JPH07103223B2 - Ring-opening copolymer hydrogenated product and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel ring-opening copolymer hydrogenated product having excellent heat resistance, optical properties, and moldability, and more specifically, a polycyclic norbornene-based ring-opening copolymer The present invention relates to a polymer hydrogenated product and a method for producing the same.

Conventional technology Conventionally, polymethylmethacrylate, polycarbonate, etc. have been used as optical polymer materials, but the former has problems such as water absorption and the latter has problems such as birefringence during injection molding. It is becoming difficult to meet the increasing demands.

In recent years, a polymer using a polycyclic norbornene-based monomer has been developed as a polymer material that has improved these drawbacks. For example, JP-A-60-26024 discloses that a hydride of a ring-opening polymer of tetracyclododecenes or a ring-opening copolymer of tetracyclododecenes and norbornenes has high transparency, water resistance and heat resistance. It is described as being excellent.

However, the hydrides of ring-opening polymers of tetracyclododecenes do not necessarily have good moldability, and it is hard to say that the birefringence value is so small that the required performance is sufficiently satisfied. Further, hydrides of ring-opening copolymers of tetracyclododecenes and norbornenes also have the same problem. When the copolymerization ratio of norbornenes becomes as high as 40 to 50 mol%, the above problems are somewhat Although improved, the glass transition temperature (Tg) is as low as 90-100 ° C, and the heat resistance is not always sufficient.

Further, JP-B-58-43412 discloses that a hydride of a dicyclopentadiene ring-opening polymer can be easily subjected to hot melt molding to give a transparent and strong sheet, This hydride has a drawback that its glass transition temperature (Tg) is as low as about 95 ° C. and its heat resistance is insufficient for use as an optical disc.

On the other hand, even a polymer or copolymer using a polycyclic norbornene-based monomer, which is not hydrogenated, is inferior in resistance to oxidative deterioration and is unsuitable as an optical material.

Problem to be Solved by the Invention An object of the present invention is to provide a novel polymer material excellent in heat resistance, optical characteristics and moldability.

A further object of the present invention is to obtain a hydrogenated product of a polycyclic norbornene ring-opening copolymer which gives a molded product having a high glass transition temperature and a small optical strain.

The present inventors have conducted extensive studies to develop a novel synthetic resin suitable as an optical polymer or a raw material thereof using a polycyclic norbornene-based monomer, and as a result, tetracyclododecenes, norbornenes and dicyclopentadienes have been obtained. The hydrogenated product of the ring-opening copolymer obtained by ring-opening the above three is a polymer having excellent thermal properties and being less likely to cause optical distortion in the molded product, and having good moldability as well. Find out,
The present invention has been completed based on the findings.

Means for Solving the Problems The gist of the present invention is (1) (A) a repeating unit represented by the following general formula [I] or an alkyl-substituted compound thereof in an amount of 90 to 10 mol%, and (B) the following general formula [ II], 5 to 50 mol% of at least one repeating unit selected from alkyl-substituted or alkylidene-substituted, and (C) a repeating unit represented by the following general formula [III] or an alkyl-substituted thereof. 5 to 80 mol%, and the intrinsic viscosity [η] measured in toluene at 25 ° C is 0.
01 to 20 dl / g and constitutes the main chain A polycyclic norbornene ring-opening copolymer hydrogenated product in which at least 50% of which are single bonds, and (However, in the formula Represents a single bond or a double bond. (2) (A) 90 to 10 mol% of a repeating unit represented by the following general formula [I '] or an alkyl-substituted product thereof, and (B) a repeating unit represented by the following general formula [II'], an alkyl substitution thereof. A repeating unit represented by the following general formula [III '] or an alkyl-substituted product thereof in an amount of 5 to 80 mol%, and Moreover, the intrinsic viscosity [η] measured at 25 ° C in toluene is 0.
A main chain characterized by hydrogenating some or all of the olefinic unsaturated groups contained in the polycyclic norbornene ring-opening copolymer of 01 to 20 dl / g with hydrogen using a hydrogenation catalyst. Constitute Of the polycyclic norbornene ring-opening copolymer hydrogenated product having at least 50% of single bonds.

(However, in the formula Represents a single bond or a double bond. ) The ring-opening polymer used in the present invention is a monomer (A)
Tetracyclododecenes, that is, tetracyclododecene and its alkyl-substituted compounds (hereinafter sometimes referred to as “component A”) and (B) unsubstituted or substituted norbornene (hereinafter sometimes referred to as “component B”, And (C) dicyclopentadiene, that is, dicyclopentadiene and its alkyl-substituted product, and / or dihydrodicyclopentadiene, that is, 2,3-dihydrodicyclopentadiene and its alkyl-substituted product (hereinafter referred to as “C component”). , Which can be produced by a known ring-opening polymerization method for cyclic olefins, and hydrogenated products of these ring-opening copolymers can be prepared by a conventional hydrogenation reaction method. Can be used for manufacturing.

Hereinafter, each component of the present invention will be described in detail. (Monomer) The component A used in the present invention is tetracyclododecene represented by the following general formula [IV] (hereinafter sometimes abbreviated as “TCD”) and its alkyl-substituted product.

These TCDs can be obtained by subjecting cyclopentadiene and norbornenes to a Diels-Alder reaction and separating them from the reaction mixture by a technique such as distillation.

The TCDs may be a lower alkyl-substituted TCD such as methyl, ethyl, or propyl, and may have a plurality of alkyl substituents.

The component B used in the present invention is an unsubstituted or substituted norbornene (hereinafter sometimes abbreviated as “NB”). As substituted norbornene, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl-
There are alkyl-substituted norbornenes such as 2-norbornene, 5-butyl-2-norbornene, or alkylidene-substituted norbornenes such as ethylidene norbornene.

The C component used in the present invention includes dicyclopentadiene (hereinafter sometimes abbreviated as "DCP"), 2,3-dihydrodicyclopentadiene ("4,7-methano-2,3,3a, 4,7"). , 7a−
“Hexahydroindene”, hereinafter sometimes abbreviated as “HDCP”), and alkyl substitution products thereof such as methyl, ethyl, propyl and butyl.

Each of these monomer components may be used alone or in an appropriate mixture.

In the present invention, the component A is 90 to 10 mol%, preferably 80 to 20 mol%, and the component B is 5 to 50 mol%, preferably
10-40 mol%, and C component 5-80 mol%, preferably
It is used in a proportion of 10 to 70 mol%. The glass transition temperature rises as the use ratio of the component A rises, but if the glass transition temperature becomes too high, it becomes difficult to process and the birefringence value, which is important in optical characteristics, increases.

The optical characteristics are improved as the proportion of the B component used is increased, but the glass transition temperature is lowered if the proportion is too large.

By using the C component in the above-mentioned specific ratio, a molded product with less optical distortion is obtained even in a higher glass transition temperature region as compared with the hydride of the ring-opening copolymer composed of the A component and the B component. be able to. If the amount of C component is too large, the glass transition temperature will not be sufficiently high, and the effect of improving the birefringence value will be poor.

In the present invention, in addition to the components A, B and C, other cycloolefins capable of ring-opening polymerization can be used within a range that does not substantially impair the effects of the present invention. Specific examples of the cycloolefin that can be used include compounds having one reactive double bond such as cyclopentene, cyclooctene, and 5,6-dihydrodicyclopentadiene.

Further, among polycyclic norbornene-based monomers, there are compounds having two or more reactive double bonds, but in the case of such a compound, gelation of the polymer is likely to occur,
It is preferable to remove as much as possible.

The monomer mixture used in the present invention is the component A prepared in advance,
Although it can be prepared by mixing the B component and the C component, direct synthesis is carried out by heat treatment of DCPs and norbornenes, or heat treatment of DCPs and norbornenes in the presence of cyclopentene. You can also

The conditions for the heat treatment include DCPs and norbornenes under an atmosphere of an inert gas such as nitrogen gas at a temperature of 120 to 250 ° C, preferably 150 to 230 ° C for 0.5 to 20 hours, preferably 1
Examples of the method include heating for 10 hours. The reaction form of the treatment may be either batch type or continuous type, and an inert solvent may be present in the reaction system.

Further, in the polymerization, in addition to the components A, B, and C, butene-1, pentene-1, hexene-1, octene-1, butene-2, pentene-2, 1,4-hexadiene and the like The mono-olefin and chain-like non-conjugated diolefins may be added in the range of up to about 10 mol% in order to control the molecular weight.

(Polymerization catalyst) A ring-opening copolymer of these monomers is produced by a usual method for polymerizing norbornenes, and examples of the polymerization catalyst include ruthenium, rhodium, palladium, osmium, iridium and platinum. Examples include platinum group metal compounds (for example, Japanese Examined Patent Publication No. 46-14910) or transition metal compounds such as titanium, vanadium, molybdenum, and tungsten and a system of an organometallic compound of Group I-IV of the periodic table. A third component such as a tertiary amine may be combined with the catalyst system (for example, JP-B-41-20111 and JP-B-57-1).
7883, Japanese Examined Patent Publication 57-61044, JP-A-54-86600, JP-A-SHO
58-127728 publication).

The polymerization catalyst is not particularly limited as long as it is a metal compound capable of ring-opening polymerization of these monomers, but is preferably a catalyst system containing a transition metal compound such as titanium tetrahalide and an organometal such as an organoaluminum compound. Alternatively, it is a catalyst system in which a third component such as an aliphatic or aromatic tertiary amine is combined.

Below, the specific example of a polymerization catalyst is given.

Transition metal compound As the metal compound, transition metal compounds such as titanium, vanadium, tungsten and molybdenum are preferable, and specifically, there are halides, oxyhalides, oxides, carbonyl compounds, organic ammonium salts and the like of these transition metals. .

Specific examples include TiCl ₄ , TiBr ₄ , VOCl ₃ , VOBr ₃ , WBr ₂ , WBr ₄ , WBr ₆ , WC
l ₂ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₄ , WI ₂ , WI ₄ , WOBr ₄ , WOC
l ₄ , WOF ₄ , MoBr ₂ , MoBr ₃ , MoBr ₄ , MoCl ₄ , MoCl ₅ , Mo
F ₄ , MoOCl ₄ , MoOF ₄ , WO ₂ , H ₂ WO ₄ , NaWO ₄ , K ₂ WO ₄ , (NH ₄ ).
₂ WO ₄ , CaWO ₄ , CuWO ₄ , MgWO ₄ , (CO) ₅ WC (OCH ₃ ) (CH ₃ ), (C
O) ₅ WC (OC ₂ H ₅ ) (CH ₃ ), (CO) ₅ WC (OC ₂ H ₅ ) (C ₄ H ₅ ), (CO) ₅ MoC
(OC ₂ H ₅ ) (CH ₃ ), (CO) ₅ Mo = C (OC ₂ H ₅ ) (N (C ₂ H ₅ ) ₂ ), tridecyl ammonium molybdate, tridecyl ammonium tungstate, etc. is there.

Examples of the organometallic compound include organometallic compounds of groups I to IV of the periodic table, for example, organoaluminum compounds, organotin compounds or lithium, sodium,
There are compounds such as magnesium, zinc, cadmium and boron.

Examples of the organic aluminum compound include trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, triphenyl aluminum, tribenzyl aluminum, diethyl aluminum monochloride, di- n-pyropyr aluminum monochloride,
Di-isobutyl aluminum monochloride, di-n-butyl aluminum monochloride, diethyl aluminum monobromide, diethyl aluminum monoiodide, diethyl aluminum monohydride, di-n-propyl aluminum monohydride, diisobutyl aluminum monohydride, methyl aluminum sesquichloride , Ethyl aluminum sesquibromide, isobutyl aluminum sesquichloride, ethyl aluminum dichloride, ethyl aluminum dibromide, propyl aluminum dichloride, isobutyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum diiodide and the like.

As the organic tin compound, tetramethyltin, diethyldimethyltin, tetraethyltin, dibutyldiethyltin, tetrabutyltin, tetraisocumyltin, tetraphenyltin, triethyltin fluoride, triethyltin chloride, triethyltin bromide, triethyltin iodide. , Diethyltin difluoride, diethyltin dichloride, diethyltin bromide, diethyltin diiodide, ethyltin trifluoride, ethyltin trichloride, ethyltin tribromide, ethyltin triiodide and the like. Other n-butyllithium, n
-Pentyl sodium, methyl magnesium iodide,
Ethylmagnesium bromide, methylmagnesium bromide, n-propylmagnesium chloride, t-butylmagnesium chloride, allylmagnesium chloride,
Examples include diethyl zinc, diethyl cadmium, trimethyl boron, triethyl boron, tri-n-butyl-boron and the like.

Third Component A third component can be added to the above catalyst system to enhance the polymerization activity and improve the selectivity of ring-opening polymerization. As specific examples, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone,
Examples thereof include nitrogen-containing 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.

(Solvent) Although the ring-opening copolymer used in the present invention can be polymerized without using a solvent, it can be polymerized in an inert organic solvent.

Specific examples include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as n-pentane, hexane and heptane, aliphatic hydrocarbons such as cyclohexane, methylene dichloride, dichloroethane, dichloroethylene and tetrachloroethane. , Halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene, and the like, and two or more kinds of these may be mixed and used.

(Polymerization temperature) The temperature condition of the ring-opening copolymerization is not particularly limited,
It is usual to select any temperature from -20 ° C to 100 ° C.

(Polymerization pressure) Generally, it is preferable to select the polymerization pressure condition from the range of 0 to 50 kg / cm ² .

(Hydrogenation) The hydrogenated product of the ring-opening copolymer of the present invention is prepared by hydrogenating the above-mentioned ring-opening copolymer to obtain its olefinic unsaturated group (double bond of main chain and double bond of unsaturated ring). It can be obtained by saturating a part or all of the polymer, and thereby, the heat deterioration resistance and the light deterioration resistance of the polymer can be further improved. The hydrogenation rate is theoretically in the range of 0 to 100% when 100% is assumed when all the double bonds of the ring-opening polymer are saturated by hydrogenation, and in practice, it is optional within that range. However, in order to improve the heat deterioration resistance and the light deterioration resistance, it is necessary that 50% or more of the main chain double bonds be hydrogenated.

The hydrogenation reaction of this ring-opening copolymer is carried out by a usual method. The hydrogenation catalyst can be used as long as it is generally used for hydrogenating an olefin compound, and is not particularly limited, but examples thereof include the following. As the heterogeneous catalyst, nickel, palladium, platinum or a solid catalyst in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina or titanium oxide, for example, nickel / silica, nickel / diatomaceous earth, palladium / Examples thereof include carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like. Further, as the homogeneous catalyst, a catalyst based on a metal of Group VIII of the periodic table, for example, nickel naphthenate /
Ni, Co compounds such as triethylaluminum, cobalt octenoate / n-butyllithium, nickel acetylacetonate / triethylaluminum and periodic table I to III
Examples include organic metal compounds of group metals, Rh compounds, and the like.

The hydrogenation reaction is a homogeneous system or a heterogeneous system, depending on the type of catalyst, under a hydrogen pressure of 1 to 150 atm, 0 to 180 ° C., preferably
It is carried out at 20-100 ° C. The hydrogenation rate can be arbitrarily adjusted by changing the hydrogen pressure, the reaction temperature, the reaction time, the catalyst concentration and the like, but in order for the hydrogenated product to exhibit excellent heat deterioration resistance and light deterioration resistance, It is necessary that 50% or more of the main chain double bonds in the
The hydrogenation rate is 80% or more, more preferably 90% or more.

(Ring-opening copolymer hydrogenated product) The ring-opening copolymer used in the present invention has an intrinsic viscosity [η] measured in toluene at 25 ° C of 0.01 to 20 dl / g, preferably 0.
1 to 10 dl / g, but the [η] of the hydrogenated product of the ring-opening copolymer of the present invention is also 0.01 to 20 dl / g, preferably 0.1
It is ~ 10dl / g. When [η] is in the above range, heat resistance, water resistance, transparency, chemical resistance, solvent resistance, processability and mechanical properties are good.

A hydrogenated product of a ring-opening polymer having TCDs alone or a copolymerization ratio of TCDs extremely large has a high glass transition temperature and excellent heat resistance, but on the other hand, it has a problem that it is difficult to process. Further, the hydrogenation product of the ring-opening copolymer of TCDs and NBs is
The birefringence value is large, and optical distortion is likely to occur in the molded product. On the other hand, the hydrogenated product of the ring-opening copolymer of the present invention is
Component (TCDs), B component (NBs) and C component (DCP)
, HDCPs) in a specific ratio, the glass transition temperature of the polymer can be appropriately controlled to balance heat resistance and processability. Specifically, the hydrogenated product of the present invention has a glass transition temperature (Tg) of about 100 ° C to about 135 ° C.
Can be appropriately controlled within the range, and as a result, the moldability is also good.

Further, as is clear from the birefringence value, a molded product with little optical distortion can be obtained even in a region where Tg is high.

Furthermore, it is highly balanced in light transmittance, water resistance, chemical resistance, solvent resistance, mechanical strength, etc., and is particularly suitable as an optical material.

Further, the hydrogenated product of the ring-opening polymer of the present invention has further improved heat deterioration resistance and light deterioration resistance as compared with the ring-opening copolymer used.

(Molding) The hydrogenated ring-opening copolymer of the present invention can be molded by a well-known method. Further, in the molding process, various additives, for example, inorganic and organic fillers,
Stabilizers, antistatic agents, lubricants and the like may be added.

(Use) The hydrogenated product of the ring-opening copolymer of the present invention has a high glass transition temperature and is excellent in heat deterioration resistance and light resistance deterioration as is apparent from the fact that the unsaturated group is hydrogenated. ,
In addition, since it is a polymer having excellent optical properties and well-balanced transparency, water resistance, chemical resistance, mechanical properties, etc., it is useful in various fields as various molded products.

For example, optical fields such as optical lenses, optical disks, optical fibers, glass window applications, water tanks for electric irons,
Microwave oven products, liquid crystal display substrates, printed circuit boards, high frequency circuit boards, electrical fields such as transparent conductive sheets and films, medical devices such as syringes, pipettes and animal gauges,
It can be used in various fields such as chemical fields, camera bodies, various instrument housings, films, sheets and helmets.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Parts are based on weight unless otherwise specified.

Example 1 A fully dried and nitrogen-substituted reactor was charged with 55 parts of tetracyclododecene (TCD), 10 parts of norbornene (NB) and 35 parts of dicyclopentadiene (DCP) (total of 100 parts), and the total of monomers. 1 mol% of 1-hexene and 300 parts of toluene were charged. Then, 16 parts of a 1 molar solution of triethylaluminum in toluene, 4 parts of triethylamine and 3 parts of a 1 molar solution of titanium tetrachloride in toluene were added and reacted at 25 ° C. for 2 hours.

Acetone / isopropyl alcohol (1/1)
Pour in to solidify the polymer, filter and dry the precipitate,
72 parts of a ring-opening copolymer (polymer) was obtained.

The composition ratio (mol%) of the units derived from each component of TCD, NB and DCPD in the obtained polymer was analyzed based on the result of analysis by proton NMR spectrum and the analysis of the amount of residual monomer after polymerization by gas chromatography. When calculated, the TCD component was 49 mol%, the NB component was 13 mol%, and the DCP component was 38 mol%.

50 parts of the above polymer was dissolved in 500 parts of cyclohexane, and 5 parts of palladium-carbon catalyst was used, and the hydrogen pressure was 60 kg / c.
Hydrogenation reaction was carried out at m ₂ and temperature of 140 ° C. for 4 hours. The resulting polymer solution was filtered to remove the catalyst, then poured into acetone / isopropyl alcohol (1/1) to coagulate, and the precipitate was filtered and dried to obtain 46 parts of a hydrogenated polymer.

As a result of proton NMR spectrum analysis of this hydrogenated polymer, it was confirmed that the absorption of protons due to the double bond disappeared and hydrogenation was almost complete (hydrogenation rate 100%).

The intrinsic viscosity of this hydrogenated polymer was 0.61 dl / g when measured in toluene at 25 ° C. The glass transition temperature measured by DSC analysis was 120 ° C.

This hydrogenated polymer was injection molded at 350 ° C. and an injection pressure of 2,000 Kg / cm ² to prepare an optical disk plate having a diameter of 13 cm and a thickness of 1.2 mm.
Light transmittance (measured at 830 nm), birefringence value (double pass, 633
(measured in nm) and water absorption (weight change rate after immersion at 25 ° C. for 24 hours) were measured. As a result, the light transmittance was 91%, the birefringence value (from the inner peripheral portion to the outer peripheral portion of the optical disc plate) was 10 to 40 nm, and the water absorption was 0.1% or less.

Regarding the solvent resistance, the above optical disc plates were immersed in ethyl acetate and acetone at room temperature for 20 hours, and the change in appearance was observed.
Regarding chemical resistance, changes in appearance were observed by immersing in 97.6% sulfuric acid and 28% ammonia water for 20 hours at room temperature. as a result,
No change in appearance was observed in either case.

From the above results, the ring-opening copolymer hydrogenated product of the present invention,
It can be seen that, in addition to being excellent in heat resistance and optical characteristics, various physical properties such as water resistance and solvent resistance are good.

Examples 2 to 5 Ring-opening copolymerization, hydrogenation and injection molding were carried out in the same manner as in Example 1 except that the composition ratio of the monomers was changed to the composition ratio shown in Table 1.

Table 1 shows the physical properties of the obtained polymer and optical disc plate measured in the same manner as in Example 1.

Comparative Examples 1 to 3 For comparison, only TCD as a monomer, only DCP, and
Also in the case of using TCD and NB, the polymer and the optical disk plate were obtained in the same manner as in Examples 1 to 5, and the physical property values thereof were measured and shown in Table 1.

As is clear from Table 1, the ring-opening copolymer hydrogenated product of the present invention has a Tg in a suitable range of 100 to 135 ° C. and has a good birefringence value even in a relatively high Tg region. It has excellent optical characteristics. It is also a well-balanced polymer with high water resistance and chemical resistance.

Effects of the Invention The novel ring-opening copolymer hydrogenated product of the present invention has excellent heat resistance and optical properties, and has transparency, water resistance, chemical resistance,
It is a polymer having a good balance of solvent resistance and the like, and has an excellent effect that it can be used in a wide range of fields including the optical field.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Io Natsuumi 1-2-1 Nikko, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd. Research and Development Center (56) Reference JP-A-60-26024 (JP, 60-26024) A) JP 59-81316 (JP, A) JP 59-81315 (JP, A) JP 59-51911 (JP, A) JP 58-127728 (JP, A) JP 58 -17700 (JP, A) JP-B-46-14910 (JP, B1)

Claims (2)

[Claims] 1. (A) 90 to 10 mol% of a repeating unit represented by the following general formula [I] or an alkyl-substituted product thereof, and (B) a repeating unit represented by the following general formula [II], an alkyl-substituted product thereof. Or 5 to 50 mol% of at least one repeating unit selected from alkylidene substituents, and (C) 5 to 80 mol% of repeating units represented by the following general formula [III] or alkyl substituted products thereof, and Intrinsic viscosity [η] measured at 25 ℃ in toluene is 0.
01 to 20 dl / g and constitutes the main chain A hydrogenated product of a polycyclic norbornene ring-opening copolymer having at least 50% of single bonds. (However, in the formula Represents a single bond or a double bond. ) 2. (A) 90 to 10 mol% of the repeating unit represented by the following general formula [I '] or its alkyl-substituted product, and (B) the repeating unit represented by the following general formula [II'], its alkyl. 5 to 50 mol% of at least one repeating unit selected from a substituent or an alkylidene substituent, and (C) 5 to 80 mol% of a repeating unit represented by the following general formula [III '] or an alkyl substituent thereof. And, the intrinsic viscosity [η] measured in toluene at 25 ℃ is 0.
A main chain characterized by hydrogenating some or all of the olefinic unsaturated groups contained in the polycyclic norbornene ring-opening copolymer of 01 to 20 dl / g with hydrogen using a hydrogenation catalyst. Configure A method for producing a hydrogenated product of a polycyclic norbornene ring-opening copolymer having at least 50% of single bonds. (However, in the formula Represents a single bond or a double bond. )