JPH02160804A - Chlorinated higher alpha-olefin polymer - Google Patents

Abstract

PURPOSE:To obtain the title polymer excellent in weathering resistance, ozone resistance, thermal aging resistance, low-temperature properties, dynamic properties such as flex resistance and adhesiveness, coatability, etc., by controlling each of the number of carbon atoms, the chlorine content and the intrinsic viscosity as measured in decalin at 135 deg.C to fall within a specified range. CONSTITUTION:A chlorinated higher alpha-olefin polymer which has 6-20C higher alpha-olefin units, an intrinsic viscosity (eta) as measured in decalin at 135 deg.C of 1-10dl/g, and a chlorine content of 5-35wt.%. The above polymer is excellent in weathering resistance, ozone resistance, thermal aging resistance, low- temperature properties, dynamic properties such as flex resistance, adhesiveness, application properties, etc., and can be used in many fields.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel and highly practical chlorinated high-α
-Relating to olefin polymers. More details include weather resistance, ozone resistance, low temperature properties, heat aging resistance, dynamic fatigue resistance,
This invention relates to a chlorinated higher α-olefin polymer that has excellent modification properties, adhesion properties, paintability, etc., and can be used as various rubber products, resin modifiers, adhesives, paint components, etc.

[Conventional technology]

Ethylene-propylene-diene copolymers have good heat resistance and ozone resistance, so they are used in automobile industrial parts, industrial rubber products, electrical insulation materials, civil engineering and construction materials, rubber products such as rubberized cloth, and polypropylene. It is widely used as a material for plastic blending with polystyrene, etc. However, this copolymer has poor dynamic fatigue resistance, so
It was unsuitable for specific uses, such as anti-vibration rubber, rubber rolls, belts, and cover materials for tire vibrating parts.

On the other hand, although natural rubber has excellent dynamic fatigue resistance, it has poor heat resistance and ozone resistance, which poses practical problems.

[Problem to be solved by the invention]

The object of the present invention is to provide a novel and useful chlorinated high-grade α- An object of the present invention is to provide an olefin polymer.

[Means to solve the problem]

The present invention is characterized in that (a) it contains a higher α-olefin unit having 6 to 20 carbon atoms, and (b) it has an intrinsic viscosity [η] measured in decalin at 135°C.
(c) a chlorinated higher α-olefin polymer having a chlorine content in the range of 5 to 35% by weight; It is an olefin polymer.

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-olefins having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms. is obtained by polymerizing a higher α-olefin having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, using a Ziegler catalyst.

Specifically, the higher α-olefin units having 6 to 20 carbon atoms include hexene-1, heptene-1, octene-1,
nonene-1, decene-1, undecene-1, dodecene-
1, linear α-olefins such as tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, eicosene-1; and 6-methylhebutene-1. 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-■, 5-methylhebutene-1,6-nityloctene-1,7-nitylnonene-1,8-ethyldecene-1,9- Examples include units derived from monomer components such as branched α-olefins such as ethylundecene-1,10-ethyldodecene-1. These monomer components may be contained alone or in combination. moreover,
In addition to these monomer components, other copolymerizable monomer components 1, e.g.
The following α-olefins and dienes may be contained in the polymer in an amount of 10 mol% or less.

The above-mentioned higher α-olefin polymers can be prepared by conventionally known methods such as JP-A-53-146292 and JP-A-55-295.
As described in No. 91, No. 56-811, No. 58-83006, and Special Publication No. 56-39767, etc.
It can be produced by polymerizing the above-mentioned higher α-olefin using a titanium-based catalyst, an organoaluminium-based catalyst, etc. containing titanium, magnesium, halogen, etc. as components.

The intrinsic viscosity [η] of these polymers measured in decalin at 135°C is 1 to 10 d12/g, preferably 1°5 to 9
dQ/g, particularly preferably in the range of 2 to 8 dll/g.

The chlorinated higher α-olefin polymer of the present invention is a chlorinated product of the above-mentioned higher α-olefin polymer, and the chlorine content is in the range of 5 to 35 weight percent or 7 to 30 weight percent. It is in.

The chlorinated higher α-olefin polymer of the present invention has the following general formula % formula % (1) (wherein R is a higher α-olefin unit having 6 to 20 carbon atoms, and may be one type or two or more types. (n is the repetition number determined by the limiting viscosity) is a polymer in which hydrogen at any position of a higher α-olefin polymer is randomly substituted with Cg.

135°C of the chlorinated higher α-olefin polymer of the present invention
The intrinsic viscosity [η] measured in decalin is 1 to 10 dQ/
g, preferably 1.5 to 9 dΩ/g, particularly preferably 2
~8 dQ/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, tetrachlorethylene, or chlorobenzene, and the solution is brought into contact with molecular chlorine to chlorinate the polymer. , or N-chloroacetamide, N-chlorsuccinimide, 1,3-dichloro-5
, 5-dimethylhydantoin is uniformly kneaded into a high-grade α-olefin polymer using a roll or Banbury mixer, and then chlorinated by heating to a temperature that liberates chlorine. Among these, a method of chlorination in a solution state is particularly preferred.

When carrying out the chlorination reaction in a solution state, it is more preferable to carry out the reaction in the presence of a radical initiator or under irradiation with ultraviolet rays or visible light because the reaction proceeds efficiently. The degree of chlorination can be adjusted by appropriately selecting the amount of molecular chlorine or other chlorinating agent used, reaction time, reaction time, temperature, etc.

The chlorinated higher α-olefin polymer of the present invention is a polymer with excellent weather resistance, ozone resistance, heat resistance, dynamic fatigue resistance, modification properties, low temperature properties, adhesiveness, paintability, etc. It is used for applications that require the following characteristics. In particular, when applied to resin modifiers, various rubber products, adhesives, resin components for paints, etc., its features are maximized.

When the chlorinated higher α-olefin polymer of the present invention is used as a resin modifier, for example, an impact modifier for polyvinyl chloride, polystyrene, AS resin, polypropylene, etc.
Non-migratory plasticizer for semi-rigid to flexible 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 type of m-lipid modifier that has been used conventionally.

In addition, 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. It can be effectively used as an adhesive with polymers or aromatic polymers such as styrene resins, polyesters, and polycarbonates. The adhesive may consist only of a chlorinated higher α-olefin polymer, but the composition may be formed by adding other polymer components and additives such as stabilizers to the extent that the adhesive performance is not impaired. I can't help it.

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

Vulcanized products of various rubber products using the chlorinated higher α-olefin polymer of the present invention are produced 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. Vulcanizing agents used during vulcanization include metal salts, sulfur compounds, organic peroxides, and combinations thereof.

The metal salts used in the vulcanization of the chlorinated higher α-olefin polymer of the present invention include magnesium oxide, higher fatty acid zinc, such as zinc stearate, zinc oleate,
Red lead, resurge, etc. are used. The blending amount of the metal salt is based on 100 parts by weight of the chlorinated higher α-olefin polymer.
It is usually appropriate to select a proportion of about 3 to 15 parts by weight, preferably about 5 to 10 parts by weight.

Examples of sulfur compounds used in the vulcanization of the chlorinated higher α-olefin polymer of the present invention include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, etc. can be exemplified.

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

When using a sulfur compound as a vulcanizing agent, it is preferable to use a vulcanization accelerator in combination. As a vulcanization accelerator, N-cyclohexyl-2-benzothiazole-sulfenamide,
N-oxydiethylene-2-benzothiazole-sulfenamide, N,N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2- Thiazole series such as (2,6-diethyl-4-morpholinothio)benzothiazole and dibenzothiazyl-disulfide; diphenylguanidine,
triphenylguanidine, diorthotolylguanidine,
Guanidine series such as orthotolyl pi-guanide and diphenylguanidine phthalate; aldehyde amines or aldehyde-ammonia series such as acetaldehyde-aniline reactants, butyraldehyde-aniline condensates, hexamethylenetetramine, acetaldehyde ammonia; 2-mercaptoimidacillin Imidacillin series such as thiocarbamic acid, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea, etc.; tetramethylthiuram monosulfide, tetramethylthiuram disulfide,
Thiuram series such as tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, butylphenyldithiocarbamate acid zinc,
Examples include dithioate salts such as sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; and santates such as zinc dibutylxanthate.

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

In order to obtain a vulcanizate that can withstand use under even harsher conditions, it is recommended to use a triazine compound as a vulcanizing agent. The triazine compound is 1 x 10-3 to 2 x 10 per 100 g of chlorinated higher α-olefin polymer.
-''2 mol, preferably 2.5 x 10-3 to 1 x 1
It can be added at a ratio of O-2 moles.

Examples of the triazine compound include 2,4.6-trimercaptotriazine, 2-dibutylamino-4,6-dimercaptotriazine, and 2-phenylamino-4,6-dimercaptotriazine.

In addition, as a vulcanization aid, an organic base with an acid dissociation constant (ρ to a) of 7 or more, or a compound capable of generating such a base, is used in an amount of 5 x 10- 4-2xlO-2 mol, preferably IX
10"" to I.times.10-" moles are used.

These vulcanization aids include 1,8-diaza-bicyclo(5,4,0)-undecene-7, laurylamine, benzylamine, dibenzylamine, N-methylmorpholine, dicyclohexylamine, zinc dibutyldithiocarbamate. , pentamethylene dithiocarbamic acid piperidine salt, benzoken piperidine salt, mixture of diethylene glycol and dicyclohexylamine, N-cyclohexyl-2-benzothiazolyl sulfenamide, dipentamethylene thiuram tetrasulfide, tetramethylthiuram disulfide, tetramethylphosphonium iodide , onium salts such as tetramethylammonium chloride, tetrabutylphosphonium bromide, and tetrabutylammonium bromide.

Furthermore, in order to cope with various rubber processing steps, addition of compounds with oxymethylene structure and addition of scorch inhibitors can be recommended.

Examples of compounds having an oxymethylene structure include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, etc. 1 These are usually used in an amount of 2 to 10 parts by weight per 100 parts by weight of the chlorinated higher α-olefin polymer.

Preferably, 3 to 5 parts by weight are used.

As the scorch inhibitor, a known scorch inhibitor can be used, and examples thereof include maleic anhydride, thioimide compounds, and sulfonamide compounds. 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, per 100 parts by weight of the chlorinated higher α-olefin polymer.

The organic peroxides used in the vulcanization of the chlorinated higher α-olefin polymer of the present invention include dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2, 5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5
-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, di-tert-butyl peroxy-3,3,
Examples include 5-trimethylcyclohexane and tert-butyl hydroperoxide, among which dicumyl peroxide, di-tert-butyl peroxide, and di-tert-butyl peroxy-3,3,5-trimethylcyclohexane are preferred.

The amount of organic peroxide to be used is usually selected at a ratio of 3 x 10- to 5XIP2 moles, preferably lXl0-3 to 3XIO-'' moles, per 100 g of the chlorinated higher α-olefin polymer. .

When using an organic peroxide as a vulcanizing agent, it is preferable to use a vulcanizing aid in combination. Vulcanization aids include sulfur, quinone dioxime types such as P-quinone dioxime; methacrylate types such as polyethylene glycol dimethacrylate;
Examples include allyl types such as diallyl phthalate and triallyl cyanurate; other maleimide types; and divinylbenzene. Such a vulcanization aid is used in an amount of 1/2 to 2 moles, preferably about equal moles, per mole of the organic peroxide used.

In addition, if an anti-aging agent is used, the chlorinated high α-
Similarly to the case of ordinary rubber, the life of the vulcanizate obtained from the olefin polymer can be extended. Antioxidants used in this case include, for example, phenylnaphthylamine, aromatic secondary amine stabilizers such as N,N'-di-2-naphthyl-P-phenyl diamine; dibutylhydroxytoluene, tetrakis [ Phenolic stabilizers such as methylene (3,5-di-t-butyl-4-hydroxy)hydrocinnamate comethane: bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t- A thioether stabilizer such as butylphenyl sulfide, and a dithiocarbamate stabilizer such as nickel dibutyl dithiocarbamate may be used alone or in combination of two or more.

The amount of such anti-aging agent to be used is usually selected at a ratio of 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, per 100 parts by weight of the chlorinated higher α-olefin polymer. is appropriate.

When the vulcanization method does not use a vulcanizing agent and uses an electron beam, the molded unvulcanized compounded rubber described below is 0.1 to 1 OMeV (megaelectron volt), preferably 0.3 to 2. Electrons having an energy of MsV may be irradiated at an absorbed dose of 0.5 to 35 Mrad (megarad), preferably 0.5 to 10 Mrad.

At this time, a vulcanization aid may be used in combination with the organic peroxide as the vulcanizing agent, and the amount thereof is 1 x 10-4 to ioo g of the chlorinated higher α-olefin polymer. I
X 10-1 mol, preferably IX 10-3 to 3
Blend 2 moles of Xio.

A reinforcing agent, a filler, a softening agent, a flame retardant, a processing aid, etc. are appropriately added to the blend of the chlorinated higher α-olefin polymer to be vulcanized.

Examples of reinforcing agents include SRF, GPF, FEF,
Various carbon blacks such as HAF, 15AF, SAF, FT, and MT, finely divided silicic acid, and the like are used as appropriate. As the filler, for example, light calcium carbonate, heavy calcium carbonate, talc, clay, etc. are used. These reinforcing agents and fillers are all chlorinated high α-
The amount is usually 300 parts by weight or less, preferably 200 parts by weight or less, per 100 parts by weight of the olefin polymer.

In addition, as a softening agent, for example, process oil, lubricating oil,
Petroleum-based substances such as paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly; Coal tars such as coal tar and coal tar pitch; Fatty oils such as castor oil, linseed oil, rapeseed oil, and coconut oil; Tall oil; Sub; Beeswax ,
Waxes such as carnauba wax and lanolin; fatty acids or their metal salts such as ricinoleic acid, palmitic acid, barium stearate, and calcium stearate; petroleum resins,
Synthetic polymer substances such as atactic polypropylene and coumaron indene resin; ester plasticizers such as dioctyl phthalate and dioctyl adipate are used. These softeners are used in an amount of about 200 parts by weight or less, preferably about 100 parts by weight or less, per 100 parts by weight of the chlorinated higher α-olefin polymer.

The chlorinated higher α-olefin polymer of the present invention is.

Although flame retardant itself, the addition of other flame retardants is recommended to obtain even higher flame retardance.

As the flame retardant that can be used in the present invention, any flame retardant commonly used for plastics and rubber can be used, such as phosphorus-based flame retardants such as triphenyl phosphate; decabromodiphenyl ether, chlorinated polyethylene, and others, such as trade names. Dechloran Plus 515 (Marusho Sangyo Co., Ltd.), product name Planeron DB-100 (Mitsui Toatsu Fine Co., Ltd.), product name Bromrite BR-128
Halogen-based flame retardants commercially available under various trade names such as F (Hitachi Chemical Co., Ltd.); antimony trioxide; inorganic flame retardants such as aluminum hydroxide commercially available under the trade name Hydride H-40; and Examples include mixtures of the above flame retardants. These flame retardants are appropriately selected depending on the intended use, but are usually blended in an amount of 50 parts by weight or less, preferably 30 parts by weight or less, per 100 parts by weight of the chlorinated higher α-olefin polymer.

As the processing aids, those used in normal rubber processing can be used, including ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate, zinc stearate, and esters of the above acids. Examples include higher fatty acids, salts thereof, and esters thereof.

These processing aids are usually used in an amount of up to about 10 parts by weight, preferably about 1 to 5 parts by weight, per 100 parts by weight of the chlorinated higher α-olefin polymer.

A rubber compound can be prepared, for example, by the following method.

The chlorinated high-grade α=niolefin polymer and additives such as reinforcing agents, fillers, and softeners are mixed at a temperature of about 80 to 170°C using a mixer such as a Banbury mixer for about 3 to 10 minutes.
After kneading for minutes, the vulcanizing agent and vulcanizing aid are further mixed using rolls such as an open roll, and the roll temperature is 40~40°C.
The mixture is kneaded and separated at 80° C. for about 5 to 30 minutes to prepare a rubber compound in the form of a ribbon or sheet. Alternatively, the chlorinated higher α-olefin polymer and compounding agents may be added to
A pelletized rubber compound can also be prepared by feeding directly into an extruder heated to 00° C. and allowing a residence time of about 0.5 to 5 minutes.

The unvulcanized rubber compound thus prepared is, for example,
After extrusion molding, it is molded into a desired shape using calender rolls, presses, etc. At the same time as molding or in a vulcanization tank, the molded product is heated to a temperature of usually about 150 to 270°C for about 1 to 30 minutes.
It is vulcanized by heating for minutes.

As the vulcanization tank, a steam vulcanization tank, a hot air heating tank, a glass beads fluidized bed, a molten salt vulcanization tank, a microwave vulcanization tank, etc. are used singly or in combination.

The rubber vulcanizate produced in the above manner can be used as a material for automotive industrial parts such as anti-vibration rubber, duct cover boots, cover materials for tire vibrating parts, industrial rubber products such as rubber rolls and belts, and electrical insulation materials. It is used as civil engineering and construction materials, rubberized cloth, etc. Further, by blending a foaming agent with the unvulcanized compounded rubber, a foamed body is produced, which can be used for applications such as heat insulating materials, cushioning materials, and sealing materials.

〔Effect of the invention〕

The chlorinated higher α-olefin polymer of the present invention is novel,
and weather resistance, ozone resistance, and heat aging resistance.

It has excellent dynamic fatigue resistance, modification properties, low-temperature properties, adhesion, paintability, etc., and can be used and useful in a wide range of fields.

〔Example〕

Next, the present invention will be specifically explained using examples.

The physical property values of the chlorinated higher α-olefin polymer and the raw material 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 the chlorinated higher α-olefin polymer is completely combusted in an oxygen flask, and the chlorine portion is absorbed into water as hydrogen chloride.

Next, AgNO3 was added to this hydrogen chloride solution, the silver chloride precipitate was collected, and the chlorine content (wt%) of the chlorinated higher α-olefin polymer was determined from the fluorescent X-ray spectrum of silver chloride.
I asked for

Example 1 1,320 g of polyhexene with [η] of 2.6 dρ/g
was dissolved in carbon tetrachloride 4Q at 70°C in a glass flask under nitrogen atmosphere. For the chlorination reaction, 0.25 g of t-butylperoxy(2-ethylhexanoate) was added, the polymer solution was kept under reflux of carbon tetrachloride in the light-shielded state, and chlorine gas was added at 23 Q/min while stirring. This was done by blowing at h for 4 hours. After the reaction is complete, add the polymer solution to a large amount of methanol to precipitate the polymer.
It was collected by filtration. Furthermore, the polymer was repeatedly washed with methanol and dried under reduced pressure at 60° C. in a nitrogen atmosphere to obtain chlorinated polyhexene-1. The chlorine content of the produced polymer was 30.1% by weight.

Examples 2 to 3 Table 1 shows the results of chlorination performed in the same manner as in Example 1 by changing the chlorine blowing time.

Examples 4 to 7 The polymer of Example 1 was used as polyoctene-1 and polydecene-1.
Table 1 shows the results of chlorination.

Table 1 Example 8 The chlorinated polyhexene-1 of Example 1 was kneaded in the formulation shown in Table 2 using an 8-inch open roll to obtain an unvulcanized compounded rubber.

This compounded rubber was heated to 160°C in a press for 20
A vulcanized sheet was prepared by heating for a minute. This sheet has tensile strength (TB) and elongation (
E8), spring hardness according to JIS A hardness (1, s
) was measured. At the same time, an aging test was conducted at 120°C for 170 hours to evaluate heat aging resistance. Furthermore, JIS K6301
A bending test was conducted according to the method, and the number of bends at which the crack grew from 2 mm to 17 mm was determined. The results are shown in Table 3.

Table 2 (heavy part) Chlorinated polyhexene-1100 Stearic acid 1 Magnesia 5 ISAF-carbon 1) 50 Naphthenic oil 2) 10 2.4.6-Drimercaptotriazine 3)
0.5 dicyclohexylamine 0.
5 Table 3 Example 9 In Example 8, chlorinated polyhexene-1 of Example 1
The entire process was carried out in the same manner as in Example 8, except that chlorinated polyoctene-1 produced in Example 4 was used instead of chlorinated polyoctene-1. The results are shown in Table 3.

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

Example 1) Chlorinated polyoctene-1 produced in Example 6 was mixed with polyvinyl chloride according to the formulation shown in Table 4.

Table 4 (parts by weight) Chlorinated polyoctene-110 Polyvinyl chloride 100Cd-Ba-Z
n-based stabilizer 1.5Cd-Zn-based stabilizer 0.5calcium stearate
1.0 Example 11 was carried out in exactly the same manner as in Example 11 except that chlorinated polyoctene-1 was not blended.

The results are shown in Table 5.

Table 5 For mixing, a 4.3Q Banbury mixer was used, and the casing was heated with steam (10 kg/cd). After kneading for 5 minutes, the resin temperature was 190°C. After dumping out, the sheet was wound for 3 minutes on an open roll with a surface humidity of 160°C, and then the sheet was taken out.

Preheat this sheet at 170℃ for 4 minutes, then 170℃
, heat press at 100 kg/cd for 2 minutes, and then 20
It was press-molded under the conditions of cooling press at 100 kg/cJ at 100 kg/cJ for 5 minutes to obtain a smooth sheet with a thickness of 2 mm.

Using this press sheet, Izot impact strength was measured in accordance with JIS K6370. The results are shown in Table 5.

Comparative Example 1 Example 12 20 g of the polymer obtained in Example 3 was dissolved in 80 g of toluene and applied to a sheet of polypropylene (manufactured by Mitsui Petrochemical Industries, Ltd.) whose surface had been wiped with white gasoline.
It was laminated in an area of 5 mm x 12.5 mm and dried. The tensile shear peel test of the obtained test piece was carried out at 50 am/l1.
It was carried out at a pulling speed of in. As a result, the peel strength was 15
kg/a#.

Example 13 In the same manner as in Example 1z, polypropylene and polyvinyl chloride (Nippon Zeon Co., Ltd.>H) were bonded together and a shear peel test was conducted. As a result, the peel strength was 13 kg/
It was a#.

Claims (1)

[Claims] (1) (a) A higher α-olefin containing a higher α-olefin unit having 6 to 20 carbon atoms, and (b) a higher α-olefin having an intrinsic viscosity [η] measured in decalin at 135°C in the range of 1 to 10 dl/g. (c) A chlorinated higher α-olefin polymer characterized in that the chlorine content is in the range of 5 to 35% by weight.