JPS5825697B2 - Japanese sagebrush - Google Patents

Description

[Detailed description of the invention] The present invention relates to a resin composition with improved impact resistance.

More specifically, (A) (1) a ring-opened homopolymer of a norbornene derivative having at least one cyan group or a substituent containing a cyan group; (2) having at least one ester group or a substituent containing an ester group; Ring-opened homopolymers of norbornene derivatives, (3) ring-opened copolymers of the norbornene derivatives, and (4) ring-opened copolymers of these norbornene derivatives with other cyclic olefin compounds having a molar ratio of at most 50. 99 to 10 parts by weight of at least one ring-opening polymer selected from the group consisting of (BX 1
) vinyl chloride homopolymer or (2) copolymer containing at least 50 moles of vinyl chloride" (hereinafter referred to as "vinyl chloride polymer-1") 1 to 90 parts by weight. On the other hand, (Q(1) butadiene-based rubbery material.

(2) Chlorinated polyethylene rubber, (3) Chlorosulfonated polyethylene rubber, (4) Ethylene-BJ pyrene rubber, (5) Isoprene rubber.

(6) Acrylic acid ester rubber, (kaisobutylene rubber, (8) alkylene oxide rubber, (9) chloroprene rubber, (10) ethylene-vinyl acetate copolymer rubber, and Uυ The present invention relates to a resin composition having improved impact resistance and comprising 1 to 50 parts by weight of at least one rubber-like material selected from the group consisting of natural rubber.

Obtained by ring-opening polymerization of 5-cyano-bicyclo(2,2,1)-hebutene=2 with a catalyst system consisting of a tungsten and/or molybdenum compound and an organoaluminum compound or these compounds and a third component. The ring-opening polymer used is a commonly used vinyl chloride resin (
Not only does it have better impact resistance than PVC) and propylene resins (PP), but its tensile strength and hardness are comparable to vinyl chloride resins and higher than propylene resins, and it also has excellent heat resistance. (The glass transition temperature is high), so it is known that it can be used at high temperatures (see JP-A-48-100.500). Some of the present inventors have already A norbornene derivative having at least one ester group or a substituent containing an ester group, a tungsten and/or molybdenum compound, an organoaluminum compound, or those compounds, and water, a peroxide, an epoxide compound, an organic halide, an acetal compound and alcohol compounds (
We discovered that a new polymer can be obtained by ring-opening polymerization using a catalyst system consisting of at least one compound selected from the group consisting of phenolic compounds (including phenolic compounds), and previously proposed it (Japanese Patent Application No. 119785-1985). Furthermore, some of the present inventors have already discovered that 5-Schif/-bicyclo(2
, 2, 1) - A norbornene derivative having at least one cyan group or a substituent containing a cyan group other than -hebutene-2 is ring-opened using the catalyst system described in the aforementioned Japanese Patent Application No. 100,500/1982. We discovered that a new polymer could be obtained by polymerization, and proposed it previously (Patent application 1973).
-108902).

A ring-opened polymer obtained by the above method, that is, a ring-opened polymer of a norbornene derivative having at least one cyan group or a substituent containing a cyanide group, or a norbornene derivative having at least one ester group or a substituent containing an ester group. Derivative polymers not only have better mechanical properties such as impact resistance and low-temperature impact resistance than the industrially produced and commonly used vinyl chloride resins and propylene resins, but also have superior transparency. Furthermore, due to its excellent moldability,
It can be processed into various shapes by processing methods used in the field of general synthetic resins (for example, injection molding, extrusion molding, press molding), and can be used as containers and films, for example.

However, although the ring-opened polymers described above have various properties superior to other commonly used synthetic resins, they are particularly useful in mechanical parts, window frames, etc. When molded products such as helmets, lighting covers (street lights), and electrical appliance parts (including telephones) are molded, the impact resistance of the resulting molded products is not necessarily satisfactory.

The present inventors have developed a ring-opening polymer (homopolymer) of a norbornene derivative having at least one cyan group or a substituent containing a cyan group, or a norbornene derivative having at least one ester group or a substituent containing an ester group; As a result of various searches for ways to improve the impact resistance of copolymers mainly composed of these norbornene derivatives, we found that by blending vinyl chloride polymers and rubber-like substances with these ring-opening polymers, impact resistance could be improved. The inventors have discovered that a composition with excellent properties can be obtained, and have arrived at the present invention.

The composition obtained according to the present invention not only has excellent impact resistance as described above, but also has the characteristic that, since a vinyl chloride polymer is further blended, the obtained composition is flame retardant.

In particular, depending on the blending ratio of the vinyl chloride polymer, some compositions may pass SE (self-extinguishing) even under the UL vertical method, which is a strict flame retardant standard.

Some rubber materials have good transparency depending on the type of rubber material used.

In addition, by limiting the type of rubber material used and the blending ratio of the rubber material and vinyl chloride polymer,
A composition whose softening point does not decrease too much can be obtained.

Furthermore, the hardness of the surface of the molded product of the composition obtained according to the present invention does not decrease much.

From the above, according to the present invention, it is possible to obtain a composition that has well-balanced properties such as various mechanical properties, softening point, and surface hardness, so that the composition obtained can be used in a wide variety of fields. Can be used across the board.

The ring-opening polymer used in the present invention is a ``norbornene derivative having at least one cyan group or a substituent containing a cyan group'' (hereinafter referred to as ``a cyanogen norbornene derivative'') or ``a norbornene derivative having at least one cyan group or a substituent containing a cyan group'' or ``a norbornene derivative having at least one cyan group or a substituent containing a cyan group'' or ``a norbornene derivative having at least one cyan group or a substituent containing a cyan group'' or "Norbornene derivatives having substituents containing groups" (hereinafter referred to as "ester-based norbornene derivatives")
Ring-opening polymers obtained by ring-opening polymerization of only one of these, ring-opening polymers obtained by copolymerizing two or more of these cyanogen norbornene derivatives and ester norbornene derivatives; It is a ring-opening polymer obtained by copolymerizing at least 50 mol% of these norbornene derivatives and at most 50 mol% of another cyclic olefin compound.

In producing the above ring-opening polymer, the cyanogen-based norbornene derivative used as a monomer is bicyclo(2,2
, 1) -Hebutene-2 has at least one cyan group or a substituent containing a cyan group at the 5 and 6 positions.

That is, it is expressed by the following formula.

(However, W,
aryl) group and an aralkyl group, at least one of which is a cyan group or a substituent containing a cyan group) Examples of the above substituent containing a cyan group include a cyanmethyl group. , cyanethyl group, cyanopropyl group.

Cyano-n-butyl group, cyano-isobutyl group and ω
-cyan-〇-heptyl group is mentioned.

In addition, hydrocarbon groups include methyl, ethyl, propyl,
n-butyl group, isobutyl group, octyl group.

Examples include phenyl group, cyclohexyl group and 2-octenyl group.

Among the cyanogen-based norbornene derivatives used as monomers in producing the ring-opening polymer used in the present invention, 5-cyano-bicyclo(
2,2,1)-Hebutene-2゜5-methyl-5-cyano-bicyclo(2,2,1)-heptene-2,5-ethyl-5-cyano-bicyclo(2,2,1)- Hebutene-2
, 5-n-propyl.

-5-cyano-bicyclo-(2,2,1,1-heptene2.5-n-butyl-5-cyano-piclo[2°2.
1]-Hebutene-2,5-ynebutyl-5-cyano-bicyclo(2,2,1)-hebutene-2,5-n-octyl-5-cyano-bicyclo(2,2,1)- Butene
2,5-phenyl-5-cyano-bicyclo(2,2,1
,]-to]butene-2,5-cyclohexyl-5-cyano-piclo(2,2,1)-hebutene-2,5-(2-
octenyl)-5-cyano-bicyclo(2,2,1)-
Hebutene-2,5,5-dicyano-bicyclo(2,2,
1)-Hebutene-2,5゜6-dicyatwobicyclo(2
,2,1)-hebutene-2,5-methyl-6-diatubicyclo(2,2,1)-hebutene-2,5-ethyl-6-diatubicyclo(2,2,1)- butene-2,
5n-butyl-6-diatubicyclo(2,2,1)-
Hebutene-2,5-isobutyl-6-diatubicyclo[2゜2.1]-hebutene-2,5-phenyl-6-diatubicyclo(2,2,1)-hebutene-2,5-cyanomethyl -bicyclo(2,2,1,1-hebutene-2
゜5-Cyanethyl-bicyclo(2,2,1)-hebutene-2,5-(cyano-n-butyl)-bicyclo(2,
2,1)-hebutene-2,5-(cyano-isobutyl)
-Piclo(2,2,1,1-hebutene-2゜5-(ω
-cyano-n-heptyl)-bicyclo(2,2,1)-
Hebutene-2 and 5-cyanophenyl-bicyclo(2
,2,1]-hebutene-2.

There are two types of substituents: endo type and exo type.

Furthermore, the ester norbornene derivative used as a monomer in producing the ring-opening polymer used in the present invention has at least one monomer at the 5 and 6 positions of bicyclo(2,2,1)-heptene-2. It has a substituent containing one ester group or costel group.

That is, it is expressed by the following formula.

(However, W, X, Y and Z are hydrogen atoms, ester groups, substituents containing ester groups, or carbon atoms of 1 to 20
alkyl group, cycloalkyl group.

A hydrocarbon group selected from the group consisting of an alkenyl group, an aryl group, and an aralkyl group, in which at least one is an ester group or a substituent containing an ester group) These ester-based norbornene derivatives are cyclopenta Synthesis by carrying out a Diels-Alder reaction between a diene and a vinyl compound having an ester group or a substituent containing an ester group alloy (e.g., methyl acrylate, methyl methacrylate, dimethyl maleate, hexyl crotonate, vinyl acetate). However, it can also be synthesized by reacting dicyclopentadiene with the above vinyl compound.

Among the ester norbornene derivatives used as monomers in producing the ring-opening polymer used in the present invention, a representative example is 5-methoxycarbonyl-bicyclo(2,2,1)- Hebutene-2,5-ethoxycarbonyl-bicyclo(2,2,1)-hebutene-2,5-butoxycarbonyl-piclo(2,2
,1)-heptene-7-2,5-allyloxycarbonyl-piclo(2,2゜1]-hebutene-2,5-methyl-5
-methoxycarbonyl-piclo(2,2,1)-hebutene-2,5-hexyloxycarbonyl-6-methyl-bicyclo[2,2,1)-hebutene-2,5-ethoxycarbonyl- 6-phenyl-piclo (2,2゜1
]-hebutene-2,5-hebutyl-6-octyloxydicarponylubicyclo(2,2,1,1-hebutene-2,
5-methoxycarbonyl-6-methoxycarbonylmethyl-bicyclo(2,2,1)-hebutene-2,5,
6-dimethoxycarponylubicyclo(2,2,1)
-hebutene-2,5,6-diethoxycarbonyl-bicyclo(2,2,1,1-hebutene-2,5,5-dibutene-dicarbonyl-bicyclo(2,2,1,1- Hebutene-2,5-methyl-6,6-dimethoxycarbonylbicyclo(2,2,1)-hebutene-2,5-ω-
Methoxycarbonylhebutyl-6-octyl-bicyclo(2,2,1)-heptene-2,5-ω-methoxycarbonyl-2-decenyl-6-pentyl-bicyclo(
2,2,1)-hebutene-2,5-ω-methoxycarbonylhebutyl-6-2-octenyl-bicyclo(2,
2゜1]-Hebutene-2,5-acetoxymethyl-bicyclo(2,2,1)-hebutene-2,5-acetoxy-bicyclo(2,2,1)-hebutene-2,5- Bropiono bovine dimethyl-bicyclo(2,2,1)-heptene-2 and 5-stearoxymethyl-bicyclo(2,2
, 1)-hebutene-2.

There are two types of substituents: endo type and exo type.

As mentioned above, although cyanogen-based norbornene derivatives and ester-based norbornene derivatives have different properties, when producing the ring-opening polymer used in the present invention,
The above norbornene derivative may be used after separating its isomers by precision distillation or the like, but it may also be used as is without separation (a mixture of isomers may be used).

In the present invention, a polymer (i.e., a single polymer) obtained by ring-opening polymerization of only one of the cyano-based norbornene derivatives and ester-based norbornene derivatives may be used; You may use the polymer (namely, copolymer) obtained by ring-opening polymerization of two or more types.

Furthermore, in the present invention, a copolymer containing the above-mentioned norbornene derivative as the main component (50 molar ratio or more) and obtained by copolymerizing these with another cyclic olefin compound having a molar ratio of at most 50 may also be used. I can do it.

Among other cyclic olefin compounds, representative examples include:
Monocyclic olefins such as cyclopentene, cycloheptene and cyclododecene, ■, 5-cyclooctadiene, 1,5.9-cyclododecatriene, 1-
Non-conjugated cyclic polyene compounds such as chloro-1,5-cyclooctadiene and norbornadiene and 5
-Metoo beef seabicyclo(2,2,1)-hebutene-2
,5-cyclohexoxy-viclo(2,2,1)-
Hebutene-2,5-methoxymethyl-piclo(2,
2,1)-Hebutene-2,5-methoxy-6-medoxymethyl-bicyclo(2,2,1)-hebutene-2 and 5-phenoxy-bicyclo(2,2,1)-hebutene- Ether based norbornene derivatives such as 2, 3,
6-methylene-1,2,3,6-titrahydrosisphthalic anhydride, 6-(5-carboxy-bicyclo(2,2,1)-2-hebutenyl)acetic anhydride, 4,7- methano-1-methyl-1,2,3,3a,
4,7.7 Acid anhydride-based norbornene derivatives such as a-8-naphthalene-1,2-dicarboxylic anhydride and 4-(bicyclo(2,2,1)-2-hebutenyl)phthalic anhydride; N-methyl-3,6-methylene-1,2,
3,6-titrahydrosis-phthalimide, N-methyl-3,6-methylene-1-methyl-1,2,3,6-
Chitrahydrosis-phthalimide, Piclo (2,2
,1,1hept-2-ene-5-spiro-3'-(N-
ethyl succinimide).

2-Methyl-2-aza-1,3-dioxo-5,8-methano-1,2,3,4,4a,5. s, 8 a-octahydronaphthalene, N-ethyl-5,8-methano-
1,2,3,4゜4 a, 5,8.8 a-octahydronaphthalene-2,3-dicarboximide, N-methyl-4-(3-norborn-2-enyl)phthalimide, N-( 5-norborn-2-enyl)methyl-maleimide.

Imide based norbornene derivatives such as N-(5-norborn-2-enyl)methyl-citraconimide and N-(5-norborn-2-enyl)methyl-naphthalene-2,3-dicarboximide.

5-Chloro-bicyclo(2,2,1)-hebutene-2゜5.5-dichloro-bicyclo(2,2,1)-hebutene-2 and 5.6-dichloro-bicyclo(2,2, 1)
-Halogenated norbornene derivatives such as hebutene-2, N,N-dimethyl-bicyclo(2,2,1)-hebutene-2-carbonamide-5,N-methyl-N-ethyl-bicyclo[2,2 ,1]-hebutene-2-carbonamide-5,N,N-di-n-propyl-bicyclo(2,
2,1)-hebutene-2-carbonamide-5,N,N
-dicyclohexyl-bicyclo(2,2,1)-hebutene-2-carbonamide-5,N,N-diphenyl-bicyclo(2,2°1]-hebutene-2-carbonamide-5,N.

N-dibenzyl-bicyclo(2,2,], , l-hebutene-2-carbonamide-5, N,N-diethyl-6
-Methyl-bicyclo(2,2,1,1-hebutene-2-
Carbonamide and N, N, N', N'
-tetramethyl-bicyclo[2,2,1]-hebutene-
Amido-based norbornene derivatives such as 2-carbonamide-5 and 5-(2-pyridyl)-piclo(2,
2,1)-Hebutene-2,5-(3-pyridyl)-bicyclo(2,2,1)-hebutene-2,5-(3-methyl-2-pyridyl)-bicyclo(2,2, 1)-Heptene-2,5-(4-methyl-2-pyridyl)-bicyclo(
2,2,1)-hebutene-2,5-(6-methyl-2-
pyridyl)-piclo(2,2゜1]-hebutene-2,
5-(5-methyl-3-pyridyl)-piclo[2,2
,1]-hebutene-2゜5-(6-methyl-3-pyridyl)-bicyclo(2,2,1)-hebutene-2,5-(
5-ethyl-2-pyridyl)-bicyclo(2,2,1)
-hebutene-2,5-(3,5-dimethyl-2-pyridyl)-bicyclo(2,2,1)-heptene-2,5-(
5-ethyl-3-methyl-2-pyridyl)-bicyclo(
2,2,1)-hebutene-2,5-(2-quinolyl)-
Bicyclo(2,2,1)-hebutene-2,5-(4-quinolyl)-piclo(2,2,1)-hebutene-2,5
-(9-carbazolyl)-bicyclo(2,2゜1]-heptene-2,5-(3-methyl-9-carbazolyl)-
Bicyclo(2,2,1)-hebutene-2,5(3n-butyl-9-carbazolyl)-bicyclo(2,2,1)-
Hebutene-2,5-(9-butyl-3-carbazolyl)
-bicyclo(2,2゜1]-hebutene-2,5-(9-
octyl-3-carbazolyl)-piclo(2,2,1
)-hebutene-2 and 5-(9-dodecyl-3-carbazolyl)-piclo(2,2,1)-hebutene-2. Examples include norbornene derivatives having substituents containing

Furthermore, other cyclic olefin compounds include 1.4-
Dihydro-1,4-methano-naphthalene, 1,4-dihydro-1,4-methano-6-methylnaphthalene, ■, 4-
Dihydro-1,4-methano-6-medoxynaphthalene, 1,4-dihydro-1,4-methano-6-medoxycarponylnaphthalene, 1,4-dihydro-6-fluoro-1,4-methanonaphthalene.

■, 4-dihydro 1,4-methano-5,6,7,8-
Tetrafluoronaphthalene, 6-chloro-1,4-dihydro-1,4-methanonaphthalene, ■,4-dihydro=
1,4-methano-5,6,7,8-tetrachloronaphthalene, 5,8-diacetoxy-1,4-dihydro-1゜4-methanonaphthalene, 5,8-diacetoxy-6゜7
-dicyano-1,4-dihydro-1,4-methanonaphthalene, 5,8-diacetoxy-1,4-dihydro-1,
4-methano-6-methylnaphthalene, 5,8-diacetoxy-1,4-dihydro-6,7-dimethyl-1,4-
Methanonaphthalene, 5,8-diacetoxy-1,4-dihydro-6,7-simethoxy1,4-methanonaphthalene, 6-dia2-1,4-dihydro-1,4-methanonaphthalene, 1,4-dihydro-1 , 4-methanoanthracene, 1,4-dihydro-1,4-methano-6-methoxycarponylanthracene.

9.10-diacetoxy-1,4-dihydro-1,4-
Methanoanthracene, 6-dia-1,4-dihydro-
1,4-methanoanthracene and 1,4-dihydro-
Aromatic norbornene derivatives such as 9,10-diphenyl-1,4-methanoanthracene and 2-methoxycarbonylbicyclo(2,2,1)-hebuta-2,5
-diene, 2-ethoxycarbonylbicyclo[2,2,
1]-hepta-2,5-diene.

2-isopropyloxycarbonylbicyclo [2゜2.
1]-Hebuta-2,5-diene, 2-pentyloxycarbonylpicro(2,2,1)-hebuta-2゜5-diene, 2-octyloxycarbonylbicyclo(2,2
, 1,1-hebuta-2,5-diene, 2-methoxycarbonyl-3-methylbicyclo(2,2,1]-he7'ter-2,5-diene, 2,3-dimethoxycarbonylpicro( 2,2,1,1-hebuta-2,5-diene, 2,
3-dibutyloxycarbonylbicyclo(2,2,1)
-hebuta-2,5-diene, 2-methoxycarbonyl-
3-ethoxycarbonylbicyclo(2,2,1)-hebuta-2,5-diene, 2,3-dipropyloxycarbonylbicyclo[2,2,1]-hebuta-2,5-diene, 2, 3-dibutyloxycarbonylbicyclo(2,2
,1)-hebuta-2,5-diene, 2-methoxycarbonyl-3-hexyloxycarbonylbicyclo(2,2
,1) -Hair'2-2゜5-diene, 2-acetoxymethylbicyclo[2゜2.1]-hebuta-2,5-diene, 2-butyryloxymethylbicyclo(2,2,1,
1-hebuta-2,5-diene, 2-valeryloxymethylbicyclo[2゜2.1]-hebuta-2,5-diene,
2-Caproyloxypiclo(2,2,1)-hebuta-2,5-diene, 2,3-di(acetoxymethyl)bicyclo[2°2.1]-hebuta-2,5-diene ,2,
3-di(propionyloxymethyl)piclo(2,2
, 1)-hebuta-2,5-diene, 2-methoxycarbonyl-3-propyl-piclo(2,2,1)-hebuta-2°5-diene, 2-methoxycarbonyl-3-hexylbicyclo (2,2,1)-hebuta-2,5-diene.

2-methoxycarbonyl-3-phenylpicro (2,
2,1)-hebuta-2,5-diene, 2-acetoxymethyl-3-methylpiclo(2,2,1)-hephtha-2
,5-diene, 2-acetoxymethyl-3-cyclohexylbicyclo(2,2,1)-hebuta-2,5-diene, 2-acetoxymethyl-3-phenylbicyclo(2,
2,1)-hebuta-2,5-diene 92-propionyloxymethyl-3-methylbicyclo(2,2,1)-hebuta-2,5-diene and 2-valeryloxymethyl-3-phenyl Bicyclo(2,2,1,1-hebuta-2
, 5-diene, or a substituent containing an ester group.

As described above, the ring-opening polymer used in the present invention includes at least 50 mol% and at most 50 mol% of one or more of cyanogen norbornene derivatives and ester norbornene derivatives. A ring-opening polymer obtained by copolymerizing with a compound can be used, but if the composition ratio of other cyclic olefin compounds in the ring-opening polymer is 50 mol% or more, for example, other cyclic olefin compounds may be used. When a copolymer (ring-opening polymer) obtained by using a monocyclic olefin compound such as cyclopentene and cyclooctene as a monomer is used as a system compound, the molded product of the final composition obtained is surface hardness.

Unfavorable because the tensile strength and softening point are lowered.0 Monopolymers of the cyanogen norbornene derivatives or ester norbornene derivatives used in the present invention, or copolymers of these norbornene derivatives or copolymers mainly composed of these norbornene derivatives. To produce the composite, a catalytic system consisting of a tungsten and/or molybdenum compound and an organoaluminum compound or a third component is heated at temperatures of -1°00°C to +200°C in an inert organic solvent or in the absence of a solvent. This can be achieved by ring-opening polymerization of the above-mentioned monomers or mixtures of monomers at a temperature range of .degree.

Among the above tungsten and molybdenum compounds, typical ones include tungsten hexachloride, molybdenum pentachloride, and tungsten oxytetrachloride (WOC).
14) and aluminum-tungsten halides obtained by reducing tungsten halides with aluminum powder (e.g. A14W3C
118) I can raise it.

In addition, the organoaluminum compound has the general formula AlR3 or AlRnX3-n [where R is an alkyl group or an aryl film, X is a halogen or hydrogen atom, or an alkoxy group, and n is 1.1.5 or 2
) or AlR3-H2O (however, the molar ratio of H
20/AlR3<1.5).

Among these organoaluminum compounds, triethylaluminum, triisobutylaluminum, and trihexylaluminum.

Diethylaluminum chloride, di-n-butyl-γ
Luminium chloride, ethylaluminum sesquichloride, diethylaluminum butoxide and triethylaluminum-water (molar ratio 1:0.5) are suitable as catalyst components.

Further, as the third component, water, peroxide (for example, benzoyl peroxide, tertiary-butyl hydroperoxide, hydrogen peroxide), epoxide-based compound (
For example, propylene oxide, epichlorohydrin, allyl glycidyl ether), halogen-containing organic compounds [for example.

aryl chloride, -α-chloroacetone] acetal compounds (e.g., acetaldehyde diethyl acecool, shedoxymethane, dichloroacetaldehyde methyl acecool), alcohol compounds (e.g., methyl alcohol).

Examples include n-butyl alcohol, phenol) oyohyorthocarboxylic acid ester compounds (for example, methyl orthoformate, ethyl orthoformate).

Further, as the inert organic solvent, it is preferable to use one that does not poison the above-mentioned catalyst. Typical examples thereof include aliphatic hydrocarbons such as pentane, hexane and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, and cyclocarbons. Hegyu-san.

Alicyclic hydrocarbons such as decalin and cyclooctane, methylene chloride, ■, 2-dichlorp O/'? 7 and chlorobenzene, and ethers such as diethyl ether and tetrahydrofuran.

To produce a ring-opened polymer by the above method, JP-A No. 4
It can be obtained in a similar manner to the method described in No. 8-100,500.

The ring-opening polymer used in the present invention consists of the cyanogen-based norbornene derivative, the ester-based norbornene derivative, each of these norbornene derivatives, or these fulbornene derivatives, and at most 50 mol% of the other cyclic olefin compound. The mixture is treated with a catalyst system consisting of an oxide of tungsten and/or molybdenum (e.g., tungsten trioxide, molybdenum trioxide) and a Lewis acid or these and the organoaluminum compound in the absence of the inert organic solvent or solvent.
It can be obtained by ring-opening polymerization at a temperature range of 0°C to +150°C.

Representative examples of Lewis acids used as catalysts include aluminum chloride, tin tetrachloride, vanadium tetrachloride, and halogen-containing organoaluminum compounds such as sialyaluminium chloride and alkylaluminum dichloride.

When producing a ring-opened polymer by this method, the above-mentioned "tungsten and/or molybdenum oxide" (hereinafter "
The ratio of Lewis acid used per 1 mole (referred to as "oxide") is generally 0.1 to 1000 moles, particularly 0.3 to 1000 moles.
5.0 mol is preferred.

Further, when an organoaluminum compound is used, the ratio of the organoaluminum compound to 1 mole of the oxide is generally at most 10.0 mol, preferably at most 5.0 mol.

In addition, when producing this polymer, the oxide and Lewis acid, or the oxide and Lewis acid, and the organoaluminum compound may be added to the polymerization system as they are, but the oxide and Lewis acid may be reacted in advance. A co-pulverized product obtained by previously co-pulverizing a reaction product or oxide and a Lewis acid, or a co-pulverized product or this reaction product or co-pulverized product and an organoaluminum compound may be added to the polymerization system. To produce the product, 0.1 to 10.0 mol (preferably 0.3 to 5.0 mol) of Lewis acid per mol of oxide is added in the inert organic solvent at room temperature to 200 ml. It can be obtained by reacting at ℃.

When producing the ring-opened polymers used in the present invention by this method, the order in which catalyst components, monomers, and inert organic solvents (if used) are added to the polymerization system (polymerization apparatus) may vary. There is.

Typical examples include adding an inert organic solvent to the reaction system, then adding the monomer and oxide, and then adding an organoaluminum compound (if used) and a Lewis acid; Examples include a method of adding the reaction product to the reaction system, then adding the monomer, and then adding a reaction product or co-pulverized product of the oxide and Lewis acid, or a method of further adding an organoaluminum compound. The components may be premixed with each other or with any of the catalysts, or may be heated.

As mentioned above, the ring-opening polymer used in the present invention is a combination of a tungsten and/or molybdenum compound, an organoaluminum compound, or these compounds and a third component, or a tungsten and/or molybdenum oxide, a Lewis acid, or these compounds. Polymerizing a cyanogen-based norbornene derivative and/or an ester-based norbornene derivative, or a mixture of the norbornene derivative and another cyclic olefin-based compound using a catalyst system consisting of and an organoaluminum compound in the presence or absence of an inert organic solvent. Although it can be obtained by,
Ethylene, propylene, butene-1 and hexene-1
Alpha-olefins, butene-2 and hexene-
Controlling the molecular weight of the ring-opening polymer by adding compounds such as internal olefins such as 2, conjugated diolefins such as butadiene and isoprene, and non-conjugated diolefins such as 1,4-hexadiene to the polymerization system. However, in general, the above compound (molecular weight regulator) is used in an amount of at most 100 parts by weight per 100 parts by weight of the monomer.

The ring-opening polymer used in the present invention can be obtained using the above two catalyst systems, but no matter which catalyst system is used for polymerization, the reaction formula is as follows (cyanonorbornene derivative or ester (in the case of homopolymerization of norbornene derivatives).

These norbornene derivatives have the potential to form polymers in the vinylene type format (the following formula), but with these catalyst systems, vinylene type polymers are hardly obtained, and even if they are obtained, it is only in trace amounts.

(In the above 2 formulas, W, and aralkyl groups, at least one of which is a cyan group, an ester group, or a cyan group or an ester group.

(n is a positive integer) The method for recovering the ring-opened polymer obtained by any of the above catalyst systems and the method for removing the catalyst present in the obtained polymer are generally used in solution polymerization of isoprene, butadiene, etc. The existing catalyst removal and polymer recovery methods may be applied.

One example is a lower alcohol containing a small amount of hydrochloric acid (
For example, by pouring the solution obtained by polymerization [ring-opened polymer, unreacted monomer, catalyst residue, and inert organic solvent (if used)] into methyl alcohol, ethyl alcohol, the catalyst residue is removed. At the same time, the resulting polymer precipitates out.

Alternatively, the polymerized organic solvent may be homogenized using a water-immiscible solvent (for example, methylene chloride) and then treated with water containing a chelating agent such as nitrilotriacetic acid and ethylenediaminetetraacetic acid to remove catalyst residues. , a method of removing an organic solvent, or a method of recovering a ring-opened polymer obtained by a steam stripping method.

In carrying out the present invention, a monopolymer of a cyanogen norbornene derivative or an ester norbornene derivative obtained by the method described above, a copolymer of two or more of these norbornene derivatives, or one or two of these norbornene derivatives. Among copolymers of the above and other cyclic olefin compounds having a molar ratio of at most 50, the purpose can be achieved even if only one of the ring-opening polymers is used. More than one species may be used.

Furthermore, the vinyl chloride-based polymer used in the present invention refers to a monopolymer obtained by polymerizing vinyl chloride alone, vinyl chloride with a molar ratio of 50 or more, vinyl acetate with a molar ratio of 50 or less, vinylitin chloride, It is a copolymer obtained by copolymerizing one or more monomers such as ethylene, acrylonitrile, and maleic acid.

These vinyl chloride homopolymers or copolymers (ie, vinyl chloride polymers) are widely produced industrially by emulsion polymerization, suspension polymerization, or bulk polymerization.

In carrying out the present invention, the degree of polymerization is 450 to 1500.
A vinyl chloride polymer is preferred.

In addition, since the vinyl chloride polymer is unstable to heat and light, there is a risk of partial deterioration during the mixing process described later.

Of course, it may contain a stabilizer (dehydrochlorination inhibitor) such as a soot-based compound and a compound having an epoxy group.

Furthermore, the rubber materials used in the present invention include butadiene-based rubber materials, chlorinated polyethylene-based rubber materials, chlorosulfonated polyethylene-based rubber materials, ethylene-propylene-based rubber materials, and isoprene-based rubber materials. , acrylic ester rubber, inbutylene rubber, alkylene oxide rubber, chlorobrene rubber, ethylene-vinyl acetate copolymer rubber, and natural rubber.

The butadiene-based rubber is a butadiene monopolymer rubber or a copolymer rubber obtained by copolymerizing butadiene as a main component with small amounts of monomers such as styrene and acrylonitrile.

When using this copolymer rubber, a random copolymer rubber or a block copolymer rubber may be used.

These butadiene-based rubbers are those produced by emulsion polymerization using redox catalysts or free radical generators as catalysts, or organic lithium compounds (for example,
It is produced by a solution polymerization method using n-butyllithium as a catalyst.

Chlorinated polyethylene rubber material is a high density (density 0
．． 93 to 0.989/cc) of an ethylene monopolymer or a copolymer of ethylene with a small amount (generally 10 molar or less) of propylene and an α-olefin such as butene-1 in a solvent or an aqueous suspension. It can be obtained by chlorination.

It is particularly preferable that the chlorine content is 25 to 45% by weight.

Chlorosulfonated polyethylene rubber is obtained by chlorosulfonating the ethylene monopolymer or copolymer used in producing the above chlorinated polyethylene rubber in an organic solvent. It is.

Preferably, the chlorine content is 24 to 45% by weight and the sulfur content is 0.5 to 1.7% by weight.

In addition, ethylene-propylene-based rubber refers to a copolymer rubber of ethylene and propylene or a copolymer rubber containing them as main components, and includes 1,4-pentadiene, 1,5-hexadiene, and 3,3-dimethyl-1,5-hexadiene. Linear or branched diolefins containing two double bonds at the ends, such as 1,4-hexadiene and 6-methyl-
monomers such as linear or branched diolefins containing only one terminal double bond, such as 1,5-hebutadiene, or cyclic diene hydrocarbons, such as picro(2,2°1]-hebutene-2); It is a multi-component copolymer rubber obtained by copolymerizing a small amount of rubber.

The weight ratio of one unit of ethylene monomer to one unit of propylene monomer in the above copolymer rubber or multicomponent copolymer rubber is 30/70.
Preferably, the ratio is between 70/30 and 70/30.

These ethylene-propylene rubber materials can be produced using a catalyst system containing an organoaluminum compound and a transition metal compound as main components.

Isoprene-based rubbery substances are lithium or organolithium compounds or so-called Ziegler catalysts (for example,
It is produced in an organic solvent using titanium tetrachloride (triethylaluminum) as a catalyst.

Isoprene has two double bonds, 1,2, 3,4, cis-1,4 and trans-1, depending on the polymerization conditions.
, 4 are possible.

When using an isoprene rubber material in the present invention,
Those with a large number of cis-1,4 bonds are preferred, particularly 90%
The above are optimal.

An acrylic ester-based rubber material is a monomer containing an acrylic ester (for example, butyl acrylate) as a main component, a small amount of other monomers (for example, acrylonitrile), and a catalyst such as a persulfate. It is obtained by emulsion polymerization in the presence of acrylic rubber, and is generally referred to as acrylic rubber.

Inbutylene-based rubber is obtained by copolymerizing isobutyne and a small amount of a monomer such as isoprene.

In general, Friedel-Craft (Friedel-Cr
aft ) in an organic solvent (eg, methyl chloride, ethyl chloride, chloroform) in the presence of a catalyst.

Alkylene oxide-based rubbers are mainly composed of alkylene oxides such as ethylene oxide, propylene oxide, or epichlorohydrin, or derivatives thereof, and are composed of organometallic compounds (e.g.,
It is obtained by polymerizing an organic aluminum compound) as a main catalyst.

In addition, chloroprene-based rubbery substances are compounds such as persulfates, peroxides, and azo compounds produced by bulk polymerization, solution polymerization, or emulsion polymerization of chloroprene alone or with a small amount of other monomers. (This polymerization is generally carried out in the presence of a polymerization regulator such as a mercaptan compound, sulfur, and sialoxanthogen disulfide.)

Ethylene-vinyl acetate copolymer rubber is obtained by copolymerizing ethylene and vinyl acetate by solution polymerization or emulsion polymerization using compounds such as persulfates, peroxides, and azo compounds as catalysts. It is something that can be done,
The content of vinyl acetate in this rubbery product is 30 to 50% by weight.
Preferably.

These rubber-like materials are manufactured industrially and used in a wide range of fields, and their manufacturing methods, properties, and uses are widely known [for example, see (Synthetic Rubber Handbook, written by Shu Kanbara, published by Asakura Shoten)]6 Furthermore, natural rubber can be used as the rubbery material in the present invention.

The above rubber-like materials may be used alone or in combination of two or more.

The type of these rubber-like materials may be selected depending on the intended use of the composition of the present invention.

In the present invention, the blending ratio of the ring-opening polymer and the vinyl chloride polymer is 1 to 90 parts by weight of the vinyl chloride polymer to 99 to 10 parts by weight of the ring-opening polymer. 20 to 8 parts by weight of vinyl chloride polymer to 80 to 20 parts by weight
0 parts by weight is preferred.

If the composition ratio of the ring-opened polymer in the above-mentioned formulation is 10% by weight or less, the excellent properties (for example, heat resistance and low-temperature brittleness resistance) possessed by the ring-opened polymer will be lost, which is not preferable.

Furthermore, if the amount of vinyl chloride polymer blended is small, no improvement in flame retardant hardness or the like will be seen.

On the other hand, the total amount of ring-opened polymer and vinyl chloride polymer is 10
The blending ratio of the rubbery material to 0 parts by weight is 1 to 50 parts by weight, particularly preferably 3 to 25 parts by weight.

If the blending ratio of the rubbery substance is 50 parts by weight or more with respect to 100 parts by weight of the total amount of the ring-opening polymer and the vinyl chloride polymer,
Although the impact resistance of the resulting composition is improved, it is not preferable because not only the hardness and tensile strength are significantly reduced, but also the properties possessed by the ring-opened polymer are lost.

In producing the composition in the present invention, the ring-opening polymer, vinyl chloride polymer, and rubber-like material may be mixed at the same time, or after mixing any one of them, other components may be mixed. 0 Examples of the mixing method include a method of dissolving or suspending the ring-opened polymer, vinyl chloride polymer, and rubber-like material (elastic material) in an organic solvent, and then removing the organic solvent.

Other mixing methods include melt kneading using mixers such as roll mills, extruders, and Banbury mixers, which are used when mixing general synthetic resins, impact-resistant resins, or elastic bodies (rubber-like materials). and tri-blending using a mixer such as a ribbon mixer or a tumbler.

As described above, the composition obtained according to the present invention has excellent impact resistance.

Furthermore, a transparent composition can be obtained by selecting the types of ring-opening polymer, rubbery material, and vinyl chloride polymer to be used.

Furthermore, since the vinyl chloride polymer is mixed in, the resulting composition is less flammable, and if the amount added is limited, it can pass SE (self-extinguishing) even under the UL standard, which is a strict flame retardant standard. There are also things.

Furthermore, the surface hardness of the composition obtained according to the present invention is not very low.

The composition obtained in the present invention has the above-mentioned properties and can be used as is. However, depending on the intended use, it may be used as a stabilizer against light (ultraviolet rays), oxygen, heat, and ozone.

By incorporating additives such as flame retardants, plasticizers, lubricants, reinforcing agents, fillers, 2 coloring agents, antistatic agents, 2 foaming agents, and electrical property improvers, the effects can be further demonstrated. These formulations are also encompassed by this invention.

Compositions of ring-opening polymers, vinyl chloride polymers, and rubber-like substances, as well as compounds containing additives, can be processed using compression molding, extrusion molding, and injection molding methods used for general synthetic resins. It can be formed into various shapes such as a film, a sheet, a boat, a pipe, a rod, two spheres, and other shapes by molding methods such as , blow molding, and casting.

The composition obtained according to the present invention or a compound containing additives has excellent properties as described above, and can be used in a wide range of applications by being molded into various shapes. Containers such as films and their secondary products (e.g. bags), packaging materials, water pipes and their joints, daily necessities 2 kitchen utensils 2 mechanical appliance parts, electrical appliances (including lighting fixtures) parts.

Examples include agricultural or fisheries equipment or their parts, as well as toys.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in Examples and Comparative Examples, Izot (i Z
Od) Impact strength was measured according to ASTM D-256-56.

The tensile strength was measured according to JISK6723 (specimen JI8 No. 2 1/2° thickness 1 mm + tensile speed 5 mm/
minutes).

Vicat softening point is ASTM D-15
Measured according to 25-58T.

Pencil hardness was measured according to JIS K5401 (load: 1 kg).

In addition, flammability is UL-94 and ASTM D-63.
5-56T (for UL-94, a horizontal method test was performed on a 1/8 inch thick specimen, and a vertical method test was performed on those that passed SB.

The ASTM method was tested on 1/8 inch thick specimens).

Example 1 After drying, 5-cyano-piclo (2,2
,1,1-hebutene-2 (contains 40 exo forms) 3kg
, 1,1-dichloroethane 91 and 33.0 ml n-hexene-1, dehydrated with calcium hydride immediately before use.
(1.2 mol ratio based on the monomer) and stirred well.

In this solution, 1,2 tungsten hexachloride was added as a polymerization catalyst.
-Dichloroethane solution (0.2 mol/l) 151.2 m
l.

1,1-jethoxyethane [CH3CH
Add 151.2 TL of a 1,2-dichloroethane solution (0.6 mol/l) of (QC2H5) 2, l and 181.6 ml of a 1,2-dichloroethane solution (1,0 mol/l!) of diethylaluminium chloride (
1.2 mmol of tungsten hexachloride, 7,2-: IJ mol, 1.2 mmol of tungsten hexachloride per mol of monomer.
(3.6 mmol of 1-jethoxyethane), polymerization was carried out at 70°C for 2 hours.

After the polymerization was completed, the solution containing the reaction product (ring-opened polymer) was taken out and cooled.

After adding 100+711 monoethanolamine to this solution and stirring well, a large amount (about 301) of methyl alcohol was added to precipitate the ring-opened polymer.

This opening! After repeating the dissolution-precipitation process twice in an acetone/methyl alcohol system, a methylene chloride solution of the ring-opening polymer was dissolved in a 1% sodium tripolyphosphate aqueous solution for 30 minutes.
Washed with water twice, and washed with water three times.

The ring-opened polymer was diluted to about 10% by weight with acetone, precipitated with methyl alcohol, and the resulting ring-opened polymer was dried at 45° C. under reduced pressure for 48 hours.

The ring-opened polymer thus purified was in the form of white flakes.

The reduced viscosity of the obtained ring-opened polymer (30° C., dimethylformamide, concentration 0.1 g/dl) was 0.50.

This ring-opening polymer was combined with dibutyl tin malate (manufactured by Sankyoki Gosei Co., Ltd., trade name: Sukun BM) of 3 weight units and 2,2'-methylenebis(4-methyl-6-tertiary) of 0.5 weight units. -butylphenol) was added as a stabilizer, and kneaded for 10 minutes with a roll whose surface temperature was set to 180°C.

This mixture was heated to 100k in a press molding machine kept at 200℃.
Pressed for 5 minutes under pressure of g/i to a thickness of 1 mm and 3 m.
A press plate of m was created.

The Izotsu impact strength of this press plate is 11.9 kg.
-crIL/cm-notch, tensile strength is 482k
g/c11t.

Further, the Vicat softening point was 129.4°C, and the pencil hardness was 2B.

The flame retardancy was SB according to the UL method, and it was flammable according to the ASTM method.

50 parts by weight of a ring-opening polymer purified (post-treated) by the above method, 50 parts by weight of a vinyl chloride polymer (manufactured by Kureha Chemical Co., Ltd., trade name: Reha PVC8901, degree of polymerization 1100), acrylonitrile with a Mooney viscosity of 75. Butadiene copolymer rubber (manufactured by Japan Synthetic Rubber Co., Ltd.).

Product name Biker 1043, Acrylonitrile content 2
8 parts by weight), 3.0 parts by weight of dibutyl tin malate and 0.5 parts by weight of 2,2'-methylenebis(4
-methyl-6-tertiary-butylphenol) was kneaded with a roll in the same manner as above.

This mixture was press-molded in the same manner as above.

The Izotsu impact strength of the obtained press plate was 20.4 kg.
・cIIL/cIrL-notch, tensile strength is 42
It was 2 kg/ffl.

The Vikat softening point of this press plate was 121.0°C, and the pencil hardness was 2B.

The flammability was 5E-1 according to the UL method, and it was nonflammable according to the ASTM method.

Moreover, this composition had very good transparency.

Examples 2 to 17 Openings were made using a roll in the same manner as in Example 1, except that the rubber materials shown in Table 1 were used instead of the acrylonitrile-butadiene copolymer rubber used as the rubber material in Example 1. The mixture was kneaded with a ring polymer, a vinyl chloride polymer, and a stabilizer (the blending ratio was the same as in Example 1).

Each of the obtained mixtures was press-molded in the same manner as in Example 1 to create a press plate.

Izotsu impact strength, tensile strength,
Vicat softening point, pencil hardness and flammability are shown in Table 1.

Examples 18 to 20 Except for changing the blending amount of the acrylonitrile-butadiene copolymer rubber used as the rubber material in Example 1 as shown in Table 2 (vinyl chloride polymer, ring-opening polymer, and stabilizer). (The blending amount was the same as in Example 1), and kneaded using rolls in the same manner as in Example 1.

The obtained mixture was press-molded in the same manner as in Example 1 to create a press plate.

Izot impact strength of each of the obtained pressed plates.

The tensile strength and Vicat softening point are shown in Table 2.

Example 21 Kneading was carried out using rolls in the same manner as in Example 1, except that the blending amount of the ring-opening polymer used in Example 1 was changed to 75 parts by weight and the blending amount of the vinyl chloride polymer was changed to 25 parts by weight. did.

The obtained mixture was press-molded in the same manner as in Example 1 to create a press plate.

The Izotsu impact strength of the obtained pressed plate was 77.8 kg.
-cm/cm-notch, tensile strength is 410kg/
It was crtl.

The Vicat softening point of this press plate is 123.0°C,
Pencil hardness was 3B.

Further, the flammability was SB according to the UL method, and nonflammable according to the ASTM method.

Mixing was carried out using a roll in the same manner as in Example 1, except that the blending amount of the ring-opening polymer used in Example 1 was changed to 25 parts by weight, and the blending amount of the vinyl chloride polymer was changed to 75 parts by weight.

The obtained mixture was press-molded in the same manner as in Example 1 to create a press plate.

The Izotsu impact strength of the obtained press plate was 14.0 kg.
-cm/cm-notch, tensile strength is 470kg/
It was d.

The Vicat softening point of this press plate is 103.0°C,
The flammability was 5E-0 according to the UL method, and it was nonflammable according to the ASTM method.

Example 23 Instead of the vinyl chloride polymer used in Example 1, a vinyl chloride-vinyl acetate copolymer with a vinyl chloride content of 85 weight (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Shin-Etsu PVC) was used.
Kneading was carried out using rolls in the same manner as in Example 1, except that MC800 and polymerization degree 800 were used.

The obtained mixture was press-molded in the same manner as in Example 1 to create a press plate.

The Izod impact strength of the obtained pressed plate was 22.3 k.
g-CrrL/cfrL-notch, and the tensile strength at one bow was 420 kg/cytt.

The Vicat softening point of this press plate is 119.6°C,
Pencil hardness was 2B.

Furthermore, the flammability was SB according to the UL method, and nonflammable according to the ASTM method.

Examples 24-29. Comparative Examples 1 to 6 5-Methyl-5-methoxycarbonyl-bicyclo(2
,2,1)-hebutene-2 (containing exo form 40φ)3
kg, 1,2-dichloroethane 91, dehydrated with calcium hydride immediately before use as a solvent and 22.4 mA as a molecular weight regulator! 1,000 cen-1 (1.0 mole relative to the monomer) was added to the n- and stirred well.

In this solution, 1,2 tungsten hexachloride was added as a polymerization catalyst.
-Dichloroethane solution (0.2 mol/13) 68.
7 ml, 1,1-jethoxyethane (C
68.7 ml of a 1°2-dichloroethane solution (0.6 mol/1) of Hs CH(QC2H5)2 ) and 71.7 ml of a 1.2-dichloroethane solution (1.2 mol/13) of diethylaluminium chloride were added ( 0.76 mol of tungsten hexachloride per mol of monomer, 3 mol of diethylaluminum chloride per mol of tungsten hexachloride.

(6 moles of 1.1-jethoxyethane per 1 mole of tungsten hexachloride), ring-opening polymerization was carried out at 45 to 50°C for 3 hours.

After completion of ring-opening polymerization, purification treatment (post-treatment) in the same manner as in Example 1
I did this.

As a result, a slightly yellow transparent ring-opened polymer was obtained.

The polymerization conversion rate was 85.0%.

The ring-based viscosity of the obtained ring-opened polymer (in 1,2-dichloroethane, temperature 30°C, concentration 0.197 dl) was 0.76.
(hereinafter referred to as "Polymer A").

After drying the autoclave used in Example 1, the autoclave was purged with nitrogen, and immediately before use it was charged with 11.47 g of 1,2-dichloroethane dehydrated with calcium hydride, and the pressure was reduced using a precision distillation apparatus immediately before use as a monomer. 22.88 kg of 5,5-dicyano-bicyclo(2,2,1)-hebutene (20 mol, monomer concentration 20% w/v) and 24.8 ml of n-hexene-1 purified by distillation under (1 mole relative to the monomer) was added, and the reaction system was sufficiently stirred.

After that, 1.2- of tungsten hexachloride was used as a polymerization catalyst.
Dichloroethane solution (0.2 mol/A') 100r
al (0.1 mol% based on monomer), t, 1-jethoxymethane dissolved in 1,2-dichloroethane t (0.6 mol/A) 100 TLl (3 mol per 1 mol of tungsten hexachloride) ) and 1 of diethylaluminum chloride
．． 2-dichloroethane solution (1.0 mol/l) 120m
1 (6 moles per mole of tungsten hexachloride) was added, and polymerization was carried out at 70° C. for 5 hours.

After the polymerization was completed, post-treatment (purification treatment) was performed in the same manner as in Example 1.

As a result, 2.08 kg of a white powdery polymer was obtained (polymerization conversion rate: 73.0%).

Reduced viscosity of the obtained polymer (in dimethylformamide).

concentration 0.1, p/dl, temperature 30°C) is 0.53
(hereinafter referred to as "polymer B").

After drying the autoclave used in Example 1, it was purged with nitrogen, and 1,2-dichloroethane was dehydrated with calcium hydride immediately before use.8. 5-cyano-5-methyl-bicyclo(2,2,1,1
-Habten-22,66 kg (20 mol, monomer concentration 2
5 weight/volume ratio) and 17.3T as a molecular weight regulator.
Ll of n-hexene-1 (0.7 molar proportion to the monomer) was added, and the reaction system was stirred to become homogeneous.

After that, 1,2-tungsten hexachloride was used as a polymerization catalyst.
Dichloroethane solution (0.2 mol/l) 80 ml (0.08 mol% based on monomer), 1°2-dichloroethane solution of 1.1-jethoxyethane (0.6 mol/l) 8
Add 0 ml (3 mol to 1 mol of tungsten hexachloride) and 96 mA' (6 mol to 1 mol of tungsten hexachloride) of a 1,2-dichloroethane solution of diethylaluminium chloride (1,0 mol, #), Polymerization was carried out at ℃ for 3 hours.

After the polymerization was completed, post-treatment was performed in the same manner as in Example 1.

As a result, 2.19 kg of a white powdery polymer was obtained (polymerization conversion rate: 82%).

Reduced viscosity of the obtained polymer (in dimethylformamide,
Concentration: 0.197 dl.

30°C) was 0.65 (hereinafter referred to as "Polymer C").

After drying the autoclave used in Example 1, it was purged with nitrogen, and 1,2-dichloroethane was dehydrated with calcium hydride immediately before use.8. 22.66 kg of 5-cyanomethyl-bicyclo(2,2,1)-hebutene (20 mol, monomer concentration) was prepared by charging O4 and purified by distillation under reduced pressure using a precision distillation apparatus immediately before use as a monomer. 25 weight/
17.3 ml of n-
Add hexene-1 (0.7 molar ratio to monomer),
The reaction system was stirred to become homogeneous.

After that, 1.2- of tungsten hexachloride was used as a polymerization catalyst.
Dichloroethane solution (0.2 mol/A') 70rn
l (0.07 mol% based on the monomer), 70 ml of a 1,2-dichloroethane solution (0.6 mol/l) of l,
mol) and 1.2 of diethylaluminum chloride
-Dichloroethane solution (1.0 mol/A) 84TIll
(6 mol per 1 mol of tungsten hexachloride) is added,
Polymerization was carried out at 70°C for 4 hours.

After the polymerization was completed, post-treatment was performed in the same manner as in Example 1.

As a result, 2.33 yu of white powdery polymer was obtained (polymerization conversion rate: 87).

Reduced viscosity of the obtained polymer (in dimethylformamide,
The concentration (0.1 g/di, 30°C) was 0.67 (hereinafter referred to as "Polymer D").

After drying the autoclave used in Example 1, it was purged with nitrogen, and N-made 1 and 2 were added to it in the same manner as in Example 1.
-dichloroethane12. OA? I prepared it.

3,34k purified in the same manner as in Example 1 as a monomer
g of 5-cyano-bicyclo(2,2,1)-hebutene-
2 (23 mol), 0.82 kg (12 mol) of cyclopentene purified using a precision distillation apparatus, and 34.6 ml of n-hexene-1 (0.7 mol relative to the monomer) as a molecular weight regulator. The mixture was added and stirred to make the reaction system homogeneous.

After that, 1.2- of tungsten hexachloride was used as a polymerization catalyst.
Dichloroethane solution (0,2 mol/l) 120r7
11 (0.06 mol% Ll based on the monomer, 120 ml of 1,2-dichloroethane solution (0.6 mol/l) of 1-jethoxyethane (3 mol per 1 mol of tungsten hexachloride) and diethylaluminium Chloride 1.
2-dichloroethane solution (1.0 mol/11) 14
4 ml (6 mol per 1 mol of tungsten hexachloride) was added, and polymerization was carried out at 70°C for 4 hours.

After the polymerization was completed, post-treatment was performed in the same manner as in Example 1.

As a result, 3.02 kg of white powdery polymer was obtained.

When this polymer was subjected to elemental analysis, it was found to be a copolymer containing 68 moles of 5-cyano-bicyclo(2,2,1)-heptene-2.

The reduced viscosity of the obtained copolymer (in 1,2-dichloroethane, 30°C, concentration 0.1 g/dl) was 0.63 (hereinafter, this obtained copolymer will be referred to as "Polymer E"). ).

After drying the autoclave used in Example 1, the atmosphere was replaced with nitrogen, and 1 and 2 purified in the same manner as in Example 1 were added to the autoclave.
- 8.01 liters of dichloroethane were charged.

1,67k purified as a monomer in the same manner as in Example 1
g of 5-cyano-bicyclo(2,2,1)-hebutene-
2 (l4 mol) and 1,0 purified in the same manner as above
0 kg of 5-methyl-5-methoxycarbonyl-piclo(2,2,1)-hebutene-2 (6 mol) and 14.8 ml of n-hexene-1 (as molecular weight regulator)
(0.6 mol % based on the monomer) was added and stirred so that the reaction system became homogeneous.

After that, 1.2- of tungsten hexachloride was used as a polymerization catalyst.
Dichloroethane solution (0.2 mol/13) 75ml
(0.075 mol% based on monomer), 1.1-jethoxyethane in 1.2-dichloroethane solution (0.6 mol%/
L// 1) 75rILl (3 mol per 1 mol of tungsten hexachloride and 1,2-dichloroethane solution of diethylaluminum chloride (1,0 mol/11)
90 rnl (6 moles per mole of tungsten hexachloride) was added, and polymerization was carried out at 70° C. for 3 hours with stirring.

After polymerization i1, post-treatment was performed in the same manner as in Example 1.

As a result, 2.25 kg of white powdery polymer was obtained.

Elemental analysis of this polymer revealed that it was a copolymer containing 73 mol% of 5-cyano-bicyclo(2,2,1)-hebutene-2.

The reduced viscosity of the obtained copolymer (in dimethylformamide, 30°C2 concentration: 0.1 g/dl) was 0.71.

(Hereinafter, the obtained copolymer will be referred to as "Polymer F").

5-cyanobisic acid used in Example 1 (
Polymer A2 Polymer B obtained by the above method instead of the ring-opened polymer of 2,2,1,1-heptene-2.

Example 1 except that the same amounts (50 parts by weight) of Polymer E and Polymer F were used.
(The resulting mixtures are hereinafter referred to as "Composition A.") using a roll.

Composition B2 Composition C2 Composition Part E and Composition F).

These respective compositions and polymers were press-molded in the same manner as in Example 1 to create press plates.

Izotsu impact strength, tensile strength,
Vicat softening point, pencil hardness and flammability (UL method and ASTM method) are shown in Table 3.

Comparative Example 7 Except that the acrylonitrile-butadiene copolymer rubber used as the rubber material in Example 1 was not blended,
The mixture was kneaded using a roll in the same manner as in Example 1.

The obtained mixture was press-molded in the same manner as in Example 1 to create a press plate.

The Izotsu impact strength of the obtained pressed plate was 7.1 kg・
cIrL/crrL-notch, tensile strength is 496
kg/crrt.

The Vicat softening point of this press plate is 121.5°C,
Pencil hardness was B.

Moreover, the flammability was 5E-1 according to the UL method, and it was nonflammable according to the ASTM method.

Comparative Example 8 5-cyano-piclo(2,
The blending amount of the ring-opening polymer of 2,1)-hebutene-2 was 100
The mixture was kneaded using a roll in the same manner as in Example 1, except that the parts by weight were changed and the vinyl chloride polymer was not blended.

The obtained mixture was press-molded in the same manner as in Example 1 to create a press plate.

The obtained pressed plate has an Izot impact strength of 110.0k.
g-cm/cm-notch, and the tensile strength is 403k
g/d.

The Vicat softening point of this press plate is 127.6°C,
Pencil hardness was 4B.

Furthermore, the flammability was SB according to the UL method, and combustible according to the ASTM method.

Comparative Example 9 The blending amount of the vinyl chloride polymer used in Example 1 was changed to 100 parts by weight, and 5-cyano-bicyclo(2
, 2,1,1-hebutene-2, except that the ring-opening polymer of 2,1,1-hebutene-2 was not blended.

The obtained mixture was press-molded in the same manner as in Example 1 to create a press plate.

The Izotsu impact strength of the obtained pressed plate was 5.5 kg.
cfrL/cIrL-notch, tensile strength is 494
It was 97 cuts.

The Vicat softening point of this press plate was 83.0°C, and the pencil hardness was B.

The flammability was 5E-0 according to the UL method, and it was nonflammable according to the ASTM method.

From the above examples, it is clear that the composition obtained according to the present invention not only has excellent impact resistance and has a well-balanced tensile strength, heat resistance, and hardness, but also is flame retardant. .

Claims (1)

[Scope of Claims] 1 (A) (1) A ring-opened homopolymer of a norbornene derivative having at least one cyan group or a substituent containing a cyanide group, (2) At least one ester group or a substituted substance containing an ester group. ring-opened homopolymers of norbornene derivatives having groups, (3) ring-opened copolymers of the norbornene derivatives, and (4) ring-opened copolymers of these norbornene derivatives with other cyclic olefin compounds having a molar ratio of at most 50. 99 to 10 parts by weight of at least one ring-opening polymer selected from the group consisting of copolymers and (BXI) a vinyl chloride homopolymer or (2) a copolymer containing at least 50 moles of vinyl chloride 1 to 90 parts by weight A formulation consisting of 100 parts by weight
Based on parts by weight (CX 1 ) butadiene-based rubbery material,
(2) Chlorinated polyethylene rubber, (3) Chlorosulfonated polyethylene rubber, (4) Ethylene-
Propylene-based rubbery material, (5) Isoprene-based rubbery material,
(6) Acrylic acid ester rubber, (kaisobutylene rubber) (8) Alkylene oxide rubber e7, (9)
A resin composition with improved impact resistance comprising 1 to 50 parts by weight of at least one rubbery material selected from the group consisting of a chloroprene rubbery material, αO) ethylene-vinyl acetate copolymer rubber, and αυ natural rubber. .