JP2676853B2 - Chlorinated higher α-olefin polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a chlorinated higher α-olefin polymer having novel and excellent practicality. More specifically, it has excellent weather resistance, ozone resistance, low temperature characteristics, heat aging resistance, dynamic fatigue resistance, reformability, adhesiveness, paintability, etc., and is used for various rubber products, resin modifiers, adhesives, paint components, etc. The present invention relates to a chlorinated higher α-olefin polymer that can be used as

[Conventional technology]

The ethylene / propylene / diene-based copolymer has good heat resistance and ozone resistance.
It is widely used as industrial rubber products, electrical insulating materials, civil engineering building materials, rubber products such as rubberized cloth, and plastic blending materials for polypropylene, polystyrene and the like.
However, since this copolymer is inferior in dynamic fatigue resistance, it was unsuitable for specific applications such as anti-vibration rubber, rubber rolls, belts and cover materials for tire vibrating parts.

On the other hand, although natural rubber is excellent in dynamic fatigue resistance, it is inferior in heat resistance and ozone resistance and has a practical problem.

[Problems to be solved by the invention]

The object of the present invention is a novel and useful chlorinated high-grade α- which is excellent in weather resistance, ozone resistance, low temperature characteristics, and heat aging resistance, and is also excellent in dynamic characteristics such as bending resistance, adhesiveness, paintability, etc.
It is to provide an olefin polymer.

[Means for solving the problem]

The present invention has a content of higher α-olefin units having 6 to 20 carbon atoms of 90 mol% or more, and has an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 1 to 10 dl / g. Chlorine content of α-olefin polymer is 5 to 35% by weight
It is a chlorinated higher α-olefin polymer characterized by comprising a chlorinated product such that

The higher α-olefin polymer before chlorination which is the base of the chlorinated higher α-olefin polymer of the present invention is a polymer of higher α-olefin having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms. A higher α having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms
-It is obtained by polymerizing an olefin using a Ziegler catalyst.

As the higher α-olefin unit having 6 to 20 carbon atoms, specifically, hexene-1, heptene-1, octene-1,
Nonene-1, decene-1, undecene-1, dodecene
1, straight chain α-olefins such as 1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, eicosene-1; and 6-methylheptene-1,
7-methyloctene-1,8-methylnonene-1,9-
Methyldecene-1,10-methylundecene-1,11-methyldodecene-1,12-methyltridecene-1,13-methyltetradecene-1,15-methylhexadecene-1,
17-Methyloctadecene-1,5-methylheptene-
1,6-ethyloctene-1,7-ethylnonene-1,
8-ethyldecene-1,9-ethylundecene-1,10
An example is a unit derived from a monomer component such as a branched α-olefin such as -ethyldodecene-1.
These monomer components may be contained alone or in plural. Further, in addition to these monomer components, other copolymerizable monomer components such as α-olefins and dienes having 5 or less carbon atoms are contained in the polymer in an amount not exceeding 10 mol% within the range not impairing the object of the present invention. You can leave.

The above-mentioned higher α-olefin polymers can be obtained by a conventionally known method, for example, JP-A Nos. 53-146292, 55-29591, and 56.
As described in No. 811, No. 58-83006, Japanese Patent Publication No. 56-39767, etc., a titanium-based catalyst containing titanium, magnesium, halogen, etc., an organoaluminum-based catalyst, etc. It can be produced by polymerizing an olefin.

The intrinsic viscosity [η] of these polymers measured in decalin at 135 ° C. is in the range of 1 to 10 dl / g, preferably 1.5 to 9 dl / g, particularly preferably 2 to 8 dl / g.

The chlorinated higher α-olefin polymer of the present invention is a chlorinated product of the above-mentioned higher α-olefin polymer and has a chlorine content of 5 to 35% by weight, preferably 7 to 30% by weight.

The chlorinated higher α-olefin-based polymer of the present invention has the following general formula —R _n —... [I] (wherein R is a higher α-olefin unit having 6 to 20 carbon atoms, and may be one type or two or more types). It is also possible that n is a repeating number determined by the above-mentioned intrinsic viscosity.), Which is a polymer in which hydrogen at any position of the higher α-olefin polymer is randomly substituted with Cl.

The chlorinated higher α-olefin polymer of the present invention has a temperature of 135 ° C.
The intrinsic viscosity [η] measured in decalin is in the range of 1 to 10 dl / g, preferably 1.5 to 9 dl / g, and particularly preferably 2 to 8 dl / g.

The chlorinated product of the higher α-olefin polymer of the present invention can be produced by the following method. That is, a method in which a higher α-olefin polymer is dissolved in a chlorine-stable solvent such as carbon tetrachloride, tetrachloroethylene, or chlorobenzene and brought into contact with molecular chlorine in a uniform solution state to chlorinate. , Or N-chloroacetamide, N-chlorosuccinimide, 1,3-dichloro-5,5-
A chlorine compound such as dimethylhydantoin is uniformly kneaded into a higher α-olefin polymer by a roll or a Banbury mixer, and is produced by a method of chlorinating by heating to a temperature at which chlorine is liberated. The method of chlorinating is particularly preferable. When the chlorination reaction is carried out in a solution state, it is more preferable to carry out the reaction in the presence of a radical initiator or under irradiation of ultraviolet rays or visible light because the reaction proceeds efficiently. The degree of chlorination depends on the amount of molecular chlorine and other chlorinating agents used, reaction time,
It can be adjusted by appropriately selecting the reaction temperature and the like.

The chlorinated higher α-olefin-based polymer of the present invention is a polymer excellent in weather resistance, ozone resistance, heat resistance, dynamic fatigue resistance, reformability, low temperature characteristics, adhesiveness, paintability, etc. It is used in applications where the characteristics of are required. Especially when it is applied to resin modifiers, various rubber products, adhesives, resin components for paints, etc., it maximizes its features.

When the chlorinated higher α-olefin polymer of the present invention is used as a resin modifier, for example, polyvinyl chloride, polystyrene, AS resin, impact modifier such as polypropylene,
Non-migratory plasticizer for semi-rigid or soft polyvinyl chloride,
It can be effectively used as a flame retardant for polyolefins such as polyethylene and polypropylene. When used as a resin modifier, it can be used under substantially the same conditions as the same kind of resin modifier used conventionally.

Further, when the chlorinated higher α-olefin polymer of the present invention is used as an adhesive, it can be widely used as a general adhesive, but especially, polyolefins such as polyethylene and polypropylene, and chlorine containing such as polyvinyl chloride and polyvinylidene chloride are contained. It can be effectively used as an adhesive with a polymer or an aromatic polymer such as a stin-based resin, polyester, or polycarbonate. The adhesive can be composed only of a chlorinated higher α-olefin polymer, but the composition is formed by adding additives such as other polymer components and stabilizers to the extent that the adhesive performance is not impaired. I don't mind.

When the chlorinated higher α-olefin-based polymer of the present invention is used as various rubber products, it can be used in an unvulcanized state, but it is preferable to use it in a vulcanized state because the properties are further exhibited.

The vulcanizates of various rubber products using the chlorinated higher α-olefin polymer of the present invention are manufactured as follows.
That is, it is produced by first preparing an unvulcanized compounded rubber using a chlorinated higher α-olefin polymer, then molding the compounded rubber into an intended shape and then vulcanizing it. As the vulcanization method, either a method of heating using a vulcanizing agent or a method of irradiating with an electron beam can be used. Examples of the vulcanizing agent used during vulcanization include metal salts, sulfur compounds, organic peroxides, and combinations thereof.

As the metal salt used for vulcanization of the chlorinated higher α-olefin polymer of the present invention, magnesium oxide, higher fatty acid zinc such as zinc stearate, zinc oleate, red lead, litharge and the like are used. The amount of the metal salt to be blended is appropriately about 3 to 15 parts by weight, preferably about 5 to 10 parts by weight, based on 100 parts by weight of the chlorinated higher α-olefin polymer.

Examples of the sulfur compound used for vulcanization of the chlorinated higher α-olefin polymer of the present invention include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. It can be illustrated.

The amount of the sulfur-based compound to be blended is appropriately about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight, based on 100 parts by weight of the chlorinated higher α-olefin polymer.

When a sulfur compound is used as the vulcanizing agent, it is preferable to use a vulcanization accelerator together. As the vulcanization accelerator, N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide, 2-mercapto Thiazoles such as benzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyl-disulfide; diphenylguanidine, triphenylguanidine , Guanidine compounds such as diorsotolyl guanidine, orthotolyl pie guanide, diphenyl guanidine phthalate; acetaldehyde-
Aniline reactant, butyraldehyde-aniline condensate,
Aldehyde amines such as hexamethylenetetramine and acetaldehyde ammonia, or aldehyde-ammonia systems; imidazoline systems such as 2-mercaptoimidazoline; thiourea systems such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, and diorthotolylthiourea; tetra Thiuram systems such as methyl thiuram monosulfide, tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, pentamethylene thiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldiocarbamate, Zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, dimethyldithiocarbami And the like Santeto systems such as dibutyl xanthate zinc; sodium acid, dimethyl dithiocarbamate selenium, dithio acid salt-based, such as tellurium diethyldithiocarbamate.

The amount of these vulcanization accelerators to be used is appropriately selected in the range of usually 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the chlorinated higher α-olefin polymer.

In order to obtain a vulcanized product that can be used under more severe conditions, it is recommended to use a triazine compound as a vulcanizing agent. The triazine compound can be added in an amount of 1 × 10 ⁻³ to 2 × 10 ⁻² mol, preferably 2.5 × 10 ⁻³ to 1 × 10 ⁻² mol, per 100 g of the chlorinated higher α-olefin polymer.

Examples of the triazine compound include 2,4,6-trimercaptotriazine, 2-dibutylamino-4,6-dimercaptotriazine, and 2-phenylamino-4,6-dimercaptotriazine.

Further, an organic base having an acid dissociation constant (pKa) of 7 or more as a vulcanization aid, or a compound capable of generating such a base is 5 × with respect to 100 g of a chlorinated higher α-olefin polymer.
It is used in an amount of 10 ^{−4 to} 2 × 10 ⁻² mol, preferably 1 × 10 ⁻³ to 1 × 10 ² mol.

As these vulcanization aids, 1,8-diaza-bicyclo (5,4,0) -undecene-7, laurylamine, benzylamine, dibenzylamine, N-methylmorpholine,
Dicyclohexylamine, Zinc dibutyldithiocarbamate, Ventamethylenedithiocarbamic acid viveridine salt, Benzoic acid piperidine salt, Mixture of diethylene glycol and dicyclohexylamine, N-cyclohexyl-
2-benzothiazolyl sulfenamide, dipentamethylene thiuram tetrasulfide, tetramethyl thiuram disulfide, tetramethylphosphonium iodide, tetramethylammonium chloride, tetrabutylphosphonium bromide, tetrabutylammonium bromide, and other onium salts. be able to.

Further, in order to cope with various rubber processing steps, it is recommended to add a compound having an oxymethylene structure and an anti-scorch agent.

Examples of the compound having an oxymethylene structure include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol and the like, and these are usually 2 to 10 parts by weight, preferably 100 parts by weight of a chlorinated higher α-olefin polymer. 3 to 5 parts by weight are used.

Known scorch inhibitors can be used as the scorch inhibitor, maleic anhydride, thioimide-based compounds,
Sulfonamide compounds can be exemplified. The above components are usually used in a proportion of 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the chlorinated higher α-olefin polymer.

Examples of the organic peroxide used for vulcanizing the chlorinated higher α-olefin polymer of the present invention include dicumyl peroxide and 2,5-dimethyl-2,5-di (tertiary butylperoxy).
Hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (tertiary butylperoxy) hexyne-3, ditertiary butyl peroxide, ditertiary butyl Peroxy-3,3,5-trimethylcyclohexane, tertiary butyl hydroperoxide and the like can be exemplified, but among them, dicumyl peroxide, ditertiary butyl peroxide and ditertiary butylperoxy-3,3,5-trimethylcyclohexane are preferred. .

The amount of the organic peroxide used is usually 3 × 10 ^{−4 to} 5 × 10 ⁻² mol, preferably 1 × 10 ^{−3 to} 3 × 10 ⁻² mol, per 100 g of the chlorinated higher α-olefin polymer. It is appropriate to choose the ratio.

When an organic peroxide is used as a vulcanizing agent, it is preferable to use a vulcanizing aid together. Examples of vulcanization aids include quinone dioximes such as sulfur and p-quinone dioxime; methacrylates such as polyethylene glycol dimethacrylate; allyls such as diallyl phthalate and triallyl cyanurate; other maleimides; divinylbenzene, etc. To be done. Such a vulcanization aid is used in an amount of 1/2 to 2 moles, preferably about equimolar, based on 1 mole of the organic peroxide used.

If an antiaging agent is used, the chlorinated higher α of the present invention can be used.
-It is the same as in the case of ordinary rubber that the life of the vulcanizate obtained from the olefin polymer can be extended. Examples of the antiaging agent used in this case include aromatic secondary amine stabilizers such as phenylnaphthylamine and N, N'-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene, tetrakis [methylene ( Phenolic stabilizers such as 3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane; bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl A thioether stabilizer such as sulfide; a dithiocarbamate stabilizer such as nickel dibutyldithiocarbamate is blended alone or in combination of two or more kinds.

The amount of such an antioxidant to be used is appropriately selected in the range of usually 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the chlorinated higher α-olefin polymer.

When using an electron beam without using a vulcanizing agent as a vulcanizing method, 0.1 to 10 MeV (megaelectron volt), preferably 0.3 to the molded unvulcanized compounded rubber described below is used.
Electrons with energy of ~ 2MeV absorbed dose 0.5 ~ 35M
Irradiation may be performed in rad (megarad), preferably 0.5 to 10 Mrad. At this time, a vulcanization aid used in combination with the organic peroxide as the vulcanization agent may be used, and the amount thereof is 1 × with respect to 100 g of the chlorinated higher α-olefin polymer.
The compounding amount is 10 ^-4 to 1 × 10 ^-1 mol, preferably 1 × 10 ^{-3 to} 3 × 10 ^-2 mol.

In the compound of the chlorinated higher α-olefin polymer to be vulcanized, an auxiliary agent, a filler, a softening agent, a flame retardant, a processing aid and the like are appropriately mixed.

Examples of the auxiliary agent include SRF, GPF, FEF, HAF, ISAF,
Various carbon blacks such as SAF, FT and MT, finely divided silicic acid, etc. are appropriately used. As the filler, for example, light calcium carbonate, heavy calcium carbonate, talc, clay and the like are used. These reinforcing agents and fillers are usually added in an amount of 300 parts by weight or less, preferably 200 parts by weight or less, per 100 parts by weight of the chlorinated higher α-olefin polymer.

As the softener, for example, process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt,
Petroleum-based substances such as petrolatum; coal tars such as coal tar and coal tar pitch; castor oil, linseed oil,
Fat oils such as rapeseed oil and coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax, lanolin; fatty acids such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate or metal salts thereof; petroleum resin, attack Synthetic polymer substances such as tic polypropylene and coumarone indene resin; ester-based plasticizers such as dioctyl phthalate and dioctyl adipate are used. These softening agents are used in an amount of about 200 parts by weight or less, preferably about 10 parts by weight, per 100 parts by weight of the chlorinated higher α-olefin polymer.
It is used in a proportion of 0 parts by weight or less.

Although the chlorinated higher α-olefin-based polymer of the present invention is itself flame retardant, it is recommended to add another flame retardant in order to obtain higher flame retardancy.

As the flame retardant that can be used in the present invention, any of the flame retardants commonly used in plastics and rubbers can be used. For example, phosphorus-based flame retardants such as triphenyl phosphate;
Decabromodiphenyl ether, chlorinated polyethylene,
In addition, it is marketed under each trade name such as trade name Dechloran Plus 515 (Marusho Sangyo Co., Ltd.), trade name Planeron DB-100 (Mitsui Toatsu Fine Co., Ltd.), trade name Bromrite BR-128F (Hitachi Chemical Co., Ltd.) Examples thereof include halogen-based flame retardants that are used; antimony trioxide; inorganic flame retardants such as aluminum hydroxide, which is commercially available under the trade name of Hydrite H-40; and mixtures of the above flame retardants. These flame retardants are appropriately selected depending on the application,
The amount is usually 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the chlorinated higher α-olefin polymer.

Next, as the processing aid, those used in the processing of ordinary rubber can be used, and ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate, zinc stearate, esters of the above acids. Examples thereof include higher fatty acids, salts thereof and esters thereof. These processing aids are usually
It is used in an amount of up to about 10 parts by weight, preferably about 1 to 5 parts by weight, based on 100 parts by weight of the chlorinated higher α-olefin polymer.

The rubber compound can be prepared, for example, by the following method. Chlorinated higher α-olefin polymer and reinforcing agent,
Additives such as fillers and softeners are kneaded using a mixer such as a Banbury mixer at a temperature of about 80 to 170 ° C for about 3 to 10 minutes, and then a vulcanizing agent and a vulcanization aid are added to a roll such as an open roll. Rolling temperature is about 40 ~ 80 ℃
The mixture is kneaded for about 5 to 30 minutes and dispensed to prepare a ribbon-shaped or sheet-shaped rubber compound. Alternatively, chlorinated higher α-
It is also possible to prepare a rubber compound in the form of pellets by directly supplying the olefin polymer and the compounding agent to an extruder heated to about 80 to 100 ° C. and setting a residence time of about 0.5 to 5 minutes.

The unvulcanized rubber compound thus prepared is, for example, extruded and then molded into a desired shape by a calender roll, a press or the like. Simultaneously with molding or in a vulcanization tank, the molded product is usually about 150 It is vulcanized by the method of heating to a temperature of ~ 270 ° C for about 1 to 30 minutes.

As the vulcanizing tank, steam vulcanizing can, hot air heating tank,
A fluidized bed of glass beads, a molten salt vulcanization tank, a microwave vulcanization tank, etc. may be used alone or in combination.

The rubber vulcanizate produced as described above is itself an anti-vibration rubber, automobile industrial parts such as duct cover boots, cover materials for tire vibration parts, rubber rolls, industrial rubber products such as belts, and electrical insulation materials. It is used as a civil engineering and building materials article, rubberized cloth, etc. When a foaming agent is added to the unvulcanized compounded rubber, a foamed product is produced and can be used for heat insulating materials, cushioning materials, sealing materials and the like.

〔The invention's effect〕

The chlorinated higher α-olefin polymer of the present invention is novel and excellent in weather resistance, ozone resistance, heat aging resistance, dynamic fatigue resistance, reformability, low temperature characteristics, adhesiveness, paintability, etc. It is available and useful in the field.

〔Example〕

 Next, the present invention will be specifically described with reference to examples.

The physical property values of the chlorinated higher α-olefin polymer and the starting higher α-olefin polymer in the examples were measured as follows.

(1) Intrinsic viscosity [η]: Measured in decalin at 135 ° C.

(2) Chlorine content: About 10 mg of a chlorinated higher α-olefin polymer is completely burned in an oxygen flask, and the chlorine part is absorbed as hydrogen chloride in water. Next, AgNO ₃ was added to this hydrogen chloride solution, the precipitate of silver chloride was recovered, and the chlorine content (% by weight) of the chlorinated higher α-olefin polymer was determined from the fluorescent X-ray spectrum of silver chloride.

Example 1 320 g of polyhexene-1 having [η] of 2.6 dl / g was dissolved in carbon tetrachloride 4 at 70 ° C. in a glass flask under a nitrogen atmosphere. The chlorination reaction is carried out by t-butylperoxy (2
-Ethylhexanoate) was added, and the polymer solution was kept under reflux of carbon tetrachloride in a light-shielded state, and chlorine gas was blown thereinto at 23 / h for 4 hours while stirring. After the reaction was completed, the polymer solution was added to a large amount of methanol to precipitate the polymer, which was collected by filtration. Further, the polymer was repeatedly washed with methanol, and under a nitrogen atmosphere,
Chlorinated polyhexene-1 by drying under reduced pressure at 60 ℃
I got The chlorine content of the produced polymer was 30.1% by weight.

Examples 2 to 3 Table 1 shows the results of chlorination in the same manner as in Example 1 except that the chlorine blowing time was changed.

Examples 4 to 7 Table 1 shows the results of chlorination by changing the polymer of Example 1 to polyoctene-1 and polydecene-1.

Example 8 Using the chlorinated polyhexene-1 of Example 1, the compounds shown in Table 2 were kneaded with an 8-inch open roll to obtain an unvulcanized compounded rubber.

This compounded rubber was heated for 20 minutes by a press heated to 160 ° C. to prepare a vulcanized sheet. This sheet allows JI
Tensile strength (T _B ), elongation (E _B ), and JIS A hardness spring hardness (H _S ) were measured according to SK6301. 120 at the same time
An aging test was conducted at 70 ° C for 70 hours to examine the heat aging resistance. In addition, a bending test was performed according to JIS K6301, and cracks from 2 mm to 17
The number of flexions that grow to mm was investigated. Table 3 shows the results. Table 2 (parts by weight) Chlorinated polyhexene-1 100 Stearic acid 1 Magnesia 5 ISAF-Carbon 1) 50 Naphthenic oil 2) 10 2,4,6-Trimercaptotriazine 3) 0.5 Dicyclohexylamine 0.5 1) Trade name: Asahi 80 Asahi Carbon Co., Ltd. 2) Product name: Sansen 4240 Sun Oil Co., Ltd. 3) Product name: ZISNET-F Sankyo Kasei Co., Ltd. Example 9 In Example 8, the chlorinated polyhexene of Example 1 was used.
Chlorinated polyoctene-1 prepared in Example 4 instead of 1
The same procedure as in Example 8 was carried out except that was used. Table 3 shows the results.

Example 10 In Example 8, the chlorinated polyhexene of Example 1 was used.
Example 8 was carried out in the same manner as in Example 8 except that the chlorinated polydecene-1 produced in Example 7 was used in place of 1. Table 3 shows the results.

Example 11 The chlorinated polyoctene-1 produced in Example 6 was blended with polyvinyl chloride according to the formulation shown in Table 4. Table 4 (parts by weight) Chlorinated polyoctene-1 10 Polyvinyl chloride 100 Cd-Ba-Zn-based stabilizer 1.5 Cd-Zn-based stabilizer 0.5 Calcium stearate 1.0 Mixing 4.3 Using a Banbury mixer, casing (10 kg / cm) Heated in ² ). After kneading for 5 minutes,
The resin temperature was 190 ° C. Surface temperature after dumping 160
The sheet was taken out after being wound on an open roll at ℃ for 3 minutes.

Preheat this sheet at 170 ° C for 4 minutes, then 170 ° C, 10
Heat press at 0kg / cm ² for 2 minutes, then 20 ℃, 100kg / cm ²
Press molding was carried out under the conditions of a cooling press for 5 minutes to obtain a smooth sheet having a thickness of 2 mm.

With this press sheet, Izod impact strength was measured according to JIS K6370. Table 5 shows the results.

Comparative Example 1 The procedure of Example 11 was repeated except that chlorinated polyoctene-1 was not added. Table 5 shows the results.

Example 12 20 g of the polymer obtained in Example 3 was dissolved in 80 g of toluene and coated on a sheet of polypropylene (manufactured by Mitsui Petrochemical Industry Co., Ltd.) whose surface was wiped with white gasoline, 25 mm.
It was laminated and dried in an area of × 12.5 mm. The tensile shear peeling test of the obtained test piece was performed at a pulling speed of 50 mm / min. As a result, the peel strength was 15 kg / cm ² .

Example 13 In the same manner as in Example 12, polypropylene and polyvinyl chloride (manufactured by Nippon Zeon Co., Ltd.) were laminated together, and a shear peeling test was conducted. As a result, the peel strength was 13 kg / cm ² .

Front page continuation (72) Inventor Keiji Okada 3 Chikusaigan, Ichihara, Chiba Mitsui Petrochemical Co., Ltd. (56) References JP 61-268703 (JP, A) JP 61-209204 (JP) , A)

Claims (1)

(57) [Claims] 1. The content of higher α-olefin units having 6 to 20 carbon atoms is 90 mol% or more, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 1 to 10 dl / g. High α-olefin polymer with chlorine content of 5 to 35% by weight
A chlorinated higher α-olefin polymer characterized by comprising a chlorinated product chlorinated so that