JPH061831A - Production of polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer having a narrow molecular weight distribution, improved flow and low birefringence by effecting the ring opening polymerization of a specified norbornene derivative while adding this derivative and a metathesis catalyst to a solution of a molecular weight modifier. CONSTITUTION:A molecular weight modifier is dissolved in a solvent to form a molecular weight modifier solution. This solution is introduced into a reactor and heated to a polymerization temperature of 0-200 deg.C. While a norbornene derivative of the formula (wherein A and B are each H or a 1-10 C hydrocarbon group; X and Y are each H, halogen or a monovalent organic group; and m is 0 or 1) and a metathesis catalyst comprising at least one member selected from among a wolfram compound, a molybdenum compound and a rhenium compound and at least one member selected from among compounds each containing an element of group IA, IIA, IIB, IIIA, IVA or IVB of the Deming's periodical table and having at least one bond of the element to carbon or a bond of the element to hydrogen are continuously or intermittently introduced into the heated solution through separate lines, the ring opening polymerization of the norbornene derivative is effected.

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 a narrow molecular weight distribution.

[0002]

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 a transparent resin preferably used for such an application, a ring-opening polymer 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, These ring-opening polymers and hydrogenated products have transparency, low water absorption, low birefringence, and high heat resistance.

However, among these ring-opening polymers, those having a large molecular weight have insufficient fluidity, are difficult to process, and are prone to form birefringence. In such a case, it is known to control the molecular weight by carrying out a metathesis ring-opening polymerization reaction in the presence of a molecular weight regulator composed of an olefin compound.

[0004]

However, the molecular weight of the ring-opening polymer cannot be sufficiently controlled only by performing the metathesis ring-opening polymerization reaction in the presence of the molecular weight regulator. That is, (1) the molecular weight modifier composed of an olefin compound has a low activity with respect to a monomer composed of a norbornene derivative, and when the ratio of the molecular weight modifier to the monomer is too small, The ring-opening polymer thus obtained has a large molecular weight. A ring-opening polymer having a large molecular weight does not have sufficient fluidity and low birefringence, and a gel may be generated during injection molding of a hydrogenated product of such a ring-opening polymer. . (2) If the ratio of the molecular weight regulator to the monomer is too large, the molecular weight of the ring-opening polymer obtained due to the excess molecular weight regulator becomes too small, and the hydrogen of such a ring-opening polymer becomes too small. Silver streaks may occur during injection molding of the additive, and stickiness may occur on the surface of the molded product. (3) The monomer composed of the norbornene derivative is dissolved in a solvent together with the metathesis catalyst and the molecular weight modifier,
Usually, they are all put together in a reaction vessel and subjected to a ring-opening polymerization reaction. Therefore, at the start of the ring-opening polymerization reaction, even if the ratio of the molecular weight modifier to the monomer is appropriate, the ratio of the molecular weight modifier to the monomer gradually increases as the ring-opening polymerization reaction proceeds. Then, the ring-opening polymer obtained in the latter stage of the reaction causes the same problem as in the above (2). this is,
Since the rate of decrease of the monomer due to the ring-opening polymerization reaction is higher than the rate of decrease of the olefin compound which is the molecular weight modifier, the ratio of the molecular weight modifier to the monomer changes (increases) with time. is there. Further, when the ratio of the molecular weight regulator to the monomer is too small in the early stage of the reaction and this ratio increases over time and becomes too large in the latter stage of the reaction, the molecular weight distribution becomes considerably wide, and The ring-opening polymer thus obtained has both the problems (1) and (2).

As described above, it is difficult to control the molecular weight by simply allowing a molecular weight regulator composed of an olefin compound to coexist in the reaction system, and a metathesis ring-opening polymer having a suitable molecular weight distribution cannot be obtained. .

[0006] Against this background, the present inventor charged a part of the monomer to be subjected to the ring-opening polymerization reaction into the reaction system together with the metathesis catalyst and the molecular weight modifier to start the ring-opening polymerization reaction, A method for producing a polymer in which the ring-opening polymerization reaction is allowed to proceed while the rest of the monomer is continuously or intermittently added to the reaction system was found, and a proposal was made (Japanese Patent Application No. 3-324031). See the book). According to this production method, a metathesis ring-opening polymer having a suitable molecular weight distribution can be obtained. However, in this method, if the addition of the rest of the monomer is not started immediately after the start of the ring-opening polymerization reaction, the ring-opening polymer cannot be obtained in a high yield, and
In order to achieve a high yield, it is necessary to accurately control the rate of addition of the rest of the monomer, and this is not sufficiently satisfactory as a method for stably obtaining a high yield polymer.

The present invention has been made based on the above circumstances, and its object is to exhibit good fluidity and low birefringence and to injection-mold a hydrogenated product of a ring-opening polymer. It is an object of the present invention to provide a method for producing a polymer, which is capable of stably producing a polymer having a suitable molecular weight distribution in which a silver streak or gel does not occur at high yield in a high yield.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a monomer composed of a norbornene derivative to be subjected to a ring-opening polymerization reaction and a metathesis catalyst are used. By adding continuously or intermittently to a solution in which a molecular weight modifier is dissolved, a low molecular weight substance causing silver streak and a high molecular weight substance causing gel generation are not contained, and the molecular weight distribution of It was found that a narrow ring-opening polymer can be stably obtained with a high yield, and the present invention was completed based on such findings.

That is, in the method for producing a polymer of the present invention, a monomer comprising at least one norbornene derivative represented by the following chemical formula 2 (hereinafter also referred to as "specific monomer") is used.
A method for producing a polymer, which comprises a ring-opening polymerization step in which metathesis ring-opening polymerization is carried out in the presence of a metathesis catalyst and a molecular weight controlling agent, wherein the molecular weight controlling agent is dissolved in a solvent in the ring-opening polymerization step to prepare a molecular weight controlling agent solution. Was prepared, and the specific monomer and the metathesis catalyst were added to the molecular weight regulator solution,
It is characterized in that the ring-opening polymerization reaction is allowed to proceed while being added continuously or intermittently.

[0010]

[Chemical 2]

[Wherein A and B are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, X and Y represent hydrogen atoms, halogen atoms or monovalent organic groups, and m is 0 or 1] Is. ]

The present invention will be specifically described below. <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 2 above. Among the specific monomers, the specific monomer in which X or Y in the above Chemical Formula ₂ is a polar group, particularly a group represented by the formula — (CH ₂ ) _n COOR ¹ , is a hydrogenated product of the resulting ring-opening polymer. Is preferable in that it has 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 2 are preferably an alkyl group, particularly a methyl group, and particularly, this 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 Further, the specific monomer in which m is 1 in the above chemical formula 2 is more preferable than the one in which m is 0 in that a ring-opening polymer having a high glass transition point is obtained.

Specific examples of the specific monomer represented by the above chemical formula 2 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-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, norbornene, dimethanooctahydronaphthalene, ethyltetracyclododecene, trimethanooctahydronaphthalene and the like can be mentioned. Of these, 8-methyl-8-carboxymethyltetracyclo [4.4.0.
1 ^2,5 . ^1,7,10 ] -3-dodecene is preferable because the polymer obtained by ring-opening polymerization of this has a high glass transition temperature and low hygroscopicity. 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 the specific monomer and the copolymerizable monomer may be combined. Ring-opening copolymerization may be carried out. Specific examples of the copolymerizable monomer used in this case include cyclobutene, cyclopentene, cycloheptene, cyclooctene, tricyclo [5.2.1.
Cycloolefins such as 0 ^2,6 ] -3-decene can be mentioned. Furthermore, polybutadiene, polyisoprene,
Ring-opening of a specific monomer in the presence of an unsaturated hydrocarbon polymer containing a carbon-carbon double bond in the main chain such as styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, polynorbornene 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> In the present invention, the ring-opening polymerization reaction is carried out in the presence of a metathesis catalyst. This metathesis catalyst comprises (a) at least one selected from compounds of W, Mo and Re, (b) an element of Group IA (for example, Li, Na, K, etc.) of the periodic table of Deming, and an element of Group IIA (for example, Mg, Ca, etc., Group IIB elements (eg Z
n, Cd, Hg, etc., III group A elements (eg, B, Al)
Etc.), IVA group elements (eg Si, Sn, Pb etc.) or IVB group elements (eg Ti, Zr etc.) compounds having at least one element-carbon bond or element-hydrogen bond. A catalyst comprising a combination with at least one selected. Further, in this case, an additive (c) described below may be added to enhance the activity of the catalyst. Representative examples of W, Mo or Re compounds suitable as the component (a) include WCl ₆ , MoCl ₅ and ReOCl.
₃ and compounds described in JP-A-1-240517 can be exemplified. Specific examples of the component (b) include n-C ₄ H ₉ Li and (C
₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C
₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl ₂ ,
Methylalumoxane, LiH, etc.
The compounds described in JP-A-7 can be mentioned. As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be preferably used, and further, the compounds shown in JP-A-1-240517 are used. be able to.

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: 500-1: 50000. , Preferably in the range of 1: 1000 to 1: 10000. The ratio of the component (a) to the component (b) is such that the metal atom ratio of (a) :( b) is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30. The molar ratio of the components (a) and (c) is such that (c) :( a) is 0.
005: 1 to 15: 1, preferably 0.05: 1 to 7:
The range is 1.

<Solvent for Ring-Opening Polymerization Reaction> Solvent used in the ring-opening polymerization reaction (solvent for the solution of the molecular weight modifier, solvent for the specific monomer and / or metathesis catalyst)
Examples include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, and norbornane; aromatics such as benzene, toluene, xylene, ethylbenzene, and cumene. Hydrocarbons, chlorobutane, bromhexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene and other halogenated alkanes, compounds such as aryl, ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate , Saturated carboxylic acid esters such as dimethoxyethane, ethers such as dibutyl ether, tetrahydrofuran, dimethoxyethane, etc. There can be used as a mixture. Of these, aromatic hydrocarbons are preferred. As for the amount of the solvent used, "solvent: specific monomer (weight ratio)" is
The amount is usually 1: 1 to 10: 1, preferably 1:
The amount is 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 and styrene, and among these, 1-butene and 1-hexene are particularly preferable.
These molecular weight regulators can be used alone or in admixture of two or more. The amount of the molecular weight modifier used is 0.005 to 0.4 mol, preferably 0.02 to 0.2 mol, relative to 1 mol of the specific monomer used in the ring-opening polymerization reaction.
It is set to 3 mol.

<Ring-Opening Polymerization Step> In the ring-opening polymerization step, first, (1) the above-mentioned molecular weight regulator is dissolved in a solvent to prepare a molecular weight regulator solution, and then (2) a specific monomer and , The metathesis catalyst is added to the solution of the molecular weight regulator to proceed the ring-opening polymerization reaction. Here, the addition of the specific monomer and the metathesis catalyst may be continuous or intermittent.

In preparing the molecular weight regulator solution,
Although all of the finally used molecular weight regulator may be dissolved in a solvent to prepare a molecular weight regulator solution, a part (60 to 99 mol%) of the molecular weight regulator is used to prepare the molecular weight regulator solution. The rest (40 to 1 mol%) of the prepared molecular weight modifier may be added to the reaction system together with the specific monomer as the ring-opening polymerization reaction proceeds. The latter method, in which the molecular weight modifier is divided and supplied to the reaction system, is preferable because the obtained ring-opening polymer can have a narrower molecular weight distribution. In addition, before the metathesis catalyst is added to the molecular weight regulator solution, the molecular weight regulator solution contains a part of the specific monomer (1 to 2 of the specific monomers to be used in the ring-opening polymerization reaction).
0 mol%) may be dissolved in advance.

As the method for adding the specific monomer and the metathesis catalyst, the specific monomer and the metathesis catalyst are dissolved in a common solvent to prepare a "monomer-catalyst solution", and the "monomer-catalyst solution" is prepared. Method of adding "catalyst solution" to molecular weight regulator solution, adding specific monomer (or specific monomer solution) and metathesis catalyst (or metathesis catalyst solution) to molecular weight regulator solution separately from different routes However, in the latter method of separately adding from different routes, the specific monomer and the metathesis catalyst are added before the start of the ring-opening polymerization reaction in the molecular weight regulator solution (reaction system). It is preferable because it does not coexist. Further, the components (a) and (b) of the metathesis catalyst are preferably added separately from different routes in order to avoid mixing before the initiation of the ring-opening polymerization reaction. Then, the specific monomer (solution), the component (a) (solution),
When the component (b) and the component (solution) are separately added from different routes, the ratio of addition to the solution of the molecular weight regulator "specific monomer: component (a): component (b)" should always be constant. In addition, it is preferable to keep each addition rate constant. The addition time of the specific monomer and the metathesis catalyst is usually 5 minutes to 24 hours, preferably 1 to 5 hours.

A specific example of the ring-opening polymerization step will be described. A solution of a molecular weight regulator obtained by dissolving a molecular weight regulator in a solvent is charged into a reaction vessel and heated to a polymerization temperature. Then, the specific monomer (solution), the component (a) (solution), and the component (b) (b) were continuously added to the molecular weight regulator solution in the reaction vessel from different lines. While allowing the ring-opening polymerization reaction to proceed, and after the addition is completed, the ring-opening polymerization reaction is continued by further heating. here,
The reaction temperature in the ring-opening polymerization reaction is usually 0 to 20.
The temperature is 0 ° C., preferably 20 to 180 ° C. The reaction pressure is usually atmospheric pressure to 30 atm, preferably atmospheric pressure to 10 atm.

By the above ring-opening polymerization step, a metathesis ring-opening polymer having a narrow molecular weight distribution can be obtained. in this way,
The reason why a ring-opening polymer having a narrow molecular weight distribution can be obtained is as follows.
This is because during the ring-opening polymerization reaction, the ratio of the molecular weight modifier to the specific monomer added continuously or intermittently is maintained at a substantially constant ratio. The molecular weight modifier is gradually consumed along with the polymerization reaction of the specific monomer, but by adding an amount commensurate with the consumed amount together with the specific monomer to the reaction system, the molecular weight can be improved. A polymer with a narrow distribution can be obtained.

The intrinsic viscosity (η _inh ) 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-opening polymer is usually 0.8 × 10 ⁴ as the number average molecular weight (M _n ).
To 10 × 10 ^4, preferably 1.5 × 10 ⁴ ~8 × 10
⁴ , more preferably 2.0 × 10 ^{4 to} 6.0 × 10 ^4, and the weight average molecular weight (M _w ) is usually 2.5 × 10 ^4.
To 30 × 10 ⁴ , preferably 3.0 × 10 ^{4 to} 25 × 1
It is set to 0 ⁴ , more preferably 4.0 × 10 ^{4 to} 20 × 10 ⁴ . The molecular weight distribution (M _w / M _n ) is usually 1.
5 to 4.5, preferably 1.5 to 4.0, 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, trichlorobistriphenylphosphine ruthenium, and chlorohydrocarbonylbistriphenylphosphine ruthenium. The catalyst may be in the form of powder or particles. These hydrogenation catalysts are "ring-opening polymer:
Hydrogenation catalyst (weight ratio) "is 1: 1 × 10 ^-4 to 1: 2
It is used at a ratio of. 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 process 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 by 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 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 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,
It can be particularly suitably used as an optical material such as lenses for video cameras, telescope lenses, lenses for laser beams, optical discs such as optical video discs, audio discs, document file discs and memory discs.

[0030]

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". Also,
In Examples 1 to 3 and Comparative Examples below, the "specific monomer" is "8-methyl-8-" represented by the following chemical formula 3.
Carboxymethyl tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene "was used.

[0031]

[Chemical 3]

Example 1 Ring-Opening Polymerization Step The inside of a reaction vessel having a jacket was replaced with nitrogen gas, and 15 parts of toluene and 0.54 part of 1-hexene (molecular weight modifier) were placed in the reaction vessel. Was charged and heated to 80 ° C. with stirring. Next, in this solution (molecular weight regulator solution) in the reaction vessel, 30 parts of the specific monomer,
A solution of tungsten hexachloride in dimethoxyethane (concentration: 0.
(05 mol / l) 0.75 part of a catalyst solution dissolved in 50 parts of toluene, and 0.6 part of a toluene solution of diethylaluminum chloride (concentration 1.20 mol / l) in 24 parts of toluene.
The catalyst solution dissolved in 1 part was continuously added from different lines over 1 hour. In the meantime,
The jacket temperature of the reaction vessel was maintained at 80 ° C. After adding the specific monomer and the total amount of each catalyst solution, the reaction temperature was adjusted to 8
While maintaining the temperature at 0 ° C., the ring-opening polymerization reaction was performed for 2 hours.
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

Ring-opening polymer A-obtained as described above
The yield of 1 is 99.4% and the intrinsic viscosity (η _inh ) is 0.53.
dl / 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 M _n = 2.1 × 10 ⁴ , weight average molecular weight M _w = 7.
It was 3 × 10 ⁴ (M _w / M _n = 3.5).

Hydrogenation Step 100 parts of the ring-opening polymer A-1 was mixed with 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 4 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 described above and found to be 2.1 × 10 ⁴ , which was the same as before hydrogenation.

Production of optical disk plate To 100 parts of the obtained hydrogenated polymer, 0.2 part of antioxidant "Irganox 1010" (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 processed by injection molding machine "DISK
5 ”(manufactured by Sumitomo Heavy Industries, Ltd .: molding temperature 300 ° C.) was used for injection molding to manufacture an optical disk plate. When the appearance of this optical disk plate was visually inspected, generation of silver streaks and gel was not observed. The birefringence value was 12 which was good.

[Example 2] In the ring-opening polymerization step, the amount of 1-hexene initially charged in the reaction vessel was changed to 0.33 part to prepare a solution of the molecular weight regulator, which was added to a toluene solution of diethylaluminum chloride. Instead, a toluene solution of triethylaluminum (concentration 1.15 mol / l) 0.1
Parts, the molecular weight regulator solution (toluene 15 parts, 1 part)
-0.33 parts of hexene), a ring-opening polymerization reaction was carried out in the same manner as in Example 1 except that 0.11 part of 1-hexene was continuously added together with the specific monomer, and a white powdery product was obtained. A ring polymer A-2 was obtained. The yield of the ring-opening polymer A-2 obtained as described above is 99.2%, the intrinsic viscosity (η _inh ) is 0.54 dl / g, and the polystyrene-converted average molecular weight by GPC measurement is several Average molecular weight M _n = 2.4 × 1
0 ⁴ , weight average molecular weight M _w = 7.4 × 10 ⁴ (M _w / M
_n = 3.1). A hydrogenation step was performed in the same manner as in Example 1 except that the ring-opening polymer A-2 was used in place of the ring-opening polymer A-1, and the obtained hydrogenated polymer was used in Examples. An optical disc was manufactured in the same manner as in 1. When the appearance of this optical disk plate was visually inspected, generation of silver streaks and gel was not observed. Also,
The birefringence value was 16, which was good.

Example 3 In the ring-opening polymerization step, the amount of 1-hexene initially charged in the reaction vessel was changed to 0.22 part to prepare a solution of the molecular weight regulator, and the solution of the molecular weight regulator (toluene) was prepared. (15 parts, 1-hexene 0.22 part), the ring-opening polymerization reaction was carried out in the same manner as in Example 1 except that 0.09 part of 1-hexene was continuously added together with the specific monomer. A powdery ring-opening polymer A-3 was obtained. The yield of the ring-opening polymer A-3 obtained as described above is 99.
1%, intrinsic viscosity (η _inh ) is 0.67 dl / g,
The polystyrene-reduced average molecular weight by GPC measurement is number average molecular weight M _n = 3.4 × 10 ⁴ , weight average molecular weight M _w.
= 1.05 × 10 ⁵ (M _w / M _n = 3.1).
A hydrogenation step was carried out in the same manner as in Example 1 except that the ring-opening polymer A-3 was used in place of the ring-opening polymer A-1, and the obtained hydrogenated polymer was used in Examples. An optical disc was manufactured in the same manner as in 1. When the appearance of this optical disk plate was visually inspected, generation of silver streaks and gel was not observed. Further, the birefringence value was as good as 15.

Comparative Example 1 The inside of a reaction vessel having a jacket was replaced with nitrogen gas, and 65 parts of toluene, 0.91 part of 1-hexene, and a toluene solution of diethylaluminum chloride (concentration) were placed in this reaction vessel. 1.20 mol /
l) 0.6 parts were added and heated to 80 ° C. with stirring. Then, 0.7 part of a solution of tungsten hexachloride in dimethoxyethane (concentration: 0.05 mol / l) was added. After 5 minutes, the reaction temperature was kept at 80 ° C., and 35 parts of a toluene solution of the specific monomer (specific monomer: toluene = 25 parts: 10
Part) was continuously added over 1 hour to carry out the ring-opening polymerization reaction. After the total amount of the specific monomer was added, the ring-opening polymerization reaction was further performed for 2 hours while maintaining the reaction temperature at 80 ° 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 then vacuum dried to obtain a white powdery ring-opening polymer a-4. It was The yield of the ring-opening polymer a-4 obtained as described above was 56%. The intrinsic viscosity (η _inh ) of this ring-opening polymer a-4 was 0.49 dl / g (in chloroform, 3
0 ° C., concentration 0.5 g / dl), and polystyrene-reduced average molecular weight by GPC measurement is number average molecular weight M _n =
1.1 × 10 ⁴ , weight average molecular weight M _w = 4.5 × 10 ^4.
(M _w / M _n = 4.1).

Comparative Example 2 The inside of a reaction vessel having a jacket was replaced with nitrogen gas, and 75 parts of toluene, 25 parts of a specific monomer, and 1-hexene 1.8 were placed in the reaction vessel.
And 0.32 part of a toluene solution of diethylaluminum chloride (concentration 1.20 mol / l) were charged and heated to 80 ° C. with stirring. Then, a solution of tungsten hexachloride in dimethoxyethane (concentration 0.05 mol / l)
0.38 parts was added to start the ring-opening polymerization reaction. The ring-opening polymerization reaction was carried out for 3 hours while maintaining the reaction temperature at 80 ° 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-5. It was
The yield of the ring-opening polymer a-5 obtained as described above is 9
4.7%, intrinsic viscosity (η _inh ) was 0.51 dl / g, polystyrene-converted average molecular weight by GPC measurement was number average molecular weight M _n = 1.1 × 10 ⁴ , weight average molecular weight M _w = 5. It was 0.0 * 10 < ⁴ > ( _Mw / _Mn = 4.6). A hydrogenation step was performed in the same manner as in Example 1 except that the ring-opening polymer a-5 was used in place of the ring-opening polymer A-1, and the obtained hydrogenated polymer was used in the examples. An optical disc was manufactured in the same manner as in 1. When the appearance of this optical disk plate was visually inspected, the occurrence of silver streaks was recognized. The birefringence value was 50 or more.

Example 4 The ring-opening polymerization reaction was carried out in the same manner as in Example 2 except that 24 parts of 6-ethylidene-2-tetracyclododecene was used as the specific monomer in the ring-opening polymerization step. , A white powdery ring-opening polymer A-6 was obtained. The yield of the ring-opening polymer A-6 obtained as described above was 98.5% and the intrinsic viscosity (η _inh ) was 0.52 dl / g.
The average molecular weight in terms of polystyrene measured by GPC is number average molecular weight M _n = 2.2 × 10 ⁴ , weight average molecular weight M _w = 6.8 × 10 ⁴ (M _w / M _n = 3.1). there were. A hydrogenation process was carried out in the same manner as in Example 1 except that the ring-opening polymer A-6 was used in place of the ring-opening polymer A-1, and the obtained hydrogenated polymer was used in Examples. An optical disc was manufactured in the same manner as in 1. When the appearance of this optical disk plate was visually inspected, generation of silver streaks and gel was not observed. The birefringence value was 25, which was good.

[0041]

According to the production method of the present invention, the ring-opening polymerization reaction is allowed to proceed while continuously or intermittently adding the specific monomer and the metathesis catalyst to the solution of the molecular weight regulator, so that the low molecular weight The formation of a polymer and a high molecular weight product is suppressed, and a ring-opening polymer having a narrow molecular weight distribution can be stably obtained with a high yield. The obtained ring-opening polymer exhibits good fluidity and low birefringence, and furthermore, silver streaks and gel do not occur during injection molding of the hydrogenated product of the ring-opening polymer.

Claims (1)

[Claims] 1. A method for producing a polymer, which comprises a ring-opening polymerization step in which a monomer comprising at least one norbornene derivative represented by the following chemical formula 1 is subjected to metathesis ring-opening polymerization in the presence of a metathesis catalyst and a molecular weight modifier. In the ring-opening polymerization step, a molecular weight regulator is dissolved in a solvent to prepare a molecular weight regulator solution, and a monomer and a metathesis catalyst consisting of a norbornene derivative are continuously added to the molecular weight regulator solution. Alternatively, the method for producing a polymer is characterized in that the ring-opening polymerization reaction is allowed to proceed while being intermittently added. [Chemical 1] [In Chemical Formula 1, A and B are a hydrogen atom or C1-C10.
Wherein X and Y represent a hydrogen atom, a halogen atom or a monovalent organic group, and m is 0 or 1. ]