weight of n-tetrabutyltin, and 7 parts by weight of a 0.8 wt% cyclohexane solution of tungsten hexachloride were added to give 6 parts.
The reaction was carried out at 0 ° C. and 1 atm for 1 hour. A part of the obtained polymerization reaction liquid was poured into about twice the weight ratio of isopropanol,
The resin was deposited, collected and dried. Using this resin as it was, the weight average molecular weight was about 47,000, the number average molecular weight was about 19,600, and the molecular weight distribution Mw / Mn was 2.4.
It was 0.

100 parts by weight of this polymerization reaction solution was poured into 200 parts by weight of methyl acetate, a part of the resin was solidified and recovered, and further dissolved in 100 parts by weight of cyclohexane.
The recovery by pouring into 1 part by weight of methyl acetate was repeated 4 times. No polystyrene was found in the cyclohexane / methyl acetate mixed solution after the fourth collection. The recovered resin had a weight average molecular weight of about 49,000, a number average molecular weight of about 21,000, and a molecular weight distribution Mw / Mn of 2.33.

IR analysis was performed after drying a part of the recovered resin. Absorption from styrene 699 cm ^-1 and 6-methyl-1,4: 4,8-dimethano-1,4,4a, 5,6,6
An absorption of 975 cm ^-1 was confirmed indicating the presence of a trans bond derived from 7,8,8a-octahydronaphthalene. Since polystyrene was substantially removed from this resin by washing, polystyrene block (A block) and 6-methyl-1,4: 4,8-dimethano-1,4,4a, 5 were contained in this resin. , 6,7,8,8a-Octahydronaphthalene was found to contain a block copolymer having a ring-opening polymer block (B block). Further, by ¹ H-NMR analysis, the amount of polystyrene remaining, that is, the amount of polystyrene introduced as the A block in the block copolymer was 92% with respect to the amount of styrene used for the reaction of the polymer monomer. Met. The polystyrene block content in the block copolymer molecule estimated from the molecular weight was 38% by weight.

Further, 20 parts by weight of the resin from which polystyrene was substantially removed was dissolved in 80 parts by weight of cyclohexane, and cobalt (III) acetylacetonate 1 was added thereto.
After adding 7 parts by weight of a 15% by weight cyclohexane solution of triethylaluminum to the autoclave, the hydrogen pressure was 10 kgf / cm ² , and the temperature was 8
The reaction was carried out at 0 ° C for 2 hours. The hydrogenation reaction liquid was poured into a large amount of isopropanol to solidify and collect the hydrogenated resin, which was then dried. The obtained hydrogenated product had a weight average molecular weight of about 69,000 and a number average molecular weight of about 28,800.
Molecular weight distribution Mw / Mn 2.40, ¹ H-NMR analysis showed that the hydrogenation rate for the olefin-derived double bond was 9
At 9.9%, the hydrogenation rate for the double bond derived from the aromatic ring was 0%.

The hydrogenated product was heated at 200 ° C. and 300 kgf / c.
Press formed with m ² , thickness 1.2mm, diameter 12.5c
A disk of m was prepared. The light transmittance of this disc is 400-
It was 92% or more in the 830 nm region, the retardation value was 20 nm or less, and the refractive index was 1.54. Also,
The volume resistivity value measured using this disk is 5 × 10 ^16.
Ωcm or more, 10 ² Hz, 10 ⁶ Hz, 10 ⁹ Hz
The dielectric constant and the dielectric loss tangent were 2.40 and 5 × 10 ⁻⁴ , respectively, at all frequencies. From this, it was found that this hydrogenated product had characteristics suitable as an optical material and an electrical insulating material.

Example 2 100 parts by weight of the polymerization reaction solution obtained in Example 1, cobalt (I
II) 1 part by weight of acetylacetonate was charged into an autoclave, followed by 15% by weight of triethylaluminum
After adding 7 parts by weight of cyclohexane solution, the hydrogen pressure was adjusted to 10
The reaction was conducted at kgf / cm ² and a temperature of 80 ° C. for 2 hours. The hydrogenation reaction liquid was poured into a large amount of isopropanol to solidify and collect the hydrogenated resin, which was then dried. The recovered 20 parts by weight of the hydrogenated resin had a weight average molecular weight of about 68,000, a number average molecular weight of about 28,300, a molecular weight distribution of Mw / Mn of 2.40, and a ¹ H-NMR analysis. Hydrogenation rate for heavy bonds is 9
At 9.9%, the hydrogenation rate for the double bond derived from the aromatic ring was 0%. In addition, in this resin, the polystyrene content derived from the polymer monomer was 25% by weight.

This resin hydrogenation product was treated at 200 ° C. and 300 k
Press formed with gf / cm ² , thickness 1.2mm, diameter 1
A 2.5 cm disk was made. The light transmittance of this disk was 92% or more in the region of 400 to 830 nm, the retardation value was 20 nm or less, and the refractive index was 1.54. The volume resistivity measured using this disk is 5 × 10 ¹⁶ Ωcm or more, 10 ² Hz, 10 ⁶ Hz,
The dielectric constant and the dielectric loss tangent were 2.41 and 5 × 10 ⁻⁴ at each frequency of 10 ⁹ Hz. From this, it was found that this hydrogenated product had characteristics suitable as an optical material and an electrical insulating material.

Comparative Example 1 200 parts by weight of cyclohexane, 30 parts by weight of styrene, n
-Butyl ether 0.81 parts by weight and n-butyllithium 0.20 parts by weight were mixed and polymerized for 1 hour at 50 ° C with stirring, and then the reaction solution was poured into 500 parts by weight of isopropanol to precipitate the polymer. The polymer was recovered and dried to obtain 30 parts by weight of polymer.

Ring-opening polymerization was carried out in the same manner as in Example 1 except that this polymer was used instead of the polymer obtained in Reference Example 1,
The obtained resin was deposited and collected.

1 part by weight of this resin was redissolved in 10 parts by weight of cyclohexane and poured into 20 parts by weight of methyl acetate.
Part of the resin was solidified, collected and washed with methyl acetate.
The methyl acetate solution was recovered, methyl acetate was removed by evaporation, the obtained solid content was dried, and IR analysis was conducted. As a result, it was found to be polystyrene. Further, after washing, the resin was further washed with methyl acetate three times, but no polystyrene was found in the last one methyl acetate.

The resin washed repeatedly was coagulated in methyl acetate, a part of the recovered resin was dried, and then IR analysis was performed. Absorption of 699 cm ^-1 derived from styrene was not recognized, and 6
-Methyl-1,4: 4,8-dimethano-1,4,4a,
Absorption of 975 cm ^-1 derived from 5,6,7,8,8a-octahydronaphthalene was observed. From this result, it was confirmed that the copolymer was not contained in this resin.

Reference Example 2 The amount of n-butyl ether was 0.20 parts by weight, the amount of n-butyllithium was 0.05 parts by weight, and the amount of allyl chloride was 0.0.
A polymer was polymerized in the same manner as in Reference Example 1 except that the amount was changed to 6 parts by weight, and a vinyl bond was introduced into the terminal to obtain a reaction liquid. When a part of this was analyzed, 30 parts by weight of polystyrene was obtained, and its weight average molecular weight was about 34,400, number average molecular weight was about 31,600, molecular weight distribution Mw / Mn was 1.09, About 84% of them had a vinyl bond introduced.

Example 3 The same as Example 1 except that instead of the cyclohexane solution of the polymer obtained in Reference Example 1, 100 parts by weight of cyclohexane was added to 190 parts by weight of the reaction solution obtained in Reference Example 2. Ring-opening polymerization was performed. The obtained resin was measured as it was, having a weight average molecular weight of 90,000, a number average molecular weight of 33,
It had a molecular weight distribution of 600 and a molecular weight distribution of 2.68. In addition, Example 1
In the same manner as above, polystyrene block and 6-methyl-1,4: 4,8-dimethano-1,4,4 are included in this resin.
It was confirmed to contain a block copolymer composed of a ring-opening polymer block of a, 5,6,7,8,8a-octahydronaphthalene. The amount of polystyrene introduced as the A block in the block copolymer was 76% with respect to the amount of styrene used for the reaction of the polymer monomer. The polystyrene block content in the block copolymer molecule estimated from the molecular weight was 59% by weight.

This resin was hydrogenated as in Example 1 without removing the polystyrene. This hydrogenated resin has a weight average molecular weight of 103,000, a number average molecular weight of 38,100, a molecular weight distribution Mw / Mn of 2.70, ¹ H
By NMR analysis, the hydrogenation rate for the olefin-derived double bond was 99.9%, and the hydrogenation rate for the aromatic ring-derived double bond was 0%. Also, in this resin,
The polystyrene content derived from the polymer monomer was 36% by weight.

This resin hydrogenated product was treated at 200 ° C. and 300 k
Press formed with gf / cm ² , thickness 1.2mm, diameter 1
A 2.5 cm disk was made. The light transmittance of this disk was 90% or more in the region of 400 to 830 nm, the retardation value was 20 nm or less, and the refractive index was 1.55. The volume resistivity measured using this disk is 5 × 10 ¹⁶ Ωcm or more, 10 ² Hz, 10 ⁶ Hz,
The dielectric constant and the dielectric loss tangent were 2.43 and 5 × 10 ⁻⁴ at each frequency of 10 ⁹ Hz. From this, it was found that this hydrogenated product had characteristics suitable as an optical material and an electrical insulating material.

Reference Example 3 200 parts by weight of cyclohexane, 30 parts by weight of styrene, n
-0.003 parts by weight of butyl ether and 0.015 parts by weight of n-butyllithium were mixed and polymerized at 50 ° C for 1 hour while stirring, and 0.04 parts by weight of allyl chloride was added,
After reacting for 1 hour at 50 ° C. with stirring, the reaction solution was poured into 500 parts by weight of isopropanol to precipitate a polymer, which was recovered and dried to obtain about 30 parts by weight of the polymer.
The weight average molecular weight of the obtained polymer is about 135,000,
Number average molecular weight of about 125,000, molecular weight distribution Mw / Mn
Was 1.08, and the rate of introduction of vinyl bond at the terminal was about 80%.

Example 4 Under a nitrogen atmosphere, 1 part by weight of the polymer obtained in Reference Example 3 was dissolved in 235 parts by weight of cyclohexane to give 6-methyl-1,
4: 4,8-Dimethano-1,4,4a, 5,6,7,
60 parts by weight of 8,8a-octahydronaphthalene, 0.30 parts by weight of 1-hexene, 0.09 of n-tetrabutyltin
By weight, 7 parts by weight of a 0.8 wt% cyclohexane solution of tungsten hexachloride was added, and the reaction was carried out at 60 ° C. and 1 atm for 1 hour. About 2 parts by weight of a part of the obtained polymerization reaction liquid
It was poured into twice the amount of isopropanol to precipitate a polymer, which was recovered and dried. Using this resin as it is, a weight average molecular weight of about 36,500 and a number average molecular weight of about 18,40 were measured.
0, the molecular weight distribution Mw / Mn was 1.98. Also,
In the same manner as in Example 1, the polymer composition contained 6-methyl-1,4: 4,8-dimethano-1,4,4a, 5,6,7,8,8a-octa. It was found that the block copolymer containing the ring-opening polymer block of hydronaphthalene was contained. Also, ¹ H-NM
According to R analysis, the amount of polystyrene remaining, that is, the amount of polystyrene introduced as the A block in the block copolymer was 86% with respect to the amount of styrene used for the reaction of the polymer monomer. The polystyrene block content in the block copolymer estimated from the molecular weight was 40% by weight.

Alumina-supported nickel catalyst was added to 100 parts by weight of the polymerization reaction liquid (0.5 parts by weight of nickel in 1 part by weight of the catalyst,
Nickel oxide 0.2 parts by weight, pore volume 0.8 cm ³ /
g, specific surface area 300 m ² / g) 1 part by weight, and reacted in an autoclave at 210 ° C. and hydrogen pressure 45 kgf / cm ² for 4 hours, and the hydrogenated resin was recovered as in Example 1.

The hydrogenated resin has a weight average molecular weight of 4
1,200, number average molecular weight 20,100, molecular weight distribution M
According to w / Mn 2.05, ¹ H-NMR analysis, the hydrogenation ratio to the olefin-derived double bond was 99.9%,
The hydrogenation rate based on the double bond derived from the aromatic ring was 32%.

An antiaging agent (Irganox 1010, manufactured by Ciba Geigy) was added to 17 parts by weight of the hydrogenated resin.
A twin screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd., screw diameter 37 mm, L / D = 3) was added in an amount of 0.008 part by weight.
2, screw rotation speed 250 rpm, resin temperature 235
It was extruded at a feed rate of 10 kg / hour) to obtain pellets.

Using this pellet, a mold clamping pressure of 350
t, resin temperature 240 ° C., mold temperature 70 ° C., injection molding,
Diameter 200mm, height 130mm, average thickness 2.0mm
Cylindrical container with one bottom and 100 mm ×
A test piece of 50 mm × 2.0 mm was prepared.

When the total light transmittance of the test piece was measured,
At 400 to 830 nm, the transparency was good at 90.1% or more. The turbidity was measured and found to be 0.1%.

300 ml of LB medium (1% by weight of bactotryptone, 0.5% by weight of yeast extract, 1% by weight of NaCl, 0.1% by weight of glucose was adjusted to pH 7.5) in a molded cylindrical container. Put 6g of agar,
It was capped with aluminum foil, sterilized with steam at 121 ° C. for 30 minutes to gel the medium, and cooled at room temperature to solidify. After incubation at 37 ° C. for 3 days, no fungal growth was observed. The appearance after the treatment was good, and no white turbidity, cracking, or deformation was visually confirmed.

Further, the test piece was immersed in an aqueous sodium carbonate solution having a pH of 9, a hydrochloric acid having a pH of 48 hours, and ethanol, and then the appearance was observed, but no change was observed, and neither turbidity nor total light transmittance was changed. Furthermore, the test piece is concentrated sulfuric acid, 30%
Dilute sulfuric acid, 70% nitric acid, phosphoric acid, hydrofluoric nitric acid (hydrofluoric acid 7% by weight, nitric acid 42% by weight, water 51% by weight), 37% hydrochloric acid, 3
0% hydrogen peroxide solution, saturated potassium hydroxide solution, 29%
Ammonia water, acetone, isopropyl alcohol, trichloroethylene, 2.38 wt% TMAHO aqueous solution,
It was immersed for 5 minutes in an aluminum etching solution (80% by weight concentrated phosphoric acid, 5% by weight nitric acid, 5% by weight glacial acetic acid, 10% by weight water). The test piece was dissolved in trichlorethylene and the surface was carbonized with concentrated sulfuric acid, but it was shown that it had good chemical resistance without being affected by other chemicals.

Further, the test piece was cut into 10 mm width, and 20
After sonicating 20 g in distilled water for 20 minutes, it was dried at 40 ° C. for 10 hours. The test piece for 20 g was put in a hard glass flask, and 200 g of distilled water was added. A lid made of hard glass was placed and the mixture was allowed to stand at 50 ° C. for 24 hours to collect distilled water.

As a control, 200 g of distilled water was placed in a hard glass flask, and a hard glass lid was placed on the hard glass flask at 50 ° C.
It was allowed to stand at room temperature for 24 hours and then distilled.

The amount of elution from the test piece was determined from the difference in the analysis results by the atomic absorption method of these two kinds of distilled water, the ion chromatography, and the combustion-nondispersion infrared gas analysis method. As a result, the atomic weight of tungsten was 0.01 ppm. (Detection limit)
The atomic weight of nickel is 0.01 ppm (detection limit) or less, and the atomic weight of aluminum is 0.01 ppm (detection limit).
Hereinafter, the total amount of organic carbon was 2 ppm (detection limit) or less.

A 10 wt% cyclohexane solution of this polymer hydrogenated product was analyzed by atomic absorption spectrometry, and as a result, the atomic weight of tungsten in the polymer hydrogenated product was 0.01 ppm.
Below the detection limit, the atomic weight of nickel is also 0.01 ppm
Below the detection limit, the atomic weight of aluminum is 0.01 pp
It was less than m (detection limit). This polymer hydrogenated product 1
As a result of burning 00 mg in a Dorman combustion device, absorbing in 5 ml of pure water, and analyzing by ion chromatography,
The chlorine atom amount was 0.02 ppm (detection limit) or less.

The above-mentioned test pieces were subjected to a gift test according to the 12th revision of the Japanese Pharmacopoeia “Plastic Test Method for Infusion”.
Effervescence disappeared within 3 minutes, pH difference was -0.03, UV absorption was 0.007, potassium permanganate reducing substance 0.10 ml, and this hydrogenated product has the characteristics suitable for medical use. are doing.

Comparative Example 2 500 parts by weight of cyclohexane, 30 parts by weight of styrene,
70 parts by weight of 1,3-butadiene, 0.90 parts by weight of tetrahydrofuran, and 0.030 parts by weight of n-butyllithium are mixed and polymerized at 50 ° C. for 1 hour while stirring,
Pour the reaction solution into 1000 parts by weight of isopropanol,
The polymer was precipitated, recovered and dried to obtain about 30 parts by weight of the polymer. The polymer obtained has a weight average molecular weight of about 20.
It was a styrene / butadiene / random copolymer having a molecular weight distribution of 2,000, a number average molecular weight of about 178,500, a molecular weight distribution Mw / Mn of 1.12 and a 1,2-vinyl bond content of butadiene units of 50%.

Instead of using the solution prepared by dissolving 15 parts by weight of polystyrene obtained in Reference Example 1 in 240 parts by weight of cyclohexane, a solution prepared by dissolving 5 parts by weight of this styrene-butadiene-random copolymer in 250 parts by weight of cyclohexane was used. Was subjected to ring-opening polymerization in the same manner as in Example 1. The obtained resin had a weight average molecular weight of about 247,350, a number average molecular weight of about 29,100, and a molecular weight distribution Mw / Mn of 8.5.

Alumina-supported nickel catalyst was added to 100 parts by weight of the polymerization reaction liquid (0.5 parts by weight of nickel in 1 part by weight of the catalyst,
Nickel oxide 0.2 parts by weight, pore volume 0.8 cm ³ /
g, specific surface area 300 m ² / g) 1 part by weight, and reacted at 210 ° C. and hydrogen pressure 45 kgf / cm ² for 4 hours in an autoclave. Recovery of the hydrogenated resin was carried out as in Example 1.

The weight average molecular weight of the hydrogenated resin is 2
91,000, the number average molecular weight is 37,300, the molecular weight distribution Mw / Mn is 7.8, and the ¹ H-NMR analysis shows that the hydrogenation rate for the olefin-derived double bond is 97.5%.
And the hydrogenation rate for double bonds derived from aromatic rings is 14%
Met.

The hydrogenated resin was heated to a resin temperature of 200
A plate having a size of 20 mm × 15 mm and a thickness of 3.0 mm was formed by hot pressing under the conditions of 300 ° C., 300 kgf / cm ² , and 3 minutes. This board was cloudy.

Comparative Example 3 Under a nitrogen atmosphere, 6-methyl-1,4: 4,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene 45 parts by weight, 1-hexene 0.022 parts by weight, 0.09 parts by weight of n-tetrabutyltin, and 7 parts by weight of a 0.8 wt% cyclohexane solution of tungsten hexachloride were added, and the mixture was reacted at 60 ° C. and 1 atm for 1 hour. The obtained polymer solution was poured into about twice the weight ratio of isopropanol to precipitate the polymer, which was recovered and dried to obtain a polymer.
This polymer had a weight average molecular weight of about 33,600, a number average molecular weight of about 14,300, and a molecular weight distribution Mw / Mn of 2.35.

IR analysis revealed that 6-methyl-
1,4: 4,8-dimethano-1,4,4a, 5,6
975c derived from 7,8,8a-octahydronaphthalene
The absorption of m ⁻¹ was confirmed, and the polymer was found to be 6-methyl-1,
4: 4,8-Dimethano-1,4,4a, 5,6,7,
It was confirmed to be a ring-opening polymer of 8,8a-octahydronaphthalene.

Further, 100 parts by weight of the polymerization reaction solution and 1 part by weight of cobalt (III) acetylacetonate were charged into the autoclave, and then 15 parts of triethylaluminum was added.
After adding 7 parts by weight of a wt% cyclohexane solution, the mixture was reacted at a hydrogen pressure of 10 kgf / cm ² and a temperature of 80 ° C. for 2 hours. The hydrogenation reaction solution was poured into a large amount of isopropanol to solidify and collect the polymer hydrogenated product, which was then dried. This hydrogenated product has a weight average molecular weight of about 42,000, a number average molecular weight of about 17,500, a molecular weight distribution Mw / Mn of 2.4, and a ¹ H-NMR analysis shows that the hydrogenation rate for the double bond derived from the olefin is high. Was 99.9%.

45 parts by weight of this polymer hydrogenated product and 25 parts by weight of the polystyrene obtained in Reference Example 1 were mixed in a Labo Plastomill heated to 220 ° C.

This mixture was heated at a resin temperature of 200 ° C. and 300 k
gf / cm ² , 20m by hot pressing under the condition of 3 minutes
A plate having m × 15 mm and a thickness of 3.0 mm was formed. This board was cloudy.

[0093]

INDUSTRIAL APPLICABILITY According to the present invention, a resin, which is a mixture containing a block copolymer composed of a hydrocarbon polymer block and a norbornene ring-opening polymer block as one component, can be easily obtained, and the thermoplastic resin A resin having the characteristics of the norbornene-based resin and the characteristics of the polymer forming the hydrocarbon polymer block is obtained.

Claims (2)

[Claims] 1. Production of a modified norbornene-based resin characterized by ring-opening polymerization of a norbornene-based monomer by a metathesis catalyst in the presence of a polymer monomer having an ethylenically unsaturated bond at least at one end of its main chain. Method. 2. A method for producing a hydrogenated modified norbornene-based resin, which comprises hydrogenating the modified norbornene-based resin according to claim 1.