JPS6139328B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a polymer with excellent impact resistance. More specifically, 5-cyano-bicyclo[2.2.1]-heptene-2 or a mixture of 5-cyano-bicyclo[2.2.1]-heptene-2 or a mixture thereof with at most 50 mol% of a cycloolefin compound is defined as "a carbon-carbon-carbon double bond in the molecule." (A) A, A, B, B, A
and an organometallic compound having at least one metal selected from the group consisting of group B metals, (B)
"Tungsten or molybdenum compounds" (hereinafter referred to as "transition metal compounds") or these compounds and (C) water, hydrogen peroxide, oxygen-containing organic compounds,
Nitrogen-containing organic compounds, halogen-containing organic compounds,
and at least one activator selected from the group consisting of phosphoric acid-containing organic compounds, sulfur-containing organic compounds and metal-containing organic compounds. The present invention relates to a method for producing a polymer. Some of the inventors have discovered that cyano groups (nitrile groups)
It was discovered that polymers with various excellent physical properties could be obtained by ring-opening polymerization of norbornene derivatives having
No. 50-23720). The ring-opened polymer obtained by the above method has superior impact resistance compared to commonly used vinyl chloride resins (hereinafter referred to as "PVC") and propylene-based resins (hereinafter referred to as "PP"). Not only the tensile strength is higher than PP, PVC
It has excellent heat resistance (high Vikato softening point), so it can be used at relatively high temperatures. (Refer to the specification of Japanese Patent Publication No. 50-23720). However, although the ring-opened polymers described above are superior in various physical properties compared to other commonly used synthetic resins, these physical properties cannot necessarily be said to be sufficient. For example, when molded products that require high impact resistance, such as mechanical parts, window frames, helmets, lighting covers, and electrical appliance parts, the impact resistance of these molded products must always be satisfactory. No, no. In order to improve the above-mentioned impact resistance, some of the inventors of the present invention have found that it is effective to blend a rubber-like material or an impact-resistant resin, and that a resin with excellent impact resistance can be obtained. , has already been proposed (see the specifications of Japanese Patent Application Laid-open Nos. 50-45853 and 50-62248). However, although the composition obtained in this way has improved impact resistance, it also reduces the tensile strength of the ring-opened polymer and causes flow marks to appear on the surface of the molded product during injection molding. Not only does this deteriorate the appearance of the object, but it may also cause problems in the reproducibility of physical properties. Furthermore, if a ring-opening polymer with a relatively small molecular weight is used to improve the processability of the composition, the effect of improving impact resistance by incorporating a rubbery material will be significantly reduced. be. Furthermore, a norbornene derivative having a polar substituent is combined with an organometallic compound in the presence of a relatively large amount (100 parts by weight or more per 100 parts by weight of the norbornene derivative) of an unsaturated polymer (generally a rubber-like material). A method for producing block and/or graft copolymers by contacting them with a contact system consisting of a transition metal compound is known (Japanese Patent Application Laid-Open No.
50-59500). This method improves the oil resistance and mechanical properties such as green strength and elongation of unsaturated polymers, and is therefore effective in modifying rubber-like (unsaturated polymers), for example. However, the effectiveness of the method of block and/or graft copolymerization of norbornene derivatives in the presence of a relatively small amount of unsaturated polymer has not been clearly demonstrated. The present inventors have discovered that 5-cyano-bicyclo[2.
As a result of various searches to improve the impact resistance of ring-opened polymers of 2.1]-heptene-2, we found that 5-cyano-bicyclo[2.2.1]-heptene-2 or at most 50 mol% of this A mixture of organic metal compounds and transition metal compounds, or these compounds and water, hydrogen peroxide, oxygen-containing organic compounds, and nitrogen-containing organic compounds, in the presence of 1 to 30% by weight of an unsaturated polymer, is converted into a cycloolefin-based compound. , at least one activator selected from the group consisting of halogen-containing organic compounds, phosphoric acid-containing organic compounds, sulfur-containing organic compounds, and metal-containing organic compounds. The inventors have discovered that it is possible to obtain a polymer that not only has dramatically superior impact properties but also has a relatively low melt viscosity (excellent processability), and has thus arrived at the present invention. That is, the polymer obtained by the present invention is
Compared to a composition of a ring-opened polymer of 5-cyano-bicyclo[2.2.1]-heptene-2 having equivalent impact resistance, it exhibits extremely superior melt fluidity. Furthermore, the polymer obtained according to the present invention can be obtained by simply blending the ring-opened polymer and an unsaturated polymer (rubber-like material or impact-resistant resin). method (i.e., blending method), the use of a very small amount of unsaturated polymer not only has the effect of improving impact resistance, but also has better transparency compared to blending method, especially unsaturated polymer. By selecting the type of saturated polymer, there is an advantage that the transparency possessed by the ring-opening polymer can be maintained. Moreover, the polymers obtained according to the present invention have advantages such as a smaller decrease in tensile strength than compositions obtained by blending methods. In the present invention, 5-cyano-bicyclo[2.
2.1] Cycloolefin compounds used for ring-opening copolymerization with heptene-2 are broadly classified into monocyclic monoolefin compounds, nonconjugated cyclic polyene compounds, and polycyclic olefin compounds. . The general formula of the monocyclic monoolefin compound is represented by the following formula [Formula (1)]. (However, n is an integer of 3 to 20.) Typical examples include cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, and these monocyclic monoolefin compounds having an alkyl group having at most 10 carbon atoms,
Examples include monocyclic monoolefin compounds substituted with at least one hydrocarbon hydroxyl group selected from the group consisting of alkenyl groups and aryl groups. The general formula of the non-conjugated cyclic polyene compound is represented by the following formulas [formula () and formula ()].

【formula】 [However, M is a metal from group A, A, B, B, A or B of the periodic table, and R is an alkyl group, alkenyl group, aryl group, or aralkyl group having at most 20 carbon atoms. , an organic group selected from the group consisting of an alkoxide group, a phenoxy group, and a cyclopentadienyl group, or a hydrogen atom or a halogen atom, which may be the same or different, but at least one of them is a hydrogen atom or the above-mentioned is an organic group, and n is the highest valence number of the metal or less.]

Other organometallic compounds include complexes of the above-mentioned organometallic compounds with equimolar amounts of pyridine, triphenylphosphine or diethyl ether, and reaction products of 1 mol of the above-mentioned organometallic compounds with at most 2.0 mol of water; Examples include double salts of the above-mentioned organometallic compounds. Typical examples include lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum, gallium, titanium,
Organometallic compounds containing zirconium, silicon, germanium, and tin are preferred, particularly organometallic compounds of lithium, sodium, magnesium, zinc, aluminum, and tin, and organoaluminium-based compounds are especially preferred. Typical examples of the organoaluminum compounds include triethylaluminum, triisobutylaluminum, trihexylaluminum, diethylaluminum chloride, di-n-butylaluminum chloride, ethylaluminum sesquichloride, diethylaluminium butoxide, and the reaction of triethylaluminum with water. The product [reaction ratio 1:0.5 (molar ratio)] is mentioned. Other representative examples are JP 50-23720, JP 49-67999, JP 49-77999, JP 50-
It is described in the following publications: No. 58200, No. 50-71800, and No. 50-75300. Examples of other organoaluminum compounds include aluminum/siloxsalene compounds, aluminum/amide compounds, dialmoxalene compounds, and double salts containing the above organoaluminum compounds. Representative examples of other organometallic compounds are
No. 12068, No. 50-112534, No. 50-116324, No.
No. 50-117664 and No. 50-120317. Furthermore, transition metal compounds include hydrogen atoms, halogen atoms, or alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkoxy groups having at most 10 carbon atoms of metals such as tungsten, molybdenum, rhenium, tantalum, or niobium; A group selected from the group consisting of phenoxy group and carboxyl group or cyclopentadienyl group, acetylacetone residue, carbon monoxide (carbonyl group)
or acetonitrile-containing compounds and complexes of these compounds with pyridine or triphenylphosphine. Among these transition metal compounds, tungsten or molybdenum compounds are preferred, and tungsten compounds are particularly preferred. Representative tungsten and molybdenum compounds include tungsten hexachloride, molybdenum pentachloride, and tungsten oxytetrachloride. Other representative examples are special public relations in the 1970s.
-23720 and JP-A-49-67999, JP-A No. 49-
No. 77999, No. 50-58200, No. 50-61500, No. 50
It is described in the specifications of the publications No.-71800 and No. 50-75300. Representative examples of other transition metal compounds and double salts containing transition metals (especially tungsten) include Japanese Patent Application No. 50-112068, No. 50-112534, and No. 50-116324.
No. 50-117664, No. 50-120317, No. 51-
It is described in the specifications of No. 15.467 and No. 51-28.127. Additionally, activators include water, hydrogen peroxide,
Mention may be made of oxygen-containing organic compounds, nitrogen-containing organic compounds, halogen-containing organic compounds, phosphorus-containing organic compounds, sulfur-containing organic compounds and metal-containing organic compounds. Typical oxygen-containing organic compounds include alkyl peroxides, allyl peroxides, alkyl hydroperoxides, aralkyl peroxides, peracids and their esters, peroxides such as ketones or aldehydes, and epoxide compounds ( (including halogen-containing substances), acetal compounds, orthocarboxylic acid ester compounds, monohydric alcohol compounds, phenolic compounds, alcohol compounds such as polyhydric alcohols, aliphatic, aromatic or alicyclic carboxylic acids, or the like. acid anhydrides, carboxylic acid esters obtained from mono- to trivalent carboxylic acids and monovalent alcohols or phenolic compounds, cyclic esters, and esters of mono- to trivalent hydroxy compounds and monovalent carboxylic acids; Carbonate ester compounds such as carbonate esters of hydroxy compounds and tetraalkyl ortho carbonate esters,
Examples include ketones and ether compounds. Nitrogen-containing organic compounds include amine compounds such as primary amines, secondary amines, tertiary amines and diamines and their N-hydrocarbon substituted derivatives, pyridine and nuclear alkyl substituted derivatives, quinoline and its nuclear alkyl substituted derivatives, carboxylic acids amides, cyclic amides, urea and its derivatives, sulfonic acid amide compounds and acid amides,
N-nitroso or O-nitroso, aliphatic nitro compounds and having at most 3 nitro groups,
Examples include aromatic nitro compounds having at most four chlorine atoms and organic compounds having a nitrogen-halogen bond. Examples of halogen-containing organic compounds include aliphatic hydrocarbons, halogenated aromatic hydrocarbons, and halogenated aromatic hydrocarbons containing one or more carbon-carbon double bonds, in which at least one carbon atom of the double bond is substituted with a halogen atom. Examples include halogen-containing organic compounds such as tertiary hypohalide compounds, ALLYL halide compounds, tertiary alkyl halide compounds, halogenated ketone compounds, and halogenated alcohol compounds. Examples of the phosphorus-containing organic compound include phosphine compounds, phosphine oxide compounds, phosphite compounds, phosphate compounds, phosphorus-containing organic compounds having a phosphorus-monochlorine bond, and halogen-containing phosphate ester compounds. Examples of sulfur-containing organic compounds include sulfide,
Sulfur-containing organic compounds such as sulfoxides, sulfones and compounds with sulfur-halogen bonds may be mentioned. Examples of metal-containing organic compounds include metal salts of carboxylic acids such as saturated monovalent carboxylic acids, cycloalkyl or alkyl-substituted cycloalkyl saturated carboxylic acids, phenyl group- or alkyl-substituted phenylcarboxylic acids, and metal alkoxides. Representative examples of each of the electron-donating compounds mentioned above are Japanese Patent Application No. 50-112068, No. 50-112534, No. 50
It is described in the specifications of No. -116324, No. 50-117664, No. 50-120317, and No. 51-17980. Among electron-donating compounds, organic compounds (including metal-containing compounds) generally have at most 20 carbon atoms, and preferably 18 or less carbon atoms. The ratio of the organometallic compound to 1 atomic equivalent of the transition metal in the transition metal compound is generally 0.2 to 50.0.
molar, and from the aspect of its activity, 0.5~
20.0 mol is desirable. When an activator is used in the present invention, the ratio of the activator to 1 atomic equivalent of the transition metal in the transition metal compound is generally at most 20.0 mol, and from the viewpoint of polymerization activity, etc., the ratio of the activating agent is 10.0 mol or less. It is preferably 6.0 mol or less. Furthermore, the contact system used in the present invention is
Although it varies depending on their types, their proportions, and whether or not an activator is used, the proportion of transition metal compounds used is 0.001 to 10.0 atomic equivalents as the transition metal per 100 moles of monomer. Yes, from 0.05 to 0.05 depending on polymerization activity and catalyst removal after contact.
5.0 atomic equivalents are preferred, and 0.02 to 1.0 atomic equivalents are particularly preferred. Monomers used in carrying out the present invention
The ratio of unsaturated polymer to 100 parts by weight is 1 to 1.
30 parts by weight, particularly preferably 1.5 to 20 parts by weight. If the ratio of the unsaturated polymer to 100 parts by weight of the monomer is 30 parts by weight or more, the above-mentioned Characteristics deteriorate, and on the other hand, if the amount is less than 1 part by weight, the effect is not observed, which is not desirable. The present invention may be carried out in the presence of a suitable inert organic solvent or in the absence of an insoluble organic solvent. Inert organic solvents include aliphatic halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane, aromatic hydrocarbons such as toluene and xylene, aromatic halogenated hydrocarbons such as chlorobenzene, dioxane, tetrahydrofuran and anisole. Examples include ethers such as ethers, carboxylic acid esters such as ethyl acetate, and nitrites such as acetonitrile. The proportion of the inert organic solvent used should be such that the monomer and unsaturated polymer used are uniformly dissolved; if a large excess of the inert organic solvent is used, the organic solvent must be recovered after the reaction. This is not desirable because it is difficult. However, if the amount used is small, the viscosity of the reaction system is high, causing problems in polymerization. The proportion of the organic solvent used is generally at most 20 parts by volume, preferably 10 parts by volume or less, per 1 part by volume of the total amount of monomers. The unsaturated polymer to be used can be used after being isolated and purified and dried. However, for some unsaturated polymers, the untreated solution after polymerization may be used as is or in an appropriate solution. It is also possible to use treated solutions. A typical example of such an unsaturated polymer is a polyachenamer obtained by metathesis polymerization. The reaction temperature is generally -50 to +200°C,
-20~+150℃ is preferable, especially 0~+100℃
°C is preferred. If the reaction temperature is -50° C. or lower, the reaction rate is slow due to lack of sufficient activity, and furthermore, the inert organic solvent containing the norbornene-based ring-opening polymer and the saturated polymer may solidify. on the other hand,
At temperatures above 200°C, it is often difficult to adequately control the reaction. Although the present invention can be carried out by the above method, α-olefins having at most 15 carbon atoms (e.g., ethylene, hexene-1, octene-1), at most 20 carbon atoms internal olefins (e.g. hexene-2, octene-2), conjugated diolefins with at most 20 carbon atoms or their halogen substitutions (e.g. butadiene, chloroprene), non-conjugated diolefins with at most 20 carbon atoms (e.g. , 1,4-hexadiene) and JP-A No. 50-56494, No. 50-
Adjustment of the molecular weight of the resulting ring-opening polymer by adding the compounds described in each publication of No. 56495, No. 50-56496, and No. 50-56497 as a molecular weight regulator to the ring-opening polymerization system. I can do it. The proportion of the molecular weight regulator added to 100 moles of the monomer is generally at most 5 moles, preferably 3 moles or less, particularly preferably 2 moles or less. Since the catalyst system used in the present invention is relatively unstable to moisture and oxygen, the reaction must be carried out in the absence of moisture and oxygen (with the exception of water used as an activator). The inert organic solvent used is dried, for example with a molecular sieve, and the reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen and helium. After completion of the ring-opening polymerization, the resulting polymer can be recovered by several methods. As an example of the recovery method, a catalyst removal and polymer recovery method commonly used in solution polymerization of isoprene, butadiene, etc. may be applied. Other purification (post-treatment) methods include Japanese Patent Publication No. 50-23720 and Japanese Patent Publication No. 49-67999;
−77999, No. 49-130500 and No. 50-58200
No. 50-71800, No. 50-75300, No. 50-
It is described in each publication specification of No. 103600, No. 50-153100, No. 50-159598, and No. 50-160400. As mentioned above, the reaction product (polymer reactant) obtained by the present invention not only has excellent impact resistance but also has transparency using a simple blending method (blend of ring-opened polymer and unsaturated polymer). It is better compared to Furthermore, compared to the blending method, the use of a smaller amount of unsaturated polymer is effective in improving impact resistance, and furthermore, the softening point decreases less. As described above, the polymer reactant obtained by the present invention can be obtained by appropriately selecting the ratio of monomers (in the case of copolymerization), the type of cycloolefin compound, the type of unsaturated polymer, and their mutual ratio. Since not only impact resistance but also other excellent mechanical properties and moldability can be obtained, it can be used depending on the purpose of use. Hereinafter, the present invention will be explained in more detail with reference to Examples. In the Examples and Comparative Examples, Izot impact strength was measured according to ASTM D-256-56, and tensile strength and elongation were measured according to ASTM D-638.
-58T, the Vikatsuto softening point is
Measured according to ASTM D-1525-58T.
In addition, the melt viscosity was measured using a Koka type flow tester.
Using a nozzle with a diameter of 1 mm and a length of 10 mm,
Measurements were made with a load of 200Kg at a temperature of 200℃. In addition, in the Examples and Comparative Examples, the inert organic solvents, monomers, and molecular weight modifiers used were essentially free of moisture before use, and the ring-opening polymerization and reaction was essentially carried out using dehydrated and dried nitrogen gas. It was held in an atmosphere of Example 1 400 g of 5-cyano-bicyclo[2.2.1]-heptene-2 as a monomer and 20 g of styrene-butadiene block copolymer rubber (manufactured by Asahi Kasei Corporation, Product name Solprene 411, styrene content 30% by weight, Mooney viscosity (270〓) 85, purified by reprecipitation with toluene-methyl alcohol and dried under reduced pressure, hereinafter referred to as "rubber-like material (A)"] , 4.15 ml of n-hexene-1 as a molecular weight regulator and 800 ml of 1.2 as an inert organic solvent.
-Dichloroethane was charged and stirred at 65°C to create a homogeneous solution. Add tungsten hexachloride () and 2,2-dimethoxypropane () to this solution.
A mixed solution of 1,2-dichloroethane with [():()=1:2 (molar ratio), concentration of ()
0.2 mol/] 16.8 ml and a toluene solution of diethylaluminum chloride (concentration 1.0 mol/
) was added, and polymerization was carried out at 65°C for 3 hours while stirring well. Then, 2.1 g of bis(2-hydroxy-3-tert-butyl-5
-methylphenyl)methane, 50 ml of methyl alcohol and 800 ml of 1,2-dichloromethane was added to terminate the polymerization. This solution was poured into 10 ml of methyl alcohol containing 5% by volume of hydrochloric acid to precipitate a polymer (reaction product). Furthermore, after repeated reprecipitation purification with 1,2-dichloroethane-methyl alcohol, drying was performed at a temperature of 60° C. for 20 hours under reduced pressure. As a result, 404
A polymer of g [hereinafter referred to as [polymer (1)]] was obtained. That is, the polymerization conversion rate was 99.2%. This polymer was mixed with 0.5% by weight of bis(2-hydroxy-3-tert-butyl-5-
Roll kneading with methylphenyl)methane (as stabilizer) was carried out at a temperature of 180° C. for 5 minutes. The obtained mixture was pressed at 20.0°C to prepare a physical property test piece (press plate).
The Izot impact strength (notched) of the obtained test piece was 108 kg·cm/cm. Tensile strength is 465Kg/
cm ² and the elongation rate was 220%. The Vikatsu softening point was 123.5. Further, the melt viscosity of the reaction product (1) was 4.98×10 ⁴ poise. Examples 2 to 12 Rubber-like material (A) as unsaturated polymer, styrene-butadiene-block copolymer rubber [manufactured by Asahi Kasei Corporation, trade name Solprene 475, styrene content 40
Weight%, hereinafter referred to as "rubber-like material (B)", styrene
Butadiene random copolymer rubber [manufactured by Asahi Kasei Corporation, trade name Solprene 1204, Mooney viscosity (212〓) 60, styrene content 25% by weight, hereinafter referred to as "rubber material (C)"], styrene-butadiene copolymer rubber [ Manufactured by Japan Synthetic Rubber Co., Ltd., product name JSR-1502,
Mooney viscosity 50, hereinafter referred to as "rubber-like material (D)"], butadiene rubber [manufactured by Nippon Gosei Rubber Co., Ltd., product name BR-01, Mooney viscosity (ML100℃) 45, cis-1.4 content 97.5%, hereinafter referred to as "rubber-like" Acrylonitrile-butadiene copolymer rubber [manufactured by Nippon Zeon Co., Ltd., product name Hiker 1043, acrylonitrile content 29, Mooney viscosity 80, hereinafter referred to as "rubber-like material (F)"], isoprene monomer Synthetic rubber [manufactured by Gutsudoritsuchi Co., Ltd., trade name AMERIPOL SN600, Mooney viscosity 86, hereinafter referred to as "rubber-like material (G)"], ethylene-propylene-
Ethylidene norbornene ternary copolymer rubber [manufactured by Mitsui Petrochemical Industries, Ltd., trade name Mitsui EPT 3045, Mooney viscosity 40, iodine value 12, hereinafter referred to as "rubber material (H)"] and methyl methacrylate-butadiene-styrene ternary Copolymer resin [graft copolymer obtained by graft copolymerizing polybutadiene with methyl methacrylate and styrene,
The reaction was carried out in the same manner as in Example 1, except that the butadiene content was 41.9% by weight, the methyl methacrylate content was 21.1% by weight, and the amounts shown in Table 1 were used. After that, each of the obtained reaction products was collected in the same manner as in Example 1.Then, each reaction product was kneaded with a stabilizer in the same manner as in Example 1. A press plate was prepared in the same manner as in Example 1. The melt viscosity of each reaction product obtained and the physical properties of the press plate are shown in Table 1.

[Table] Comparative Example 1 Opening of 5-cyano-bicyclo[2.2.1]-heptene-2 was carried out under the same conditions as in Example 1, except that the rubbery substance (A) used in Example 1 was not added. After carrying out the ring homopolymerization, the obtained ring-opened homopolymer was recovered and purified in the same manner as in Example 1.
As a result, 376 g of polymer was obtained. The logarithmic viscosity (7 inh) of this polymer measured in dimethylformamide (temperature 30°C, concentration 0.2 g/dl) was 0.426. The mixing of this polymer and the stabilizer and the preparation of a press plate from the resulting mixture were carried out under the same conditions as in Example 1. The pressed plate had an Izot impact strength (notched) of 4.6 kg·cm/cm and a Vicat softening point of 124.0°C. The tensile strength was 484 Kg/cm ² and the elongation was 195%. Moreover, the melt viscosity of the mixture was 5.39×10 ⁴ . Comparative Example 2 Ring-opened monopolymer of 5-cyano-bicyclo[2.2.1]-heptene-2 obtained in Comparative Example 1
100 parts by weight, 2.5 parts by weight of the rubbery material (A) and 0.5 parts by weight of the stabilizer used in Example 1 were kneaded for 5 minutes with a roll (surface temperature 180°C). A press plate was prepared from the obtained mixture in the same manner as in Example 1. The obtained press plate had an Izot impact strength (notched) of 5.2 kg·cm/cm and a Vicat softening point of 120.4°C. The tensile strength was 431 Kg/cm ² and the elongation was 225%. The melt viscosity of the mixture was 3.37×10 ⁴ poise. Comparative Example 3 A press plate was prepared from the mixture obtained by kneading under the same conditions as in Comparative Example 2, except that the amount of rubber material (A) used in Comparative Example 2 was changed to 5.0 parts by weight. The obtained press plate had an Izot impact strength (notched) of 5.5 Kg·cm/cm and a Vicat softening point of 119.2. The tensile strength was 398 Kg/cm ² and the elongation was 235%. Further, the melt viscosity of the mixture was 3.91×10 ⁴ poise. Examples 13-15 Instead of 400 g of monomer (1) used as monomer in Example 3, the amount of monomer (1) shown in Table 2 was used.
and dicyclopentadiene [hereinafter referred to as "monomer (2)"], norbornene [hereinafter referred to as "monomer (3)"], or 1.4:5.8-dimethano in the amounts shown in Table 2. Ring-opening copolymerization was carried out in the same manner as in Example 3, except that -1,4,5,6,7,8,9,10-octahydronaphthalene [hereinafter referred to as "monomer (4)"] was used. I did this. After completion of the ring-opening copolymerization, the obtained polymer was recovered and purified in the same manner as in Example 1, and then
The respective polymers and stabilizers were kneaded, and the resulting mixture was molded into a press plate. Table 2 shows the mechanical properties and Vicat softening point of the obtained press plate.

[Table] Comparative Example 4 Same as Example 1, except that the amount of styrene-butadiene block copolymer rubber used in Example 1 was 160 g, and the amount of each catalyst component was twice that of Example 1. Polymerization was carried out in the same manner. After the polymerization was completed, post-treatment and separation, purification and drying of the obtained polymer were carried out in the same manner as in Example 1. The tensile strength of the polymer thus obtained was 196Kg/
It was warm in ^cm2 . Examples 16-20 Instead of diethylaluminum chloride used in Example 1, toluene solutions (concentration 1.0 mol/) of various organoaluminum compounds or their reaction products whose usage amounts are shown in Table 3 were used. Polymerization was carried out under the same conditions as in Example 1. After completion of the polymerization, reprecipitation purification and drying were performed in the same manner as in Example 1. The results obtained are shown in Table 3.

【table】

[Table] Example 21 Instead of the mixed solution of tungsten hexachloride and 2,2-dimethoxypropane used in Example 1, molybdenum pentachloride () (as a transition metal compound) and butyl alcohol () (as an activator) were used. ) and 1,2-dichloroethane [():()=1:1 (molar ratio), concentration of ()
Polymerization was carried out in the same manner as in Example 1, except that 33.6 ml of 0.1 mol/] was used and the polymerization was carried out at 80°C for 6 hours. After completion of the polymerization, reprecipitation purification and drying were performed in the same manner as in Example 1. The polymerization conversion rate was 93.7%. The obtained polymer had an Izot impact strength (notched) of 74 kg·cm/cm. Examples 22-35 2. used as an activator in Example 1
The same conditions as in Example 1 were used, except that instead of 2-dimethoxypropane, an activator whose type and molar ratio to tungsten hexachloride were shown in Table 4 was used, and the polymerization was carried out at 75°C for 8 hours. Polymerization was carried out using After completion of the polymerization, reprecipitation purification and drying were performed in the same manner as in Example 1.

【table】

【table】

Claims (1)

[Claims] 1 () 5-cyano-bicyclo [2.2.1]
-heptene-2 or at most 50 mol% thereof
(A) A, A, B, B, A
and (B) compounds of tungsten or molybdenum, or these and (C) water, hydrogen peroxide, oxygen-containing organic compounds, and nitrogen-containing organic compounds. compound, a halogen-containing organic compound, a phosphorus-containing organic compound, a sulfur-containing organic compound, and a metal-containing organic compound. A method for producing a polymer with excellent impact properties.