JPH0753679A - Production of polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer, capable of suppressing the evolution of hydrogen chloride, polymerizing at low temperatures and being prevented from the deterioration of the polymerized product, and excellent in hue by carrying out the metathetic ring opening polymerization of a specific monomer in the presence of a solution of a metallic compound and a metathetic catalyst. CONSTITUTION:This method for producing the objective polymer is to carry out the metathetic ring opening polymerization of (C) a monomer composed of a norbornene derivative, e.g. a compound expressed by the formula [A and B are each H or 1-10C hydrocarbons; X and Y are each H, halogens or monovalent organic group; (m) and (p) are 0 or 1], etc., in the presence of (A) a solution of a metallic compound prepared by dissolving a modified substance of a metallic compound expressed by the formula MOXClY (M is molybdenum or tungsten; X is 0 or 1; Y is 1-6) with a dissolvent and (B) a metathetic catalyst composed of a trialkylaluminum or a dialkylaluminum hydride in a solvent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polymer,
In particular, it relates to a method for producing a metathesis ring-opening polymer having an improved hue by suppressing side reactions during the polymerization reaction and in the hydrogenation step.

2. Description of the Related Art Conventionally, transparent resins have been used as materials for molded articles requiring ordinary transparency such as automobile parts, lighting equipment, and electric parts, and more recently, as an optical material in which optical properties are important. Is being applied. As transparent resins preferably used for such applications, ring-opening polymers obtained by subjecting a monomer consisting of a norbornene derivative to metathesis ring-opening polymerization in the presence of a metathesis catalyst and hydrogenated products thereof are known. The ring-opening polymer and the hydrogenated product (1) have transparency, low water absorption, low birefringence, and high heat resistance.

[0002]

However, when tungsten hexachloride (WCl ₆ ) and monochlorodialkylaluminum or dichloromonoalkylaluminum are used as a metathesis catalyst, a large amount of hydrogen chloride is generated,
The heating of the polymerization and hydrogenation steps causes polymer deterioration. Further, when the polymerization temperature is high, side reactions such as a cationic reaction that causes coloring during heating may occur, and in order to obtain a polymer having a good hue, polymerization at a temperature as low as possible is necessary. preferable. However, metathesis polymerization catalysts generally have low polymerization activity at low temperatures, and no practically highly active catalysts have been found. Under the circumstances as described above, it was necessary to develop a metathesis catalyst which can stably obtain high activity at a low temperature with a catalyst system containing as few chlorine atoms as possible. Its purpose is to suppress the hydrogen chloride generated from the metathesis catalyst to prevent polymer deterioration in the polymerization and hydrogenation steps, and to carry out the polymerization at a low temperature to obtain a hue not containing a side reaction product that causes coloring. It is to provide a good method for producing a polymer.

[0003]

That is, the present invention is represented by (a) MO _X Cl _Y (M is molybdenum or tungsten, X is a number of 0 or 1 and Y is an integer of 1 to 6). Metathesis of a norbornene derivative in a solvent in the presence of a metal compound solution in which a modified metal compound is dissolved using a solubilizer and (b) a metathesis catalyst consisting of trialkylaluminum or dialkylaluminum hydride. The present invention provides a method for producing a polymer, which comprises performing ring-opening polymerization. Hereinafter, the present invention will be specifically described. <Specific Monomer> The specific monomer used in the production method of the present invention is a compound having a norbornene structure represented by Chemical Formula 1 above.

[0004]

[Chemical 1]

(In the formula, A and B are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, X and Y are hydrogen atoms, halogen atoms or monovalent organic groups, and m and p are 0 or 1)

Among the specific monomers, the specific monomer in which X or Y in the above chemical formula 1 is a polar group, particularly a group represented by the formula — (CH ₂ ) _n COOR ¹ , is a ring-opening polymer obtained. Hydrogenated products are preferable in that they have a high glass transition temperature and a low hygroscopicity. In the above formula, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms. Further, the smaller the value of n is, the higher the glass transition temperature of the obtained ring-opening polymer is, which is preferable. Further, the specific monomer in which n is 0 is easy to synthesize and It is preferable in that the ring-opening polymer obtained has a high glass transition temperature. Further, A and B in the above chemical formula ¹ are preferably an alkyl group, particularly a methyl group. In particular, the alkyl group is the same as the carbon atom to which the group represented by-(CH ₂ ) _n COOR ¹ is bonded. Is preferably bonded to the carbon atom of Also, in the above chemical formula 1, m is 1
The specific monomer is preferably a monomer having m of 0 in that a ring-opening polymer having a high glass transition point can be obtained.

Specific examples of the specific monomer represented by the above chemical formula 1 include bicyclo [2.2.1] hept-2-ene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, tricyclo [5.2.1.0 ^2,6 ] -8-decene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0
^9,13 ] -4-Pentadecene, tricyclo [4.4.0.
1 ^2,5 ] -3-undecene, 5-methylbicyclo [2.
2.1] Hept-2-ene, 5-ethylbicyclo [2.
2.1] hept-2-ene, 5-carboxymethylbicyclo [2.2.1] hept-2-ene, 5-methyl-5
-Carboxymethylbicyclo [2.2.1] hept-2
-Ene, 5-cyanobicyclo [2.2.1] hept-2
-Ene, 8-carboxymethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-carboxyethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-
3-dodecene, 8-carboxy n-propyl tetracyclo [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-propyl tetracyclo [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-butyl tetracyclo [4.
4.0.1 ^2,5 . ^1,7,10 ] -3-dodecene, dimethanooctahydronaphthalene, ethyltetracyclododecene,
6-ethylidene-2-tetracyclododecene, trimethanooctahydronaphthalene, pentacyclo [8.4.
0.1 ^2,5 . 1 ^9,12 . 0 ^8,13] -3-hexadecene, pentacyclo [7.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13 ]-
3-pentadecene, heptacyclo [8.7.0.
1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^{11, 16]} -4-eicosene, heptacyclo [8.8.0.1 ^4,7.
1 ^11,18 . 1 ^13,16 . 0 ^3, 8. 0 ^12,17 ] -5- ^heneicosene , 8-ethylidene tetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3 Dodecene etc. can be mentioned. The above-mentioned specific monomers are not necessarily used alone, and the ring-opening copolymerization reaction can be carried out using two or more kinds.

<Copolymerizable Monomer> In the ring-opening polymerization step, the above-mentioned specific monomer may be subjected to ring-opening polymerization alone, but with respect to the specific monomer and the specific monomer, Ring-opening copolymerization may be performed with 50 mol% or less of a copolymerizable monomer.
Specific examples of the copolymerizable monomer used in this case include 5-ethylidene-2-norbornene, dicyclopentadiene, cyclobutene, cyclopentene, cycloheptene, cyclooctene and tricyclo [5.2.1.0].
Cycloolefins such as ^2,6 ] -3-decene can be mentioned. Further specified in the presence of an unsaturated hydrocarbon-based polymer having a carbon-carbon double bond in the main chain such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, polynorbornene The monomer may be subjected to ring-opening polymerization. The hydrogenated product of the ring-opening copolymer obtained in this case is useful as a raw material for a resin having high impact resistance.

<Metathesis Catalyst> In the present invention, the ring-opening polymerization reaction is carried out in the presence of a metathesis catalyst. This metathesis catalyst modifies a metal compound represented by (a) MO _X Cl _Y (M is molybdenum or tungsten, X is 0 or 1, and Y is an integer of 1 to 6) and a solubilizer is used. A catalyst comprising a combination of a dissolved metal compound solution and (b) a trialkylaluminum or a dialkylaluminum hydride. In the component (a),
As the metal compound, tungsten hexachloride and molybdenum pentachloride are preferable. Further, a modifier is used to modify the metal compound. Examples of the modifier used here include t-butanol, cumene hydroperoxide, lauroyl peroxide, benzoyl peroxide, sodium peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, and 1,4-dioxane. The amount used is 5 to 100 mol% with respect to the metal compound.

Further, the metal compound is dissolved by the dissolving agent. Examples of the solubilizer include methanol, ethanol, propanol, butanol, pentanol, hexanol, ethylene chlorohydrin, epichlorohydrin, propylene oxide and ethylene oxide, and the amount used is 0 with respect to the metal compound. .5-
It is 1500 mol%. The order of treatment of the metal compound with these modifiers and solubilizers is not particularly limited, but after the metal compound is diluted with a solvent such as toluene, the modifier is first reacted and then the solubilizer is added to complete the reaction. It is preferable to prepare a homogeneous catalyst solution. Specific examples of the component (b) include trimethyl aluminum, triethyl aluminum, diethyl aluminum hydride and the like. The ratio of the component (a) and the component (b) is
The metal atomic ratio of (a) :( b) is in the range of 1: 1 to 1:30, preferably 1: 2 to 1:20.

Regarding the amount of the metathesis catalyst to be used, "(a) component: specific monomer" is usually 1: 500 to 1: 50000 in terms of the molar ratio of the component (a) to the specific monomer. A range, preferably a range of 1: 1000 to 1: 10000.

<Solvent for Ring-Opening Polymerization Reaction> Examples of the solvent used in the ring-opening polymerization reaction include alkanes such as pentane, hexane, heptane, octane, nonane and decane, cyclohexane, cycloheptane, cyclooctane, decalin and norbornane. Cycloalkanes, such as
Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobutane, bromhexane, methylene chloride, dichloroethane, hexamethylene dibromide, halogenated alkanes such as chlorobenzene, chloroform and tetrachloroethylene, compounds such as aryl, ethyl acetate, Examples thereof include saturated carboxylic acid esters such as n-butyl acetate, iso-butyl acetate, methyl propionate and dimethoxyethane, and ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane, which may be used alone or in combination. Can be used. Of these, aromatic hydrocarbons are preferred. The amount of the solvent used is such that "solvent: specific monomer (weight ratio)" is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. .

<Molecular Weight Controlling Agent> The molecular weight of the ring-opening polymer can be controlled by the polymerization temperature, the type of catalyst and the type of solvent. In the present invention, the molecular weight controlling agent is allowed to coexist in the reaction system. Adjust by. Here, suitable molecular weight regulators include, for example, ethylene, propene, 1
Α-, such as butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene
Examples thereof include olefins, dienes such as 1,3-butadiene and 1,3-pentadiene, and styrene. Of these, 1-butene and 1-hexene are particularly preferable. These molecular weight regulators may be used alone or
A mixture of two or more species can be used. The amount of the molecular weight modifier used is the specific monomer 1 used in the ring-opening polymerization reaction.
0.005-1.0 mol, preferably 0.1.
It is set to 02 to 0.7 mol. The polymerization temperature of the ring-opening polymerization reaction is 40 to 100 ° C, preferably 40 to 80 ° C, and more preferably 40 to 60 ° C.

The intrinsic viscosity (ηinh) of the obtained ring-opening polymer is preferably in the range of 0.2 to 5.0. The polystyrene-reduced average molecular weight (solvent: tetrahydrofuran) of the ring-opened polymer is usually 0.8 × 10 ⁴ as the number average molecular weight (Mn).
To 10 × 10 ^4, preferably 1.0 × 10 ⁴ ~8 × 10
⁴ , more preferably 1.2 × 10 ^{4 to} 6.0 × 10 ^4.
And the weight average molecular weight (Mw) is usually 2.0 × 10
⁴ to 30 × 10 ⁴ , preferably 2.5 × 10 ^{4 to} 25 ×
10 ⁴ , more preferably 3.0 × 10 ^{4 to} 20 × 10
It is said to be ⁴ . The molecular weight distribution (Mw / Mn) is usually 1.5 to 4.5, preferably 1.5 to 4.0, and more preferably 1.5 to 3.5. If the average molecular weight is too large, the obtained ring-opening polymer and its hydrogenated product do not have sufficient fluidity, and birefringence is likely to occur. On the other hand, if the average molecular weight is too small, silver streak may occur during injection molding of the hydrogenated product of the ring-opening polymer, and stickiness may occur on the surface of the molded product.

<Hydrogenation Step> The ring-opening polymer obtained as described above can be hydrogenated using a hydrogenation catalyst. The hydrogenation reaction is carried out by an ordinary method, that is, a hydrogenation catalyst is added to a solution of the ring-opening polymer, and the reaction is carried out at atmospheric pressure to 300.
Atmospheric pressure, preferably 3 to 200 atm of hydrogen gas 0 to 20
It is carried out by operating at 0 ° C, preferably 20 to 180 ° C. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. Heterogeneous catalysts and homogeneous catalysts are known as the hydrogenation catalyst. Examples of the heterogeneous catalyst include solid catalysts in which a noble metal catalyst substance such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. Further, as a homogeneous catalyst, nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride /
Examples thereof include diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichlorotristriphenylphosphine ruthenium, and chlorohydrocarbonyl tristriphenylphosphine ruthenium. The catalyst may be in the form of powder or particles.

These hydrogenation catalysts are used in such a ratio that the ring-opening polymer: hydrogenation catalyst (weight ratio) is 1: 1 × 10 ^-5 to 1: 2. As described above, by hydrogenation, the hydrogenated polymer obtained has excellent thermal stability, and its characteristics are not deteriorated by heating during molding or use as a product. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably 90% or more.

The polymers produced by the production method of the present invention include known antioxidants such as 2,6-di-t-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; UV absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone can be added for stabilization. Further, additives such as a lubricant may be added for the purpose of improving processability. The polymer produced by the production method of the present invention and the hydrogenated polymer thereof can be used to produce a molded article using a known molding means such as injection molding, compression molding, extrusion molding or the like.

On the surface of the formed article, an inorganic compound, an organic silicon compound such as a silane coupling agent, an acrylic resin, a vinyl resin, a melamine resin, an epoxy resin, a fluorine resin, a silicone resin, or the like is used. A hard coat layer can be formed. Examples of means for forming the hard coat layer include known methods such as a heat curing method, an ultraviolet curing method, a vacuum deposition method, a sputtering method, and an ion plating method. As a result, the heat resistance, optical characteristics, chemical resistance, abrasion resistance, moisture permeability and the like of the molded product can be improved.

The use of the polymer produced by the production method of the present invention is not particularly limited, and it can be used in a wide range. For example, lenses for general cameras,
Lenses for video cameras, telescope lenses, spectacle lenses, laser beam lenses, optical video discs, audio discs, document file discs, optical discs such as memory discs, optical materials such as optical fibers, image transfer sheets and various It can be particularly preferably used as a film, a sheet, a sealant, or a binder of an inorganic or organic compound.

[0020]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to these. In the following, "part" means "part by weight".

Example 1 Preparation of Modified WCl ₆ Solution In a container whose inside was replaced with nitrogen gas, 5 parts of WCl ₆ and 219 parts of dry toluene were mixed to prepare a 0.05 M suspension. To this suspension was added 0.33 parts of t-butanol to adjust the molar ratio to tungsten to 0.35 / 1.0, and then the mixture was stirred and sparged with nitrogen to remove the by-product HCl. Then 1.21 parts of methanol was added. The mixture was stirred for an additional at least 1 hour. WC in the mixture
The molar ratio of ₁₆ / t-BuOH / MeOH is 1.0 / 0.
It was 35 / 3.0.

Ring-Opening Polymerization Step In a reaction vessel having a jacket whose interior is replaced with nitrogen gas, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] -3
-Using dodecene, 30 parts of specific monomer and 90 parts of toluene
And 4.9 parts of 1-hexene, which is a molecular weight regulator, were charged and heated to 60 ° C. with stirring, and then a toluene solution of triethylaluminum (concentration: 1.15 mol /
1) WCl ₆ solution adjusted to 0.10 parts (concentration: 0.1.
(05 mol / l) 0.45 part was added, and metathesis ring-opening polymerization was performed for 3 hours. During this period, the jacket temperature of the reaction vessel was maintained at 60 ° C. After completion of the ring-opening polymerization reaction, the solution of the reaction system is added to a large amount of methanol to precipitate the ring-opening polymer, which is separated by filtration and vacuum dried to obtain a white powdery ring-opening polymer A-1. It was The yield of the ring-opening polymer A-1 obtained as described above is 99.1% and the intrinsic viscosity (ηin
h) is 0.43 dl / g (in chloroform, 30 ° C., concentration 0.5 g / dl), and the polystyrene-reduced average molecular weight (developing solvent: tetrahydrofuran) measured by GPC is number average molecular weight Mn = 1.5 ×. 10 ⁴ , and the weight average molecular weight Mw was 5.3 × 10 ⁴ .

Hydrogenation Step 100 parts of the ring-opening polymer A-1 was added to 20 parts of tetrahydrofuran.
A polymer solution was prepared by dissolving in 100 parts. To this polymer solution, 10 parts of a palladium catalyst (activated carbon-supported catalyst: palladium concentration = 5% by weight) as a hydrogenation catalyst was added, and hydrogen gas pressure was 150 kg / cm ^{2 at} a temperature of 1 in an autoclave.
The hydrogenation reaction was performed by heating at 50 ° C. for 3 hours. After completion of the reaction, the reaction system was cooled and the hydrogen gas was depressurized, the hydrogenation catalyst was filtered off, methanol was added to the filtrate to coagulate the hydrogenated polymer, which was dried and recovered. The hydrogenation rate of this hydrogenated polymer is substantially 100%.
Met. Further, the number average molecular weight was measured in the same manner as above, and it was 15,000, which was the same as before hydrogenation.

Manufacture of molded article To 100 parts of the obtained hydrogenated polymer, 0.2 part of an antioxidant "Irganox 1076" (manufactured by Ciba Geigy) was added, and pellets were formed by an extruder (extrusion temperature of 290 ° C). It was made. The produced pellets are injected into an injection molding machine "IS90.
B ”(manufactured by Toshiba Machine Co., Ltd .: molding temperature 320 ° C.) was used to perform injection molding to obtain a molded product.

Evaluation of Hue Regarding the hue of the molded product, the degree of yellowness was measured according to JIS K7105 (transmission method). The yellowness of the obtained molded product (thickness: 3 mm) was 1.5. Example 2 In preparing a modified WCl ₆ solution, the amount of t-butanol was 0.47 part, that is, WCl ₆ / t-BuO.
A metathesis ring-opening polymerization reaction was performed in the same manner as in Example 1 except that the H / MeOH molar ratio was changed to 1.0 / 0.5 / 3.0 to obtain a white powdery ring-opening polymer A-2. Obtained. The yield of the ring-opening polymer A-2 obtained as described above is 99.
3%, intrinsic viscosity (ηinh) is 0.42 dl / g (in chloroform, 30 ° C, concentration 0.5 g / dl), GP
The polystyrene-reduced average molecular weight (developing solvent: tetrahydrofuran) measured by C was the number-average molecular weight Mn = 1.
It was 4 × 10 ⁴ , and the weight average molecular weight Mw was 5.2 × 10 ⁴ . The hydrogenation step was performed in the same manner as in Example 1 except that the ring-opening polymer A-2 was used instead of the ring-opening polymer A-1. The hydrogenation rate was 100% in the reaction for 3 hours. A molded article was produced in the same manner as in Example 1 using the obtained hydrogenated polymer. The yellow degree of the obtained molded product is 1.
It was 6.

Example 3 In the ring-opening polymerization step, 8-ethylidenetetracyclo [4.4.
0.1 ^2,5 . 1, ^{7, 10} ] -3 dodecene, 30 parts of specific monomer, 90 parts of toluene, and a molecular weight regulator 1
-Charge with 6.1 parts of hexene and stir at 60 ° C.
Except that 0.12 parts of a toluene solution of triethylaluminum (concentration 1.15 mol / l) and 0.56 parts of a WCl ₆ solution (concentration 0.05 mol / l) prepared by heating were added. Carried out a metathesis ring-opening polymerization reaction in the same manner as in Example 1 to obtain a white powdery ring-opening polymer A-3. The yield of the ring-opening polymer A-3 obtained as described above was 99.0%, and the intrinsic viscosity (ηinh) was 0.45 dl / g.
(In chloroform, 30 ° C., concentration 0.5 g / dl), and the polystyrene-reduced average molecular weight (developing solvent: tetrahydrofuran) measured by GPC is the number average molecular weight M.
n = 1.7 × 10 ⁴ , weight average molecular weight Mw = 6.1 × 1
It was 0 ⁴ . The hydrogenation step was carried out in the same manner as in Example 1 except that the ring-opening polymer A-3 was used instead of the ring-opening polymer A-1. The hydrogenation rate was 99.9% after 3 hours. A molded article was produced in the same manner as in Example 1 using the obtained hydrogenated polymer. The yellowness of this molded product is 1.
It was 7.

Example 5 In the ring-opening polymerization step, pentacyclo [7.4.0.1 ^2,5 .
1 ^9,12 . 0 ^8,13 ] -3-pentadecene, 30 parts of a specific monomer, 90 parts of toluene, and a molecular weight modifier 1
-Prepare 5.7 parts of hexene and stir at 60 ° C.
And then 0.11 part of a toluene solution of triethylaluminum (concentration 1.15 mol / l) and Example 1
WCl6 solution (concentration 0.05 mol / l) prepared in
A metathesis ring-opening polymerization reaction was performed in the same manner as in Example 1 except that 52 parts of the ring-opening polymer A was obtained.
-8 was obtained. The yield of A-8 of the obtained ring-opening polymer was 9
8.9%, intrinsic viscosity (ηinh) is 0.43 dl / g (in chloroform, 30 ° C., concentration 0.5 g / dl),
The polystyrene-reduced average molecular weight (developing solvent: tetrahydrofuran) measured by GPC is the number average molecular weight Mn =
It was 1.8 × 10 ⁴ , and the weight average molecular weight Mw was 6.2 × 10 ⁴ . Then, the hydrogenation step was carried out in the same manner as in Example 1 except that the ring-opening polymer A-8 was used in place of the ring-opening polymer A-1. The hydrogenation rate was 99.9% after 3 hours. A molded article was produced in the same manner as in Example 1 using the obtained hydrogenated polymer. The yellow degree of the obtained molded product is 1.
It was 7.

Comparative Example 1 Preparation of a modified WCl ₆ solution was carried out without adding t-butanol (WCl ₆ /
The metathesis ring-opening polymerization reaction was performed in the same manner as in Example 1 except that the molar ratio of MeOH was 1.0 / 3.0) to obtain a white powdery ring-opening polymer a-4. The yield of the ring-opening polymer a-4 obtained as described above was 83.4%. The intrinsic viscosity (ηinh) of this ring-opening polymer a-4 is 0.45 dl
/ G (in chloroform, 30 ° C, concentration 0.5g / dl)
The polystyrene-equivalent average molecular weight (developing solvent: tetrahydrofuran) measured by GPC is number-average molecular weight Mn = 1.6 × 10 ⁴ , weight-average molecular weight Mw = 6.1 ×.
It was 10 ⁴ . The hydrogenation step was carried out in the same manner as in Example 1 except that the ring-opening polymer a-4 was used instead of the ring-opening polymer A-1. Hydrogenation rate is 99.9% in 3 hours
Met. A molded article was produced in the same manner as in Example 1 using the obtained hydrogenated polymer. The yellowness of this molded product was 4.7.

Comparative Example 2 Metathesis ring-opening was carried out in the same manner as in Example 1 except that 0.40 parts of a toluene solution of diethylaluminum chloride (concentration: 1.15 mol / l) was used in place of the toluene solution of triethylaluminum. A polymerization reaction was performed to obtain a white powdery ring-opening polymer a-5. The yield of the ring-opening polymer a-5 thus obtained was 99.3.
%, Intrinsic viscosity (ηinh) is 0.43 dl / g (in chloroform, 30 ° C., concentration 0.5 g / dl).
Measured polystyrene average molecular weight (developing solvent:
Tetrahydrofuran) has a number average molecular weight Mn = 1.2 ×
10 ⁴ , and the weight average molecular weight Mw was 5.5 × 10 ⁴ .
The hydrogenation step was carried out in the same manner as in Example 1 except that the ring-opening polymer a-5 was used instead of the ring-opening polymer A-1. The hydrogenation rate was 99.9% in 5 hours. A molded article was produced in the same manner as in Example 1 using the obtained hydrogenated polymer. The yellowness of this molded product was 5.1.

Comparative Example 3 A metathesis ring-opening polymerization reaction was carried out in the same manner as in Example 1 except that the jacket temperature of the reaction vessel was kept at 120 ° C. and the amount of 1-hexene was 2.2 parts. The ring-opening polymer a-6 of was obtained. The yield of the ring-opening polymer a-6 obtained as described above is 99.7%,
The intrinsic viscosity (ηinh) is 0.42 dl / g (in chloroform, 30 ° C., concentration 0.5 g / dl), and the polystyrene-reduced average molecular weight (developing solvent: tetrahydrofuran) by GPC measurement is number average molecular weight Mn = 1. .4 × 10
⁴ , and the weight average molecular weight Mw was 5.1 × 10 ⁴ . The hydrogenation step was carried out in the same manner as in Example 1 except that the ring-opening polymer a-6 was used instead of the ring-opening polymer A-1.
The hydrogenation rate was 100% in 3 hours. A molded article was produced in the same manner as in Example 1 using the obtained hydrogenated polymer. The yellowness of this molded product was 5.7.

Example 4 In the hydrogenation step, 100 parts of the ring-opening polymer A-1 obtained in Example 1 was dissolved in 400 parts of toluene to prepare a polymer solution. To this polymer solution, 0.075 part of chlorohydrocarbonyl tristriphenylphosphine ruthenium was added as a hydrogenation catalyst, and hydrogen gas pressure was 100 kg / cm in an autoclave.
² , hydrogenated polymer A-7 was obtained in the same manner as in Example 1 except that the hydrogenation reaction was performed by heating at a temperature of 165 ° C for 3 hours. The hydrogenation rate of this hydrogenated polymer was substantially 100%. Further, the number average molecular weight was measured in the same manner as above, and it was 15,000, which was the same as before hydrogenation. A molded article was produced in the same manner as in Example 1 by using the obtained hydrogenated polymer A-7. The yellowness of this molded product was 1.7.

[0032]

According to the production method of the present invention, hydrogen chloride generated from the polymerization catalyst system can be suppressed, polymerization can be carried out at a lower temperature than before, and hydrogenation time can be shortened, thereby preventing polymer deterioration. You can The hue of the obtained ring-opened polymer molded product is very good.

Front page continued (72) Inventor Noboru Oshima 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. A modified metal compound represented by (a) MO _X Cl _Y (M is molybdenum or tungsten, X is a number of 0 or 1, and Y is an integer of 1 to 6) is dissolved. In the presence of a metal compound solution dissolved with an agent and (b) a metathesis catalyst composed of trialkylaluminum or dialkylaluminum hydride, a monomer composed of a norbornene derivative is subjected to metathesis ring-opening polymerization in a solvent. Polymer production method.