JPH0873571A - Production of thermoplastic polymer - Google Patents

Abstract

PURPOSE: To obtain a high-quality polymer which is highly colorless and transparent by ring-opening polymerization of a monomer comprising a norbornene derivative in a solvent using a specific metathesis catalyst. CONSTITUTION: A monomer comprising a norbornene derivative represented by the formula (wherein D, E, G, and J each is H, a halogen, or a monovalent organic group and may be bonded to each other to form a mono- or polycyclic group, and D may be bonded to E to form an alkylidene group; k is 0 or a positive integer; and q is 0 or 1) is polymerized in a solvent by ring-opening polymerization in the presence of a metathesis catalyst comprising a metal compound (A) represented by the formula, MOx Cly (wherein M is Mo, W, Ru, Re, or Ta; x is 0-2; and y is l-6), a modifier (B) represented by Rm AOn Bp (wherein R is a 1-20C hydrocarbon group; A is P, C, or S; B is a halogen; m is 0-2; n is 1 or 2; and p is 1-3), and an organoaluminum compound (C). Thus, the metals contained in the catalyst are prevented from remaining in the polymer resulting from the ring-opening polymerization. As a result, the polymer has a high quality and is highly colorless and transparent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a thermoplastic polymer, and more particularly to a method for producing a metathesis ring-opening polymer having excellent colorless transparency.

[0002]

2. Description of the Related Art Conventionally, a transparent resin has been used as a material for molded articles requiring ordinary transparency such as automobile parts, lighting equipment, and electric parts, and particularly recently, an optical material in which optical properties are emphasized. The application as is progressing. As transparent resins preferably used for such applications, ring-opening polymers obtained by subjecting a monomer comprising 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 hydrogenated product of are transparent, low water absorption, low birefringence,
Combines high heat resistance. And as a metathesis catalyst used for ring-opening polymerization, tungsten hexachloride (W
A catalyst system composed of Cl ₆ ) and monochlorodialkylaluminum or dichloromonoalkylaluminum is known as a typical one.

[0003]

However, when the above-mentioned catalyst system is adopted, in the ring-opening polymerization step or hydrogenation step carried out under heating conditions, due to the large amount of hydrogen chloride generated from the catalyst system, There is a problem that the obtained (hydrogenated) polymer deteriorates. Also,
Conventional metathesis catalysts, including the catalyst system, generally have low catalytic activity at low temperatures, and therefore, it is necessary to carry out the ring-opening polymerization step under a certain high temperature condition. When the ring polymerization step is carried out under high temperature conditions, side reactions other than the ring-opening polymerization reaction occur, and there is a problem that the resulting polymer is colored due to the side reaction product. Further, there is a problem in that a considerable amount of a metal derived from a catalyst remains in the obtained polymer, and the metal causes the polymer to be colored. On the other hand, when the monomer used in the ring-opening polymerization reaction has a functional group such as an ester bond-containing group or a cyano group, the functional group in the monomer acts as a catalyst poison for the metathesis catalyst, For this reason, there is also a problem that the catalytic activity becomes lower than when a monomer having no functional group is used.

Against the background of the above problems, the present inventors have previously proposed that a metathesis catalyst composed of a specific metal compound solution and a specific organoaluminum compound is used,
We proposed a technique for metathesis ring-opening polymerization of a monomer composed of a norbornene derivative in a solvent (Japanese Patent Application No. 5-2.
19184).

By using such a specific metathesis catalyst, the generation of hydrogen chloride is suppressed, the deterioration of the polymer is prevented, and the coloring problem caused by the side reaction product is solved. I was able to.

However, even with such a technique, the above-mentioned problem that the polymer is colored by the metal derived from the catalyst cannot be solved. Therefore, in order to obtain a polymer having colorless transparency, it is necessary to reduce the amount of residual metal in the polymer, and therefore, a high detouching step is required, which leads to an increase in production cost and an industrial viewpoint. Was significantly disadvantageous. Therefore, it has been desired to develop a metathesis catalyst capable of producing a polymer having excellent colorless and transparent properties without requiring a high-grade detouching step.

Further, the above-mentioned technique cannot solve the above-mentioned problem that the metathesis catalyst is poisoned by the functional group of the monomer, and a catalyst system which is not easily poisoned by the functional group is provided. It was requested.

The present invention has been made based on the above circumstances. A first object of the present invention is to provide a high-quality ring-opening polymer that is excellent in colorless transparency, in which the metal derived from the catalyst is suppressed from remaining in the polymer without using a high-grade detouching step. It is to provide a method for producing a polymer that can be obtained. A second object of the present invention is to provide a method for producing a polymer capable of executing a ring-opening polymerization reaction with high efficiency by using a metathesis catalyst which is hardly poisoned by a functional group of a monomer. .. The third object of the present invention is to
It is an object of the present invention to provide a method for producing a polymer which does not cause a coloring problem due to a side reaction product in the obtained ring-opening polymer.

[0009]

[Here, M represents a metal atom selected from the group consisting of molybdenum, tungsten, ruthenium, rhenium and tantalum. x is an integer of 0 to 2 and y is an integer of 1 to 6. ]

Component (b): Modifier represented by the general formula R _m AO _n B _p [where R represents a hydrocarbon group having 1 to 20 carbon atoms, and A
Represents a phosphorus atom, a carbon atom or a sulfur atom, and B represents a halogen atom. m is a number from 0 to 2, n is 1 or 2, and p is a number from 1 to 3. ] (C) component: Organoaluminum compound

[0010]

[Chemical 2] [In Chemical Formula 2, D, E, G and J each represent a hydrogen atom, a halogen atom or a monovalent organic group, which may be bonded to each other to form a monocyclic or polycyclic group, and The monocyclic or polycyclic group may have a double bond,
D and E may form an alkylidene group. k is 0 or a positive integer, and q is 0 or 1. ]

In the production method of the present invention,
The monomer represented by is preferably one having a polar group. The amount of the metathesis catalyst used is in the range of 1:500 to 1:50000 in the component (a):specific monomer in molar ratio of the component (a) to the specific monomer, and further 1 It is preferably in the range of 1:1000 to 1:40000, and particularly preferably in the range of 1:10,000 to 1:30000. Further, the component (a) may be a modified form of a metal compound which has been modified in advance with a modifier other than the component (b). Furthermore, as a method for adding the metathesis catalyst,
It is preferable that the modified catalyst component is obtained by previously contacting the component (a) and the component (b), and the modified catalyst component is added to the polymerization reaction system together with the component (c).

The present invention will be described in detail below. <Specific monomer> Specific monomer used in the production method of the present invention
Is a compound having a norbornene structure represented by Chemical Formula 2 above.
It is a thing. As such a specific monomer, a linear polymer is
What can be obtained, specifically, in a ring
Monomers with one double bond are used. Specific monomer
In the above, “J” shown in Chemical formula 2 above is a polar group,
"-(CH ₂)_nCOOR¹Is a polar group represented by
The specific monomer has a high hydrogenated product in the obtained ring-opening polymer.
Good in that it has a glass transition temperature and low hygroscopicity.
Good. In this formula, R¹Has 1 to 12 carbon atoms
Is a hydrocarbon group. Also, the smaller the value of n,
The resulting ring-opening polymer has a high glass transition temperature, which is preferable.
Furthermore, the synthesis of the specific monomer in which n is 0 is
In addition, the glass ring of the obtained ring-opening polymer is easy.
It is preferable in that the transfer temperature becomes high. In addition, above
“D”, “E” and “G” shown in
It is preferably a hydrogen atom or an alkyl group, and
When it is a kill group, a methyl group is particularly preferred. further,
"G" is a methyl group, and "J" is "-(CH
₂)_nCOOR¹Specific monomer that is a polar group represented by
Is particularly preferable because it is easy to manufacture. In addition, above
The specific monomer having k of 1 has a high glass transition point.
Is preferred over k having a value of 0 in that a ring-opening polymer is obtained.
Yes.

Specific examples of the specific monomer represented by the above chemical formula 2
As bicyclo[2.2.1]hept-2-ene,
Tricyclo[5.2.1.0]^2,6]-8-Decene, Tet
Lacyclo[4.4.0.1^2,5． 1^7,10]-3-Dodese
Pentacyclo[6.5.1.1^3,6． 0^2,7． 0
^9,13]-4-Pentadecene, Pentacyclo[7.4.
0.1^2,5． 1^9,12． 0^8,13]-3-Pentadecene, To
Ricyclo[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-carboxymethyi
Rutetracyclo[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-carbo
Xy-n-propyltetracyclo[4.4.0.1^2,5．
1^7,10]-3-Dodecene, 8-carboxyisopropyl
Tetracyclo[4.4.0.1^2,5． 1^7,10]-3-D
Decene, 8-carboxy n-butyl tetracyclo[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-cal
Boxyethyl tetracyclo[4.4.0.1^{2, Five}． 1
^7,10]-3-Dodecene, 8-methyl-8-carboxyn
-Propyltetracyclo[4.4.0.1^2,5．
1^7,10]-3-Dodecene, 8-methyl-8-carboxy
Isopropyltetracyclo[4.4.0.1^2,5． 1
^7,10]-3-Dodecene, 8-methyl-8-carboxyn
-Butyltetracyclo[4.4.0.1^2,5． 1^7,10]
-3-dodecene, dimethanooctahydronaphthalene, d
Cyltetracyclododecene, 6-ethylidene-2-teto
Lacyclododecene, Trimethanooctahydronaphthale
Pentapentacyclo[8.4.0.1^2,5． 1^9,12． 0
^8,13]-3-Hexadecene, 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, 5-ethylidenebicyclo[2.2.
1] hept-2-ene, 8-ethylidene tetracyclo
[4.4.0.1^2,5． 1^7,10]-3-Dodecene, 5-
Fluorobicyclo[2.2.1]hept-2-ene, 5
-Fluoromethylbicyclo[2.2.1]hept-2-
Ene, 5-trifluoromethylbicyclo[2.2.1]
Hept-2-ene, 5-pentafluoroethylbicyclo
[2.2.1] Hept-2-ene, 5,5-difluoro
Bicyclo[2.2.1]hept-2-ene, 5,6-di
Fluorobicyclo[2.2.1]hept-2-ene,
5,5-bis(trifluoromethyl)bicyclo[2.
2.1] Hept-2-ene, 5,6-bis(trifluor
Lomomethyl)bicyclo[2.2.1]hept-2-ene,
5-methyl-5-trifluoromethylbicyclo[2.
2.1] Hept-2-ene, 5,5,6-trifluoro
Bicyclo[2.2.1]hept-2-ene, 5,5,6
-Tris(fluoromethyl)bicyclo[2.2.1]
Put-2-ene, 5,5,6,6-tetrafluorobic
Chloro[2.2.1]hept-2-ene, 5,5,6,6
-Tetrakis(trifluoromethyl)bicyclo[2.
2.1] Hept-2-ene, 5,5-difluoro-6,6
6-bis(trifluoromethyl)bicyclo[2.2.
1] hept-2-ene, 5,6-difluoro-5,6-
Bis(trifluoromethyl)bicyclo[2.2.1]
Put-2-ene, 5,5,6-trifluoro-5-tri
Fluoromethylbicyclo[2.2.1]hept-2-e
5-fluoro-5-pentafluoroethyl-6,6
-Bis(trifluoromethyl)bicyclo[2.2.1]
Hept-2-ene, 5,6-difluoro-5-heptaph
Luoro iso-propyl-6-trifluoromethyl bis
Chloro[2.2.1]hept-2-ene, 5-chloro-
5,6,6-Trifluorobicyclo[2.2.1]hep
To-2-ene, 5,6-dichloro-5,6-bis(tri
Fluoromethyl)bicyclo[2.2.1]hept-2-
Ene, 5,5,6-trifluoro-6-trifluorome
Toxibicyclo[2.2.1]hept-2-ene, 5,
5,6-trifluoro-6-heptafluoropropoxy
Bicyclo[2.2.1]hept-2-ene, 8-fluor
Rotetracyclo[4.4.0.1^2,5． 1^7,10]-3-
Dodecene, 8-fluoromethyltetracyclo[4.4.
0.1^2,5． 1^7,10]-3-Dodecene, 8-difluoro
Methyl tetracyclo[4.4.0.1^2,5． 1^7,10]-
3-dodecene, 8-trifluoromethyltetracyclo
[4.4.0.1^2,5． 1^7,10]-3-Dodecene, 8-
Pentafluoroethyl tetracyclo[4.4.0.1
^2,5． 1^7,10]-3-Dodecene, 8,8-difluorothene
Tracyclo[4.4.0.1^2,5． 1^7,10]-3-Dode
Sene, 8,9-difluorotetracyclo[4.4.0.
1^2,5． 1^7,10]-3-Dodecene,8,8-bis(tri
Fluoromethyl)tetracyclo[4.4.0.1^2,5．
1^7,10]-3-Dodecene, 8,9-bis(trifluoro
Methyl)tetracyclo[4.4.0.1^2,5． 1^7,10]
-3-dodecene, 8-methyl-8-trifluoromethyl
Tetracyclo[4.4.0.1^2,5． 1^7,10]-3-D
Decene, 8,8,9-trifluorotetracyclo[4.
4.0.1^2,5． 1^7,10]-3-Dodecene, 8,8,9
-Tris(trifluoromethyl)tetracyclo[4.
4.0.1^{2, Five}． 1^7,10]-3-Dodecene, 8,8,
9,9-Tetrafluorotetracyclo[4.4.0.1
^2,5． 1^7,10]-3-Dodecene, 8,8,9,9-tet
Lakis(trifluoromethyl)tetracyclo[4.4.
0.1^2,5． 1^7,10]-3-Dodecene,8,8-diflu
Oro-9,9-bis(trifluoromethyl)tetrasic
B [4.4.0.1^2,5． 1^7,10]-3-dodecene,
8,9-difluoro-8,9-bis(trifluoromethyi)
Le) tetracyclo[4.4.0.1^2,5． 1^7,10]-3
-Dodecene, 8,8,9-trifluoro-9-triflu
Oromethyl tetracyclo[4.4.0.1^2,5．
1^7,10]-3-Dodecene, 8,8,9-trifluoro-
9-trifluoromethoxytetracyclo[4.4.0.
1^2,5． 1^7,10]-3-Dodecene,8,8,9-trif
Luoro-9-pentafluoropropoxytetracyclo
[4.4.0.1^2,5． 1^7,10]-3-Dodecene, 8-
Fluoro-8-pentafluoroethyl-9,9-bis
(Trifluoromethyl)tetracyclo[4.4.0.1
^2,5． 1^7,10]-3-Dodecene, 8,9-difluoro-
8-Heptafluoroiso-propyl-9-trifluor
Romethyltetracyclo[4.4.0.1^2,5． 1^7,10]
-3-dodecene, 8-chloro-8,9,9-trifluor
Rotetracyclo[4.4.0.1^2,5． 1^7,10]-3-
Dodecene, 8,9-dichloro-8,9-bis(triflu
Oromethyl)tetracyclo[4.4.0.1^2,5． 1^7,
Ten]-3-Dodecene, 8-(2,2,2-trifluoro
Carboxyethyl)tetracyclo[4.4.0.
1^2,5． 1^7,10]-3-Dodecene, 8-methyl-8-
(2,2,2-trifluorocarboxyethyl) tetra
Cyclo[4.4.0.1^{2, Five}． 1^7,10]-3-Dodecene
And so on. These specific monomers are always
However, it is not necessary to use them alone, and two or more kinds of
It is also possible to carry out a polymerization reaction.

Further, polybutadiene, polyisoprene,
Ring-opening of a specific monomer in the presence of an unsaturated hydrocarbon polymer such as a styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, polynorbornene containing a carbon-carbon double bond in the main chain It may be polymerized. 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> The production method of the present invention is characterized in that the metathesis ring-opening polymerization is carried out in the presence of a metathesis catalyst comprising a combination of components (a) to (c) described in detail below. It is a thing.

Component (a) The component (a) constituting the metathesis catalyst is MO _x Cl _y.
[Wherein M represents a metal atom selected from the group consisting of molybdenum, tungsten, ruthenium, rhenium and tantalum]. x is 0-2
Is an integer of 1 and y is an integer of 1-6. ]. Specific examples of the component (a) include tungsten hexachloride, tungsten oxytetrachloride, tungsten pentachloride, molybdenum pentachloride, molybdenum oxytetrachloride, molybdenum oxytrichloride, ruthenium trichloride, rhenium pentachloride, rhenium oxytetrachloride, Rhenium tetrachloride, tantalum pentachloride, tungsten dioxydichloride, molybdenum dioxydichloride and the like can be mentioned as preferable ones, of which tungsten hexachloride is particularly preferable.

The component (a) may be a modified metal compound represented by MO _x Cl _y . Examples of the compound for modifying the metal compound include t-butanol, cumene hydroperoxide, lauroyl peroxide, benzoyl peroxide, sodium peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, 1,4.
-Dioxane and the like can be mentioned. The amount of these modifiers used is 5 to 100 mol% with respect to the metal compound.

Further, a metal compound solution prepared by dissolving a metal compound or a modified product thereof using a solubilizer may be used as the component (a). Here, as the solubilizer, alcohols such as methanol, ethanol, propanol, butanol, pentanol and hexanol, epoxies such as ethylene chlorohydrin, epichlorohydrin, propylene oxide and ethylene oxide, ethers such as diethyl ether, etc. Can be mentioned. The amount of these solubilizers used is 0.5 to 1500 mol% with respect to the metal compound.

The method for treating the metal compound with these modifiers and solubilizers (method for preparing the metal compound solution) is not particularly limited, but the metal compound is diluted with a solvent such as toluene and then the modifier is added thereto. A method of adding and reacting, and then adding a dissolving agent to prepare a completely homogeneous catalyst solution is preferable. Such modified metal compound (a)
By using it as a component, it is possible to effectively prevent coloring due to a side reaction product, and it is possible to produce a polymer having more excellent colorless transparency.

Component (b) The component (b) constituting the metathesis catalyst has a general formula R _m A
Is O _n B modifier represented by _p [where, R represents a hydrocarbon group having 1 to 20 carbon atoms, A represents a phosphorus atom, a carbon atom or a sulfur atom, B represents a halogen atom. m is a number from 0 to 2, n is 1 or 2, and p is 1 to 3.
Is the number of. ]. Specific examples of the component (b) include dichlorophenylphosphonic acid, dichloromethylphosphonic acid, chlorodiphenylphosphonic acid, chlorodimethylphosphonic acid, phenyl dichlorophosphate, phenyl dibromophosphate, methyl dichlorophosphate, methyl dibromophosphate, oxychloride. Phosphorus, phosphorus oxybromide, acetyl chloride, acetyl bromide, benzoyl chloride, benzoyl bromide, benzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, thionyl chloride, thionyl bromide and the like can be mentioned. Of these, dichlorophenylphosphonic acid and phosphorus oxychloride are particularly preferable.

Component (c) The component (c) constituting the metathesis catalyst is an organoaluminum compound, and specific examples thereof include trimethylaluminum, triethylaluminum, diethylaluminum hydride, diethylaluminum chloride and methylalumoxane. Of these, triethylaluminum is particularly preferred.

<Component ratio> (a) component, (b) component,
The ratio of the component (c) is “(a) component:(b) component:
(C) component (metal atomic ratio)" is 1:0.1:1 to 1:1
The range is 0:30, preferably 1:0.5:2.
The range is 1:7:20. If the relative proportion of each component deviates from the above range, high polymerization activity cannot be stably obtained.

The amount of the metathesis catalyst to be used is such that the molar ratio of the component (a) to the specific monomer is such that "(a) component:specific monomer" is usually 1:500 to 1:50000. And preferably from 1:1000 to 1:40000
Range, more preferably 1:10,000 to 1:3
The range is 0000.

<Method of Adding Metathesis Catalyst> The method of adding each catalyst component [components (a) to (c)] to the polymerization reaction system is not particularly limited. For example, the component (a) and the component (b) may be separately added to the polymerization reaction system,
The modified catalyst component may be obtained by previously contacting the component (a) with the component (b), and the modified catalyst component may be added to the polymerization reaction system. The component (c) may be added to the polymerization reaction system after being mixed with the component (a) and/or the component (b), or the modified catalyst component in advance, or with other catalyst component. Instead, it may be added to the polymerization reaction system and contacted with another catalyst component in the polymerization reaction system. Each catalyst component may be added to the specific monomer and/or reaction solvent in advance and then supplied to the polymerization reaction system, or may be supplied to the polymerization reaction system separately from the specific monomer and reaction solvent. May be. As a preferable addition method, there is a method in which the modified catalyst solution is prepared by adding the component (b) to the dispersion liquid of the component (a), and the modified catalyst solution is added to the polymerization reaction system together with the component (c). it can. According to such an addition method, high polymerization activity can be stably obtained.

<Solvent for Ring-Opening Polymerization Reaction> In the production method of the present invention, the ring-opening polymerization reaction is carried out in a solvent. Examples of the solvent used in the ring-opening polymerization reaction include alkanes such as pentane, hexane, heptane, octane, nonane, and decane, cyclohexane, cycloheptane,
Cycloalkanes such as cyclooctane, decalin and norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene, chlorobutane,
Bromhexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, halogenated alkanes such as tetrachloroethylene,
Compounds such as aryl, ethyl acetate, n-butyl acetate,
Examples thereof include saturated carboxylic acid esters such as iso-butyl acetate and methyl propionate, and ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane, and these can be used alone or in combination. 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, and 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 120°C, preferably 50 to 100°C.

The intrinsic viscosity (η _inh ) of the obtained ring-opening polymer is preferably in the range of 0.2 to 5.0. The number average molecular weight (Mn) is usually 0.8×10 ⁴ as the polystyrene-reduced average molecular weight (solvent: tetrahydrofuran) of the ring-opening polymer measured by GPC.
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 the 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 the hydrogenation reaction of ordinary olefinic compounds can be used. As this hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are known. 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 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. 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 lubricants 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.

Further, the surface of the produced molded article is made of 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. 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 vapor deposition method, a sputtering method, and an ion plating method. As a result, the heat resistance, optical characteristics, chemical resistance, abrasion resistance, moisture permeability, etc. of the molded product can be improved.

The application of the polymer produced by the production method of the present invention is not particularly limited and can be used in a wide range, for example, for general camera lenses,
Lenses such as video camera lenses, 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.

[0033]

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 Step of Modified WCl ₆ Solution In a container purged with nitrogen gas, 5 parts of tungsten hexachloride [(a) component] and 219 parts of dry toluene were mixed to obtain 0.05 M. A suspension of was prepared. Dichlorophenylphosphonic acid [component (b)] 7.3 was added to this suspension.
After adding 7 parts and stirring for 1 hour or more, methanol 1.
A modified WCl ₆ solution was prepared by adding 21 parts and further stirring the system for 1 hour or more. This modified WC
The concentration of WCl ₆ in the l ₆ solution is 0.05 mol/l,
“WCl ₆ :(C ₆ H ₅ )P(O)Cl ₂ :CH ₃ OH
(Molar ratio)" is 1.0:3.0:3.0.

Ring-Opening Polymerization Step In a reaction vessel having a jacket whose inside is replaced with nitrogen gas, 8-methyl-8-carboxymethyltetracyclo[4.4.0.1 ^2,5 . 1 ^{7, 10} ]-3
-400 parts of dodecene, 1200 parts of toluene, and 65 parts of 1-hexene, which is a molecular weight modifier, were charged and heated to 80°C with stirring. Then, 1.6 parts of a toluene solution of triethylaluminum (concentration 1.15 mol/l) as the component (c) and 6.0 parts of the modified WCl ₆ solution (concentration 0.05 mol/l) prepared above. Was added, and ring-opening polymer solution A-1 was obtained by carrying out metathesis ring-opening polymerization for 3 hours while maintaining the jacket temperature at 80°C. In this example, “WCl ₆ :specific monomer (molar ratio)” is 1:5000. In the ring-opening polymer solution A-1 obtained as described above, the yield of the ring-opening polymer was 99.5.
%, intrinsic viscosity (η _inh ) is 0.36 dl/g (in chloroform, 30° C., concentration 0.5 g/dl), GPC
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 4.0×10 ⁴ .

Hydrogenation Step The solution of ring-opening polymer A-1 obtained above (concentration: 25 wt.
%) to 400 parts of chlorohydrocarbon as a hydrogenation catalyst.
Rubonyl tristriphenylphosphine ruthenium 0.
075 parts was added and the hydrogen gas was put in the autoclave.
Pressure 100kg/cm²At 4 o'clock under temperature of 165°C
The hydrogenation reaction was performed by heating for a while. Got
After cooling the reaction solution, the hydrogen gas is released and hydrogenation polymerization is performed.
Body solution A-1 was obtained. In this hydrogenated polymer solution A-1
In addition, the hydrogenation rate was substantially 100%. Also,
When the number average molecular weight Mn was measured in the same manner as described above,
1.2 x 10 ^FourAnd the same value as before hydrogenation
It was.

Detouching Step 400 parts of the hydrogenated polymer solution A-1 obtained above and 100 parts of toluene were charged into a reaction vessel, and lactic acid of 0.
71 parts and 1.15 parts of water are added and stirred at 60° C. for 30 minutes, then 260 parts of methanol are added to give 6 parts.
The mixture was stirred at 0°C for another hour. Then, the inside of the reaction vessel was cooled to room temperature, the poor solvent phase (methanol phase) and the good solvent phase (polymer-containing phase) were separated, and only the poor solvent was extracted.
Next, methanol corresponding to 45% by weight of the extracted poor solvent and toluene corresponding to 55% by weight were added to the reaction vessel and stirred at 60° C. for 1 hour. It cooled to room temperature again, the poor solvent phase and the good solvent phase were isolate|separated, and only the poor solvent was extracted. After repeating this extraction operation with methanol once more, the good solvent phase was separated, and the hydrogenated polymer was recovered from the good solvent phase.

Manufacture of Molded Article 100 parts of the hydrogenated polymer recovered above was added to the antioxidant "Irganox 1076" (manufactured by Ciba Geigy).
After adding 0.2 part, pelletization was carried out using an extruder (extrusion temperature: 290° C.). This pellet-shaped hydrogenated polymer was injection-molded using an injection molding machine "IS90B" (manufactured by Toshiba Machine Co., Ltd.: molding temperature 320°C) to obtain a molded product.

Measurement of Yellowness In order to evaluate the colorless transparency of the molded article, JIS K71
When the yellowness of the molded product was measured according to 05 (transmission method), the yellowness was 2.4 (thickness 3 mm), which was an extremely low value.

[Example 2] A toluene solution of triethylaluminum as the component (c) (concentration: 1.15 mol/l)
Was changed to 0.8 part, and the modified WCl ₆ solution (concentration 0.05 mol/l) was added to 3.0 parts, except that the ring-opening polymerization step of Example 1 was changed. Then, the ring-opening polymer solution A-2 was obtained by the metathesis ring-opening polymerization. In this example, “WCl ₆ :specific monomer (molar ratio)” is 1:10000. In the ring-opening polymer solution A-2 obtained as described above, the yield of the ring-opening polymer was 99.0% and the intrinsic viscosity (η _inh ) was 0.40 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=1.4×10 ⁴ , weight average molecular weight Mw=4.9×1
It was 0 ⁴ . A hydrogenated polymer solution A-2 was obtained by performing the same operation as in the hydrogenation step of Example 1 except that the ring-opened polymer solution A-2 was used instead of the ring-opened polymer solution A-1. .. In this hydrogenated polymer solution A-2, the hydrogenation rate was substantially 100%. Hydrogenated polymer solution A-
In the same manner as in Example 1 except that the hydrogenated polymer solution A-2 was used in place of 1, detouching, production of a molded product, and measurement of yellowness were carried out. 3 mm), which is an extremely low value.

Example 3 A toluene solution of triethylaluminum, which is the component (c), (concentration: 1.15 mol/l)
Was changed to 0.4 part and the modified WCl ₆ solution (concentration 0.05 mol/l) was added to 1.5 part, except that the ring-opening polymerization step of Example 1 was changed. Then, the ring-opening polymer solution A-3 was obtained by the metathesis ring-opening polymerization. In this example, “WCl ₆ :specific monomer (molar ratio)” is 1:20000. In the ring-opening polymer solution A-3 obtained as described above, the yield of the ring-opening polymer was 98.5%, and the intrinsic viscosity (η _inh ) was 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 the number-average molecular weight M.
n=1.5×10 ⁴ , weight average molecular weight Mw=5.2×1
It was 0 ⁴ . A hydrogenated polymer solution A-3 was obtained by performing the same operation as in the hydrogenation step of Example 1 except that the ring-opened polymer solution A-3 was used in place of the ring-opened polymer solution A-1. .. In this hydrogenated polymer solution A-3, the hydrogenation rate was substantially 100%. Hydrogenated polymer solution A-
In the same manner as in Example 1 except that the hydrogenated polymer solution A-3 was used in place of 1, detouching, production of a molded article, and measurement of yellowness were carried out. 3 mm), which is an extremely low value.

[Comparative Example 1] The component (b), dichlorophine
Example except that no phenylphosphonic acid was added
Modified WCl of 1₆Perform the same operation as the solution preparation process
WCl for comparison ₆A solution was prepared. This comparison WC
l₆WCl in solution₆The concentration is 0.05 mol/l,
"WCl₆: CH₃OH (molar ratio)" is 1.0:3.
It is 0. Modified WCl₆Instead of solution, comparative WCl
₆6.0 parts of solution (concentration 0.05 mol/l) was added
Except for the above, metathesis was carried out in the same manner as in the ring-opening polymerization step of Example 1.
The cis ring-opening polymerization was performed to obtain a ring-opening polymer solution B-1. that's all
In the ring-opening polymer solution B-1 obtained as described above,
The yield of ring-opened polymer was 90.5%. Also unique
Viscosity (η_inh) Is 0.37 dl/g (in chloroform,
30°C, concentration 0.5g/dl), measured by GPC
Polystyrene equivalent average molecular weight (developing solvent: tetrahi
Dorofran) has a number average molecular weight Mn=1.1×10.^Four,
Weight average molecular weight Mw=4.2×10^FourMet. Ring opening weight
The ring-opening polymer solution B-1 was used instead of the combined solution A-1.
Except for this, the same operation as in the hydrogenation step of Example 1 was performed.
A hydrogenated polymer solution B-1 was obtained. This hydrogenated polymer
In solution B-1, the hydrogenation rate was substantially 99.9%.
there were. Hydrogenated polymer solution A-1 instead of hydrogenated polymer
Same as Example 1 except that the combined solution B-1 was used.
, Touching, manufacturing molded products, and measuring yellowness
The yellowness was a large value of 6.2 (thickness 3 mm).

Comparative Example 2 A toluene solution of triethylaluminum as the component (c) (concentration: 1.15 mol/l)
Was changed to 0.8 parts, and the addition amount of the comparative WCl ₆ solution (concentration 0.05 mol/l) was changed to 3.0 parts. Similarly, the ring-opening polymer solution B-2 was obtained by carrying out metathesis ring-opening polymerization.
In this example, “WCl ₆ :specific monomer (molar ratio)” is 1:10000. In the ring-opening polymer solution B-2 obtained as described above, the yield of the ring-opening polymer was 80.4%. Also, the intrinsic viscosity (η _inh ) is 0.41 dl/g (in chloroform, 30° C., concentration 0.
5 g/dl), and the average molecular weight in polystyrene conversion by GPC measurement (developing solvent: tetrahydrofuran) is
Number average molecular weight Mn=1.3×10 ⁴ , weight average molecular weight M
w=5.1×10 ⁴ . A hydrogenated polymer solution B-2 was obtained by performing the same operation as in the hydrogenation step of Example 1 except that the ring-opened polymer solution B-2 was used instead of the ring-opened polymer solution A-1. In this hydrogenated polymer solution B-2, the hydrogenation rate was substantially 99.9%. When detouching, production of a molded article and measurement of yellowness were performed in the same manner as in Example 1 except that the hydrogenated polymer solution B-2 was used in place of the hydrogenated polymer solution A-1, yellow was obtained. The degree is 4.4
It was a large value (thickness 3 mm).

Example 4 The same operation as in the step of preparing the modified WCl ₆ solution of Example 1 was performed except that 0.33 parts of t-butanol (modifying agent) was further added to the toluene suspension. A modified WCl ₆ solution was prepared. This modified WC
The concentration of WCl ₆ in the l ₆ solution is 0.05 mol/l,
_{"WCl 6: t-C 4 H} 9 OH: (C 6 H 5) P (O)
Cl ₂ :CH ₃ OH (molar ratio)" is 1.0:0.35:
It is 3.0:3.0. (C) the amount of a toluene solution of triethylaluminum as the component (concentration 1.15 mol / l) was changed to 0.4 parts in place of the modified WCl ₆ solution above modified WCl ₆ solution (concentration 0.05 Mol/l)
Ring-opening polymer solution A-4 was obtained by carrying out metathesis ring-opening polymerization in the same manner as in the ring-opening polymerization step of Example 1 except that 1.5 parts was added. In the ring-opening polymer solution A-4 obtained as described above, the yield of the ring-opening polymer was 98.0%,
The intrinsic viscosity (η _inh ) 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 the number average molecular weight Mn= 1.4 x 10
⁴ , and the weight average molecular weight Mw was 5.1×10 ⁴ . A hydrogenated polymer solution A-4 was obtained by performing the same operation as in the hydrogenation step of Example 1 except that the ring-opened polymer solution A-1 was used in place of the ring-opened polymer solution A-1. .. In this hydrogenated polymer solution A-4, the hydrogenation rate was substantially 100.
%Met. When detouching, production of a molded article, and measurement of yellowness were performed in the same manner as in Example 1 except that the hydrogenated polymer solution A-4 was used in place of the hydrogenated polymer solution A-1, the result was yellow. The degree was 0.9 (thickness 3 mm), which was an extremely low value.

Example 5 In a reaction vessel having a jacket whose inside was replaced with nitrogen gas, 8-
Ethylidene tetracyclo[4.4.0.1 ^2,5 .
^1,7,10 ]-3-dodecene 400 parts and cyclohexane 1
200 parts and 81 parts of 1-hexene, which is a molecular weight modifier, were charged and heated to 80° C. with stirring. Then
0.5 parts of a toluene solution of triethylaluminum (concentration: 1.15 mol/l), which is the component (c), and modified WCl ₆
A solution (concentration: 0.05 mol/l) (1.85 parts) was added, and ring-opening polymer solution A-5 was obtained by performing metathesis ring-opening polymerization for 3 hours while maintaining the jacket temperature at 80°C.
In this example, “WCl ₆ :specific monomer (molar ratio)” is 1:20000. In the ring-opening polymer solution A-5 obtained as described above, the yield of the ring-opening polymer was 98.0% and the intrinsic viscosity (η _inh ) was 0.44 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=1.4×10 ⁴ , weight average molecular weight Mw=5.3×1
It was 0 ⁴ . The ring-opening polymer solution A-5 was added to a large amount of isopropyl alcohol to precipitate a ring-opening polymer, which was filtered to collect the ring-opening polymer and vacuum dried. 100 parts of the obtained ring-opened polymer was dissolved in 2000 parts of cyclohexane, 10 parts of palladium (palladium concentration 5%) supported on activated carbon as a catalyst was added thereto, and hydrogen pressure was 150 kg/cm ² in an autoclave. Temperature 150
The hydrogenation reaction was carried out by heating for 4 hours under the condition of °C. After the obtained reaction solution was cooled, hydrogen gas was released, and the catalyst was filtered from the reaction solution. Then, isopropyl alcohol was added to coagulate the hydrogenated polymer, which was dried and recovered. Hydrogenation rate is virtually 100%
Met. A molded article was produced in the same manner as in Example 1 except that the obtained hydrogenated polymer was used, and the yellowness was measured. The yellowness was 1.0 (thickness 3 mm), which was an extremely low value. It was

Example 6 The modified WCl ₆ solution was prepared in the same manner as in the preparation example of the modified WCl ₆ solution except that 3.50 parts of epichlorohydrin was added in place of methanol.
A Cl ₆ solution was prepared. The concentration of WCl ₆ in this modified WCl ₆ solution was 0.05 mol/l, and "WCl ₆ :
_{(C 6 H 5) P (} O) Cl 2: epichlorohydrin (molar ratio) "is preferably 1.0: 3.0: 3.0. (C) the amount of a toluene solution of triethylaluminum as the component (concentration 1.15 mol / l) was changed to 0.4 parts in place of the modified WCl ₆ solution above modified WCl ₆ solution (concentration 0.05 Mol/l) except that 1.5 parts were added
Metathesis ring-opening polymerization was carried out in the same manner as in the ring-opening polymerization step of Example 1 to obtain a ring-opening polymer solution A-6. In the ring-opening polymer solution A-6 obtained as described above, the yield of the ring-opening polymer was 97.8% and the intrinsic viscosity (η _inh ) was 0.42d.
1/g (in chloroform, 30° C., concentration 0.5 g/d
1), and the polystyrene-reduced average molecular weight (developing solvent: tetrahydrofuran) measured by GPC is number average molecular weight Mn=1.4×10 ⁴ , weight average molecular weight Mw=5.
It was 2×10 ⁴ . A hydrogenated polymer solution A- was prepared in the same manner as in the hydrogenation step of Example 1 except that the ring-opened polymer solution A-6 was used in place of the ring-opened polymer solution A-1.
Got 6. In this hydrogenated polymer solution A-6, the hydrogenation rate was substantially 100%. In the same manner as in Example 1 except that the hydrogenated polymer solution A-6 was used in place of the hydrogenated polymer solution A-1, detouching/manufacturing of a molded article
When the yellowness was measured, the yellowness was 1.0 (thickness: 3 m
m), which was an extremely low value.

Example 7 As the component (b), the modified WCl ₆ solution was prepared in the same manner as in the preparation example of the modified WCl ₆ solution except that 5.80 parts of phosphorus oxychloride was added instead of dichlorophenylphosphonic acid. _Six solutions were prepared. The concentration of WCl ₆ in this modified WCl ₆ solution is 0.05.
The mol/l, “WCl ₆ :POCl ₃ :CH ₃ OH (molar ratio)” is 1.0:3.0:3.0. (C) the amount of a toluene solution of triethylaluminum as the component (concentration 1.15 mol / l) was changed to 0.4 parts in place of the modified WCl ₆ solution above modified WCl ₆ solution (concentration 0.05 Mol/l) except that 1.5 parts were added
Metathesis ring-opening polymerization was carried out in the same manner as in the ring-opening polymerization step of Example 1 to obtain a ring-opening polymer solution A-7. In the ring-opening polymer solution A-7 obtained as described above, the yield of the ring-opening polymer was 97.7%, and the intrinsic viscosity (η _inh ) was 0.42d.
1/g (in chloroform, 30° C., concentration 0.5 g/d
1), and the polystyrene-reduced average molecular weight (developing solvent: tetrahydrofuran) measured by GPC is number average molecular weight Mn=1.4×10 ⁴ , weight average molecular weight Mw=5.
It was 1×10 ⁴ . The hydrogenated polymer solution A- was subjected to the same operations as in the hydrogenation step of Example 1 except that the ring-opened polymer solution A-7 was used in place of the ring-opened polymer solution A-1.
Got 7. In this hydrogenated polymer solution A-7, the hydrogenation rate was substantially 100%. In the same manner as in Example 1 except that the hydrogenated polymer solution A-7 was used in place of the hydrogenated polymer solution A-1, detouching/manufacturing of a molded article
When the yellowness was measured, the yellowness was 1.0 (thickness: 3 m
m), which was an extremely low value.

Example 8 In a reaction vessel having a jacket whose inside was replaced with nitrogen gas, pentacyclo[7.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13 ]-3
-400 parts of pentadecene, 1200 parts of toluene, and 76 parts of 1-hexene that is a molecular weight modifier were charged and heated to 80°C with stirring. Next, a toluene solution of component (c), triethylaluminum (concentration: 1.15)
Mol/l) 0.45 parts and modified WCl ₆ solution (concentration 0.05 mol/l) 1.75 parts were added, and metathesis ring-opening polymerization was carried out for 3 hours while maintaining the jacket temperature at 80° C. A ring-opening polymer solution A-8 was obtained. In this example, “WCl ₆ : specific monomer (molar ratio)” is 1:2
It is 0000. In the ring-opening polymer solution A-8 obtained as described above, the yield of the ring-opening polymer was 97.7%,
Intrinsic viscosity (η _inh ) is 0.43 dl/g (in chloroform, 30° C., concentration 0.5 g/dl), and polystyrene-converted average molecular weight (developing solvent: tetrahydrofuran) by GPC measurement is number average molecular weight Mn= 1.4 x 10
⁴ , and the weight average molecular weight Mw was 5.2×10 ⁴ . A hydrogenated polymer solution A-8 was obtained by performing the same operation as in the hydrogenation step of Example 1 except that the ring-opened polymer solution A-8 was used in place of the ring-opened polymer solution A-1. .. In this hydrogenated polymer solution A-8, the hydrogenation rate was substantially 100.
%Met. When detouching, production of a molded article, and measurement of yellowness were performed in the same manner as in Example 1 except that the hydrogenated polymer solution A-8 was used in place of the hydrogenated polymer solution A-1. The degree was 1.0 (thickness 3 mm), which was an extremely low value.

[Comparative Example 3] The dichlorophine component (b)
Example except that no phenylphosphonic acid was added
Modified WCl of 4₆Perform the same operation as the solution preparation process
WCl for comparison ₆A solution was prepared. This comparison WC
l₆WCl in solution₆The concentration is 0.05 mol/l,
"WCl₆: T-C_FourH₉OH:CH₃OH (mole
Ratio)" is 1.0:0.35::3.0. Modified WC
l₆Instead of solution, comparative WCl₆Solution (concentration 0.
05 mol/l) Example 4 except that 1.5 parts was added
Metathesis ring-opening polymerization similar to the ring-opening polymerization step of
A ring-opening polymer solution B-3 was obtained. Obtained as above
In the ring-opening polymer solution B-3, the yield of the ring-opening polymer was
It stopped at 90.3%. In addition, the intrinsic viscosity (η_inh) Is
0.45 dl/g (in chloroform, 30° C., concentration 0.
5 g/dl) and polystyrene conversion by GPC measurement
The calculated average molecular weight (developing solvent: tetrahydrofuran) is
Number average molecular weight Mn=1.6×10^Four, Weight average molecular weight M
w=5.5×10^FourMet. In ring-opening polymer solution A-1
Example except that the ring-opening polymer solution B-3 was used instead
Perform the same operation as the hydrogenation process of 1 to dissolve the hydrogenated polymer.
Liquid B-3 was obtained. In this hydrogenated polymer solution B-3
The hydrogenation rate was substantially 100%. Hydrogen addition weight
Use the hydrogenated polymer solution B-3 instead of the combined solution A-1.
In the same manner as in Example 1 except that
When manufacturing and measuring the yellowness, the yellowness was 1.6 (thickness
It was 3 mm).

Example 9 A toluene solution of triethylaluminum as the component (c) (concentration: 1.15 mol/l)
Was changed to 0.27 part, and the modified WCl ₆ solution (concentration 0.05 mol/l) was added to 1.0 part, except that the ring-opening polymerization step of Example 1 was changed. Then, the ring-opening polymer solution A-9 was obtained by the metathesis ring-opening polymerization.
Incidentally, in this example, "WCl _6: specific monomers (molar ratio)" is 1: 30000. In the ring-opening polymer solution A-9 obtained as described above, the ring-opening polymer yield was 98.0%, and the intrinsic viscosity (η _inh ) was 0.44 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=1.4×10 ⁴ , weight average molecular weight Mw=5.3×1
It was 0 ⁴ . A hydrogenated polymer solution A-9 was obtained by performing the same operation as in the hydrogenation step of Example 1 except that the ring-opened polymer solution A-9 was used in place of the ring-opened polymer solution A-1. .. In this hydrogenated polymer solution A-9, the hydrogenation rate was substantially 100%. Hydrogenated polymer solution A-
In the same manner as in Example 1 except that the hydrogenated polymer solution A-9 was used in place of 1, detouching, production of a molded article, and measurement of yellowness were carried out. 3 mm), which is an extremely low value. The above results are summarized in Table 1 below.
Shown in.

[0051]

[Table 1]

In Table 1, "*1" means 8-methyl-8-carboxymethyltetracyclo[4.4.
0.1 ^2,5 . ^1,7,10 ]-3-indicates dodecene, "*2"
Is 8-ethylidenetetracyclo[4.4.0.
1 ^2,5 . 1 ^7,10 ]-3-dodecene, and "*3" is
Pentacyclo[7.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13 ]
Indicates 3-pentadecene.

[0053]

Industrial Applicability According to the production method of the present invention, it is possible to produce a high-quality ring-opening polymer excellent in colorless transparency as a result of suppressing the metal derived from the catalyst from remaining in the polymer. it can. Further, the catalyst system in the production method of the present invention is not easily poisoned by the functional group of the monomer, and the ring-opening polymerization reaction can be carried out with high efficiency (yield) with a small amount of catalyst. .. Furthermore, according to the production method of the present invention, generation of hydrogen chloride from the catalyst is suppressed, and as a result, deterioration of the ring-opening polymer is prevented. Moreover, since the ring-opening polymerization reaction is carried out at a relatively low temperature, side reactions do not occur, and the problem of coloring due to side reaction products is avoided.

Claims (1)

[Claims] 1. A method for producing a thermoplastic polymer, which comprises a step of ring-opening polymerization of a monomer comprising at least one norbornene derivative represented by the following chemical formula 1, wherein the following components (a) to (c): Component) in the presence of a metathesis catalyst consisting of a component, in the solvent metathesis ring-opening polymerization, a method for producing a thermoplastic polymer. Component (a): Metal compound represented by MO _x Cl _y [where M represents a metal atom selected from the group consisting of molybdenum, tungsten, ruthenium, rhenium and tantalum. x is an integer of 0 to 2 and y is an integer of 1 to 6. Component (b): Modifier represented by the general formula R _m AO _n B _p [wherein R represents a hydrocarbon group having 1 to 20 carbon atoms, and A
Represents a phosphorus atom, a carbon atom or a sulfur atom, and B represents a halogen atom. m is a number from 0 to 2, n is 1 or 2, and p is a number from 1 to 3. ] Component (c): Organoaluminum Compound embedded image [In Chemical Formula 1, D, E, G and J each represent a hydrogen atom, a halogen atom or a monovalent organic group, which may be bonded to each other to form a monocyclic or polycyclic group, and The monocyclic or polycyclic group may have a double bond,
D and E may form an alkylidene group. k is 0 or a positive integer, and q is 0 or 1. ]