JP3346012B2 - Norbornene polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel norbornene resin having excellent transparency, chemical resistance, electric properties and the like, which is made from industrially available and inexpensive dicyclopentadiene (DCP), and its production. About the method.

[0002]

2. Description of the Related Art A metathesis ring-opened polymer made from a cyclic olefin represented by norbornene is characterized by its excellent heat resistance and transparency, and is expected to be used as an optical material. Focusing on the polymerization of the monomer, it utilizes ring-opening polymerization of the double bond of the norbornene skeleton. On the other hand, dicyclopentadiene (DCP) is known as an industrial raw material for the C5 fraction. However, since it has the structure of norbornene and the structure of cyclopentene at the same time, even if DCP is subjected to metathesis polymerization, Gelation occurs without selective polymerization. Therefore, after converting the double bond of the poorly reactive cyclopentene skeleton into another functional group, it is necessary to carry out metathesis ring-opening polymerization as a norbornene derivative, and industrially dicyclopentadiene (DC
P) could not be used directly. Norbornene-based polymers that have been conventionally developed have a high glass transition temperature (Tg) of 200 to 300 ° C, and require high melting temperatures in heat-melting molding methods such as injection molding, compression molding, and extrusion molding. Therefore, there arises a problem that the inside of the resin is gelled and blackened.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to use an industrially inexpensive raw material such as dicyclopentadiene and to obtain norbornene having excellent characteristics. An object of the present invention is to provide a resin and a method for producing the resin.

[0004]

According to the present invention, there is provided a polystyrene-equivalent number average molecular weight of 5,000 to 1,000, comprising a monomer unit represented by the following general formula 1.
000 norbornene polymers and a method for producing the same.

[0005]

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(In the general formula, X is a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and A, B and Y are a hydrogen atom or a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a chain thereof. Represents a functional group containing an oxygen atom or a nitrogen atom, n is an integer, and m is an integer of 0 to 5.) Hereinafter, the present invention will be described in more detail.

[0007] In the norbornene polymer of the present invention, the monomer unit represented by the above-mentioned general formula 1 contains 50 to 100% of the whole polymer.
Mol%, preferably 80 to 100 mol%, more preferably 100 mol%. In the general formula 1, examples of the hydrocarbon group having 1 to 10 carbon atoms represented by X include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group. In the general formula 1, as the halogen atom represented by A, B, and Y, a chlorine atom, a fluorine atom, a bromine atom, and the like, and as the hydrocarbon group having 1 to 10 carbon atoms,
The same groups as those described above for X include, as a functional group containing an oxygen atom or a nitrogen atom, a carboxyl group, a group represented by —CH ₂ COOR (R represents an alkyl group such as a methyl group or an ethyl group), or an epoxy group. , Isocyanate group, amino group,
Examples thereof include a nitro group. Furthermore, general formula 1
M is 0 to 5, preferably 0 to 3. In the present invention, preferred monomer units are those in which all of X, Y, A and B in the general formula 1 are hydrogen atoms. In the norbornene polymer of the present invention, as the monomer unit that can be contained other than the general formula 1, a monomer unit represented by the following general formula 3 is preferable, and 0 to 50% by mole in the norbornene polymer is preferable. Is 0 to 20 mol%.

[0008]

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(In the general formula, X, Y, A and B are the same as those in the general formula 1.) In the general formula 3, X and A are hydrogen atoms, and B is -CH
_The group represented by ₂ COOR, Y is preferably an alkyl group. The average molecular weight (solvent: tetrahydrofuran) of the norbornene polymer of the present invention in terms of polystyrene by GPC measurement is such that the number average molecular weight (Mn) is usually 0.5 ×.
10 ⁴ to 1 × 10 ⁶ , preferably 1.0 × 10 ^{4 to} 5 × 1
0 ⁵ , more preferably 1.2 × 10 ^{4 to} 2.0 × 1
0 ⁵ , particularly preferably in the range of 1.5 × 10 ^{4 to} 1.0 × 10 ⁵ .

If the molecular weight is less than 5,000, it cannot be used as a molding material.
If it is more than 00, fluidity is poor and molding becomes difficult. The intrinsic viscosity (ηinh) of the norbornene polymer of the present invention is 0.1 to
It is preferably in the range of 5.0. The norbornene polymer of the present invention can be produced by subjecting a compound represented by the following general formula 2 to metathesis ring-opening polymerization. The monomer represented by the following general formula 2 used in the present invention has a double bond of a norbornene moiety among two double bonds of a norbornene moiety and a cyclopentene moiety possessed by a compound represented by the following general formula 4. It can be obtained by selective hydrogenation or by introducing a halogen or a substituent into the double bond of the norbornene moiety.

[0011]

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(In the general formula, X, A, B and Y are the same as in the general formula 1. m is an integer of 0 to 5.)

[0013]

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(In the general formula, m is an integer of 0 to 5.)

First, a method for hydrogenating the compound represented by the general formula 4 will be described. Regarding dicyclopentadiene which is a typical compound among the compounds represented by the general formula 4,
For example, CA Brown, UK Ahuja, J. Org. Chem., 38 , 2226 (197
3). And F. Bergmann, H. Japhe, J. Amer. Chem. Soc., 69 , 1826.
(1947). It is known that the double bond of the norbornene moiety reacts selectively. As the selective hydrogenation catalyst, those used for hydrogenation of ordinary olefinic compounds can be used. As the hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are known.
Heterogeneous catalysts include palladium, platinum, nickel,
Noble metal catalyst materials such as rhodium, ruthenium, etc.
Examples include a solid catalyst supported on a carrier such as silica, alumina, or titania. Examples of homogeneous catalysts include nickel / triethylaluminum naphthenate, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, and chlorotris (triphenylphosphine) rhodium. , Trichlorobistriphenylphosphine ruthenium, chlorohydrocarbonylbistriphenylphosphine ruthenium and the like. The form of the catalyst may be powdery or granular.

These hydrogenation catalysts have a compound represented by the general formula 4: hydrogenation catalyst (weight ratio) of 1: 1 × 10 ^-4 to 1: 2.
It is used at a ratio of The hydrogenation reaction is usually carried out at normal pressure to 3
Under a hydrogen gas atmosphere of 00 atm, preferably 3 to 150 atm, 0 to 180 ° C, preferably 20 to 150 ° C
Can be done with

Next, the introduction of a halogen or a substituent into the double bond of the norbornene moiety of the compound represented by the general formula 4 will be described. The compound represented by the general formula 4 has two different double bonds (olefin) of a cyclopentene moiety and a norbornene moiety. Of these double bonds, the norbornene moiety has high activity, and the reaction proceeds selectively. By utilizing this property, the norbornene moiety of the general formula 4 can be epoxidized. (J.Am.Chem.So
c., 1960, 82, 4328 M. Korack, DRNielsen and WHRid
eout) A compound represented by the general formula 4
The norbornene moiety can be selectively epoxidized using a acetic acid solution of 0% peracetic acid in the presence of anhydrous sodium carbon. Further, even if m-chloroperbenzoic acid is used as peracetic acid, epoxidation under milder conditions is possible.
(J.Org.ChEM., 1965,30,1271 DJPasto and CCCumb
o) Further, the epoxy compound obtained by epoxidizing the norbornene moiety is a lithium aluminum halide (LiAlH
4) Alternatively, it can be reduced to monoalcohol by sodium in liquid ammonia. (J. Org. Chem., 197
1.36,330 EM Kaiseret. Al.) The epoxy compound reduced to the monoalcohol can then be reacted with hydrohalic acid or thionyl chloride to form an alkyl halide. In this reaction, the olefin in the cyclopentene moiety may be halogenated, so that Fe (CO)
It is preferred to protect the olefin with 5 or the like before halogenating.

Specific examples of the monomer represented by the general formula 3 obtained as described above include tricyclo [4 ^1,5 3 ^1,5
0,1 ^6,8 ] -2-decene, 7-hydro-tricyclo [4
^1,5 3 ^1,5 0,1 ^6,8 ] -3-decene, 7-methylcarboxy-tricyclo [4 ^1,5 3 ^{1,5 0,16,8} ] -3-decene,
7-carboxy-tricyclo [4 ^1,5 3 ^1,5 0,1 ^6,8 ]-
3-decene, 7-trifluoromethyl-tricyclo [4
^1,5 3 ^1,5 0,1 ^6,8 ] -3-decene, 7,7-difluoro-
8-trifluoromethyl-tricyclo [4 ^1,5 3 ^1,5 0,1
^6,8 ] -3-decene, 7-ethylidene-tricyclo [4 ^1,5
3 ^1,5 0,1 ^6,8 ] -3-decene, 7-propylidene-tricyclo [4 ^1,5 3 ^{1,5 0,16,8} ] -3-decene, oxa-tetracyclo- [44 ^{, 8} , 3 ^4,8 , 0,1 ^3,9 , 1 ^2,10 ] −
6-dodecene and the like.

In the present invention, the monomer represented by the general formula 3 and another monomer can be copolymerized. Other monomers include 8-carboxymethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-carboxyethyltetracyclo [4.4.0.1 ^7,10 ] -3-
Dodecene, 8-carboxy n-propyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Carboxyisopropyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-carboxy n-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxyethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Methyl-8-carboxy n-propyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Methyl-8-carboxyisopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Methyl-8-carboxy n-butyltetracyclo [4.
4.0.1 ^{2, 5} . ^{17, 10} ] -3-dodecene, norbornene, dimethanooctahydronaphthalene, ethyltetracyclododecene, trimethanooctahydronaphthalene and the like. Of these, preferred examples are 8-
Methyl-8-carboxymethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like.

In the present invention, the ring-opening polymerization is carried out in the presence of a metathesis catalyst. As the metathesis catalyst, usually, (a) at least one selected from compounds of W, Mo and Re, and (a) periodic table IA, II of Deming
A catalyst comprising at least one combination selected from the group A, IIIA, IVA or IV compounds having at least one element-carbon bond or element-hydrogen bond. Agents may be added. (A) Compounds of W, Mo or Re suitable as the component include halides, oxyhalides, alkoxyhalides, alkoxides, carboxylate salts,
(Oxy) acetylacetonate, carbonyl complex, acetonitrile complex, hydride complex, and derivatives thereof,
Alternatively, a combination of these compounds is preferred, and compounds of W and Mo, particularly, halides, oxyhalides, and alkoxy halides thereof are preferable from the viewpoint of polymerization activity and practicality. These compounds may be complexed with a suitable complexing agent such as P (C ₆ H ₅ ) ₅ , C ₅ H ₅ N and the like.

As specific examples, WCl ₆ , WOCl ₄ , Mo
Cl ₅ , MoOCl ₃ , ReCl ₃ , WCl ₂ (OC ₆ H ₅ )
₄ , MoO ₂ (acac) ₂ , W (OCOR) ₅ , W (C
O) ₆ , WCl ₅ .P (C ₆ H ₅ ) _{3 and the} like. Among these compounds, particularly preferred compounds include WCl
₆ , MoCl _{5 and the} like. Specific examples of compounds suitable as component (a) include n-
C ₄ H ₅ Li, (C ₂ H ₅ ) ₂ Zn, (C ₂ H ₅ ) ₃ Al, (C
_{2 H 5) AlCl, C 2} H 5 AlCl 2, (C 2 H 5) Al
H, (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ , (C ₂ H ₅ ) ₂ AlOC
_{2 H 5, (iso-C} 4 H 9) 2 AlH, (iso-C 4 H 9) 3 Al,
(CH ₃ ) ₄ Ga, (CH ₃ ) ₄ Sn, (n-C ₄ H ₉ ) ₄ S
n, Ph ₄ Sn and the like. Of these, particularly preferred compounds include (CH ₃ ) ₄ Sn and (n-C ₄ H ₉ ) ₄
Sn, Ph ₄ Sn and the like. The quantitative relationship between the component (a) and the component (a) is such that the ratio of the component (a) / the component (a) is 1 in terms of metal atomic ratio.
/ 1 to 1/30, preferably 1/2 to 1/20. The catalyst prepared from the above two components (a) and (a) usually has a high activity sufficient for use in the production method of the present invention, but if necessary, the following ( C) By adding the component, the activity can be further enhanced.

As the compound preferably used as the component (c), alcohols, aldehydes, ketones, amines and the like can be suitably used, and further, compounds described in JP-A-1-240517 are used. be able to. The ratio of the component (A) to the component (U) is such that the molar ratio of the component (U) / the component (A) is 0.005: 1 to 15:
1, preferably in the range of 0.05: 1 to 7: 1.
Solvents used in the ring-opening polymerization reaction include, for example, alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, and norbornane; benzene, toluene, and xylene , Ethylbenzene, aromatic hydrocarbons such as cumene, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chloroform, tetrachloroethylene, chlorobenzene, dichlorobenzene, halogenated alkanes such as trifluoromethylbenzene, compounds such as aryl, Saturated carboxylic esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, and methyl propionate; ethers such as dibutyl ether, tetrahydrofuran, and dimethoxyethane And the like can be illustrated, they may be used singly or in combination. Of these, aryl halides and saturated carboxylic esters are preferred. In the present invention, the ratio of the monomer is (A)
The amount of the component: monomer (weight ratio) is from 1: 1 to 1: 10000, preferably from 1: 500 to 1: 5000.

The amount of the solvent used is such that the solvent: monomer (weight ratio) is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. . The molecular weight of the ring-opening polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight is adjusted by coexisting a molecular weight modifier in the reaction system. Examples of such a molecular weight regulator include α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. And 1-butene and 1-hexene are particularly preferable. These are one or two
A mixture of more than one species can be used. The amount of the molecular weight modifier added to the reaction system is 0.001 to 0.4 mol, based on the total 1 mol of the monomers subjected to the ring-opening polymerization reaction.
Preferably it is 0.005-0.3 mol. In the ring-opening polymerization step, a monomer is introduced into a reactor together with a metathesis catalyst, a molecular weight regulator, and a polymerization solvent to cause a ring-opening polymerization reaction. The polymerization temperature is usually -10 to 100
° C, preferably -10 to 50 ° C.

The norbornene polymer obtained as described above can be hydrogenated using a hydrogenation catalyst. As the hydrogenation catalyst, the same hydrogenation catalyst and hydrogenation conditions as those used in the synthesis of the compound represented by the general formula 4 can be used. Further, in the present invention, an unsaturated hydrocarbon polymer containing a carbon-carbon double bond in the main chain such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, and polynorbornene. The monomer represented by the general formula 2 may be subjected to ring-opening polymerization in the presence of-. The hydrogenated norbornene polymer obtained in this case is useful as a raw material for a resin having high impact resistance.

The norbornene polymer of the present invention may contain a known antioxidant such as 2,6-di-tert-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t.
-Butyl-5,5'-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate] methane or an ultraviolet absorber such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, or the like. Further, additives such as a lubricant can be added to improve the processability.

The norbornene polymer of the present invention can be formed into a molded article by using known molding means, for example, injection molding, compression molding, extrusion molding and the like. Since the norbornene polymer of the present invention has a low melting temperature, the above-mentioned molding can be easily performed, and the processability is improved. Further, on the surface of the molded article comprising the norbornene polymer of the present invention, an inorganic compound, an organic silicon compound such as a silane coupling agent, an acrylic resin,
A hard coat layer made of a vinyl resin, a melamine resin, an epoxy resin, a fluorine resin, a silicone resin, or the like can be formed. Examples of the means for forming the hard coat layer include known methods such as a thermosetting method, an ultraviolet curing method, a vacuum deposition method, a sputtering method, and an ion plating method. As a result, the heat resistance of the molded product,
Optical properties, chemical resistance, abrasion resistance, moisture permeability and the like can be improved.

The use of the norbornene polymer of the present invention is not particularly limited and can be used in a wide range. For example, a semiconductor protective film (α-ray protective film, passivation film, buffer coat, interlayer insulating film) , High frequency substrate, pellicle (photomask dust cover), EP
Protective film for ROM (ultraviolet erasable and programmable ROM), window material, insulating material, lens such as optical fiber, general camera lens, video camera lens, telescope lens, laser beam lens, optical video Optical discs such as discs, audio discs, document file discs, and memory discs; optical materials such as low-reflection coating materials, eyeglass lenses, CCD lids, and OH
It can be suitably used as a transparent film such as a P sheet, a sheet for animated cel images, and a transparent conductive film.

[0028]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. In the following, the values of the hydrogenation ratio and the copolymerization ratio are based on nuclear magnetic resonance (NMR) measured at 100 MHz. Based on the magnitude of the decrease in the peak at δ = 5.5 to 6.0 ppm derived from the norbornene skeleton olefin, and the copolymerization ratio,
8-methyl-8-carboxymethyltetracyclo [4.
4.0.1 ^2,5 . Based on the integrated value of the peak at δ = 3.5 ppm derived from the carboxymethyl group of ^1,7,10 ] -3-dodecene, and for the hydrogenation of the polymer, the peak at δ = 5.5 to 6.0 ppm decreases. It is calculated based on the value of the size.

Reference Example: Synthesis of Monomer Represented by General Formula 2 Reference Example 1 0.4 kg of dehydrated cyclopentadiene was charged into a 1 dm ³ autoclave equipped with a stirrer and a thermometer, and then alkoxylithium was added. 0.5 g was added, and the mixture was stirred at 80 ° C. for 5 minutes. Next, 1.54 g of benzophenone was added and stirred for 10 minutes. Next, a component in which 0.10 g of bis (cyclopentadienyl) titanium dichloride and 0.43 g of diethylaluminum chloride dissolved in 20 ml of toluene were mixed in advance in a nitrogen atmosphere was charged, and the mixture was added to the system and stirred. . Then, 1.5 kg of hydrogen gas
The mixture was supplied at a pressure of f / cm ² G, and a hydrogenation reaction was performed at 90 ° C. The reaction was terminated when the hydrogen absorption reached 74,01 dm ³ (calculated at 25 ° C). The reaction time was 4 hours. The resulting mixture was rectified by a vacuum distillation method to obtain a target product.
The degree of hydrogenation was 99.5%, and the yield was 95%.

Reference Example 2 A reaction was carried out in the same manner as in Reference Example 1 except that 0.5 kg of dehydrated tetracyclopentadiene was used instead of cyclopentadiene to obtain a desired product. The degree of hydrogenation was 99.5%, and the yield was 95%. Instead 7-methyl cyclopentadiene in Reference Example 3 Reference Example 1 - tricyclo [4 ^{1, 5} 3 ^1,5 0,1 ^6,8] -3-decene
The intended product was obtained in the same manner as in the Reference Ordinance except that 0.4 kg was used. The degree of hydrogenation was 99.5%, and the yield was 92%. Instead 7-carboxymethyl cyclopentadiene in Reference Example 4 Reference Example 1 - tricyclo ^{[4, 5} 3 ^1,5 0,1 ^6,8 -
The desired product was obtained in the same manner as in Reference Example 1 except that 0.4 kg of 3-decene was used. The degree of hydrogenation was 99.5%, and the yield was 92%.

[0031] oxa instead of cyclopentadiene in Reference Example 5 Reference Example 1 - tetracyclo - [4 ^{4, 8,} 3 ^4,8, 0,1 ^3,9, 1 ^2,10] -
The desired product was obtained in the same manner as in the Reference Instruction except that 0.4 kg of 6-decene was used. The degree of hydrogenation was 99.5%, and the yield was 92%.

Example 1 A 100 ml flask equipped with a stirrer and a three-way cock was replaced with nitrogen gas, and 1.2 ml of a toluene solution of diethylaluminum chloride (1.25 mol / dm ³ ) was placed in a nitrogen stream.
, Toluene solution of tungsten hexachloride (0.01 mol / dm ³ )
Was added and stirred at 0 ° C. for about 5 minutes. afterwards,
10 g of the monomer synthesized in Reference Example 1 above and 1-hexene 0.
A solution of 1 g in 24 ml of toluene was added little by little, and the mixture was stirred at 0 ° C. for 3 hours to polymerize. After the completion of the polymerization reaction, the polymerization solution was poured into a large amount of methanol to precipitate a ring-opened polymer. Next, 10 g of the obtained ring-opened polymer was dissolved in 100 ml of toluene to prepare a polymer solution of about 10%. This was charged into a 1 dm3 autoclave equipped with a stirrer and thermometer, and Inorganic Synthesis Vol. 15
1.7 mg of RuH ₄ [P (C ₆ H ₅ ) ₃ ] ₄ produced as described above was added as a hydrogenation catalyst. Thereafter, hydrogen gas was introduced into a high-pressure autoclave, and the temperature was raised to 165 ° C. with stirring. The hydrogen pressure was 60 kgf / cm ² . This temperature was maintained for 10 hours, then the temperature was returned to room temperature, hydrogen gas was released, the reaction solution was dropped into a large amount of methanol to precipitate a hydrogenated polymer, and dried under vacuum to obtain a 93% yield of norbornene. A polymer was obtained. The hydrogenation rate was 99%. The weight average molecular weight of this norbornene polymer in terms of polystyrene is 10
3000, glass transition temperature (Tg) measured by DSC is 11
It was 3 ° C. and the dielectric constant was 2.7 (1 MHz).

Examples 2 to 5 Instead of the monomer synthesized in Reference Example 1 in Example 1, the monomer synthesized in Reference Example 2 (Example 2) and the monomer synthesized in Reference Example 3 (Example Example 3) Ring-opening polymerization was performed in the same manner as in Example 1 except that 5 g of each of the monomer synthesized in Reference Example 4 (Example 4) and the monomer synthesized in Reference Example 5 (Example 5) was used in an amount of 5 g. And hydrogenated to obtain a norbornene polymer of the present invention. The yield, hydrogenation rate, and number average molecular weight of each norbornene polymer were as shown in Table 1.

[0034]

[Table 1]

Example 6 5 g of the monomer synthesized in Reference Example 1, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1
A solution of 5 g of ^7,10 ] -3-dodecene and 0.1 g of 1-hexene in 24 ml of toluene was added little by little, and the mixture was stirred at room temperature for 3 hours to polymerize. After the completion of the polymerization reaction, the polymerization solution was poured into a large amount of methanol to precipitate a ring-opened polymer. The ring-opened polymer was hydrogenated in the same manner as in Example 1, collected by filtration and dried under vacuum to obtain a norbornene polymer with a yield of 85%. The hydrogenation rate was 99%. The norbornene polymer had a polystyrene-equivalent number average molecular weight of 105000 and a glass transition temperature (Tg) measured by DSC.
Was 140 ° C. and the dielectric constant was 3.1 (1 MHz).

Example 7 10 g of the monomer synthesized in Reference Example 1, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1
A solution of 0.1 g of ^7,10 ] -3-dodecene and 0.1 g of 1-hexene in 24 ml of toluene was added little by little, and the mixture was stirred at room temperature for 3 hours to polymerize. After the polymerization reaction,
The polymerization solution was poured into a large amount of methanol to precipitate a ring-opened polymer. This ring-opened polymer was hydrogenated in the same manner as in Example 1, collected by filtration and dried in vacuo to obtain a norbornene polymer with a yield of 83%. The hydrogenation rate was 99%. The polystyrene equivalent number average molecular weight of this polymer was 125,000.

Example 8 In Example 1, a solution prepared by dissolving 3.5 g of cyclopentene and 0.1 g of 1-hexene in 24 ml of toluene was successively added, and polymerized in the same manner as in Example 1 except that the mixture was stirred for 3 hours. Was. After the completion of the polymerization reaction, the polymerization solution was poured into a large amount of methanol to precipitate a ring-opened polymer. This ring-opened polymer was hydrogenated in the same manner as in Example 1 and dried under vacuum to obtain a norbornene polymer with a yield of 53%. The degree of hydrogenation was 95%. The norbornene polymer had a polystyrene-equivalent number average molecular weight of 85,000 and a glass transition temperature (Tg) of 75.
° C and a dielectric constant of 2.8 (1 MHz). Example 9 In Example 1, a solution prepared by dissolving 6.5 g of cyclopentene and 0.1 g of 1-hexene in 24 ml of toluene was successively added, and polymerized in the same manner as in Example 1 except that the mixture was stirred for 3 hours. After the completion of the polymerization reaction, the polymerization solution was poured into a large amount of methanol to precipitate a ring-opened polymer. This ring-opened polymer was hydrogenated in the same manner as in Example 1 and dried under vacuum to obtain a norbornene polymer with a yield of 42%. The hydrogenation rate was 93%. The number average molecular weight in terms of polystyrene of this norbornene polymer was 77,000.

Test Examples Solvent resistance was tested using the polymers obtained in Examples 1, 6 and 8. That is, each polymer is 5cm5cm1c
m and immersed in each of the organic solvents shown in Table 2 at a temperature of ° C. for a time, and then visually observed. Table 2 shows the results. ：: No change at all, Δ: Part or all of the test piece lost transparency, ×: Part or all of the test piece dissolved

Table 2

[0040]

[0041]

According to the present invention, inexpensive dicyclopentadiene (DCP) is partially hydrogenated by using a hydrogenation catalyst to selectively hydrogenate only highly active norbornene moieties among a plurality of olefin moieties in the molecule. Thus, the olefin moiety can be converted to only the cyclopentene skeleton. Further, the monomer synthesized here is well copolymerized with a norbornene derivative having high activity, though it is conventionally considered to have low activity. Also,
8-methyl-8-carboxymethyltetracyclo [4.
4.0.1 ^2,5 . By copolymerizing 5 to 10% of a norbornene derivative represented by [ ^17,10 ] -3-dodecene, the polymerization activity can be remarkably improved. In addition, this polymer can be easily hydrogenated with a suitable hydrogenation catalyst. The polymer obtained by the present invention is a novel norbornene-based polymer having excellent transparency, chemical resistance, electrical properties, and the like, and has a glass transition temperature lower than that of the conventional polymer, and a material having excellent workability. Is obtained.

[0042]

[Brief description of the drawings]

FIG. 1 is a view showing an IR chart of a polymer obtained in Example 6.

FIG. 2 is a view showing an IR chart of a polymer obtained in Example 8.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-170425 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 61/06-61/08

Claims (2)

(57) [Claims] 1. A polystyrene reduced number average molecular weight of 50 comprising a monomer unit represented by the following general formula 1.
From 100 to 100,000 norbornene polymers. Embedded image (In the general formula, X is a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and A, B and Y are a hydrogen atom or a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms or an oxygen atom in the chain thereof. Or a functional group containing a nitrogen atom.
n is an integer, and m is an integer of 0-5. ) 2. The norbornene polymer according to claim 1, wherein at least one of the monomers represented by the following general formula 2 is polymerized in the presence of a metathesis ring-opening polymerization catalyst, and further hydrogenated. Manufacturing method. Embedded image (In the general formula 2, X, Y, A and B are the same as in the general formula 1, and m is an integer of 0 to 5.)