JPH0428701A - Production of chlorinated and modified olefin polymer having branched chain and its composition - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having high heat resistance and solvent resistance and useful for coating composition, etc., by graft-polymerizing a monomer to a branched olefin polymer having high melting point in the presence of a radical initiator and reacting the graft polymer with chlorine until the chlorine content of the product reaches a specific level. CONSTITUTION:The objective chlorinated and modified olefin polymer having branched chain can be produced by graft-polymerizing a radically polymerizable monomer to a branched olefin polymer having a melting point of >=250 deg.C in the presence of a radical initiator and reacting the product with chlorine until the contents of the radically polymerizable monomer unit and chlorine reach 0.01-40wt.% and 10-70wt.%, respectively. The branched olefin polymer is preferably a polymer containing 55-100wt.% of a branched olefin unit such as 3-methylbutene-1 and 0-45wt.% of a 2-20C olefin unit.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method and composition for producing a chlorinated modified polymer. More specifically, the present invention relates to a method for producing a chlorinated modified branched olefin polymer having excellent heat resistance, and a coating composition and adhesive composition containing the chlorinated modified branched olefin polymer.

[Conventional technology and its! ! ! ! ] The chlorinated modified olefin polymer obtained by graft polymerizing maleic anhydride etc. to an olefin polymer such as polypropylene or polyethylene and further chlorinating it is a chlorinated modified olefin polymer which is also used as a useful film forming material. Clear lacquers have superior adhesion to the base, solvent resistance, and compatibility with other resins compared to lacquers.
It is widely used as a component of coating compositions such as paints and inks, and as a component of adhesives. However, coating compositions or adhesive compositions containing these chlorinated modified olefin polymers as main components have poor heat resistance,
There was a problem with softening.

In an attempt to improve the heat resistance of coating compositions or adhesive compositions mainly composed of such chlorinated modified olefin polymers, chlorinated modified 4-methylpentene-1 polymers, or copolymers, are used as the main components. A coating composition or an adhesive composition as a component has been proposed (Japanese Patent Application Laid-open No. 59-59-711
No. 60-179.413, Japanese Patent Application Laid-open No. 1983
Although the heat resistance of these proposed coating compositions and adhesive compositions has been improved, they are still insufficient.

The present inventors have conducted extensive research into improving the heat resistance of coating compositions and adhesive compositions according to the above-mentioned conventional techniques. As a result, coating compositions and adhesive compositions containing as an active ingredient a chlorinated modified branched olefin polymer obtained by graft polymerization modification of a branched olefin polymer having a melting point of 250°C or higher and further chlorination. It was discovered that the heat resistance was significantly improved when this material was used, and the present invention was completed based on this knowledge.

As is clear from the above description, the objects of the present invention are a method for producing a chlorinated modified olefin polymer with excellent heat resistance, a coating composition with excellent heat resistance containing the chlorinated modified olefin polymer, and an adhesive. An object of the present invention is to provide a drug composition.

[Means to solve the problem] The present invention has the following configuration.

(1) A branched olefin polymer with a melting point of 250°C or higher,
A radically polymerizable monomer is graft-polymerized in the presence of a radical initiator, and chlorine is further reacted to reduce the content of radically polymerizable monomer units and the chlorine content to 0.
．． A method for producing a chlorinated modified branched olefin polymer, characterized in that the amount is 01% to 40% by weight and 10% to 70% by weight.

(2) The branched olefin polymer is 3-methylbutene-1
, 3-methylpentene-1,4,4-dimethylpentene-1, and 4,4-dimethylhexene-1.
-100% by weight, and the branched olefin polymer and/or branched olefin copolymer having 0 to 45% by weight of olefin component units having 2 to 20 carbon atoms other than the branched olefin, item 1 above. The manufacturing method described in.

(3) The first monomer in which the radically polymerizable monomer is an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride.
The manufacturing method described in section.

(4) A branched olefin polymer with a melting point of 250°C or higher,
Obtained by graft polymerizing radically polymerizable monomers in the presence of a radical initiator and further reacting with chlorine, the content of radically polymerizable monomer units and the chlorine content are each 0.01% by weight. ~40% by weight, 10% by weight ~70
A coating composition containing 1% by weight of a chlorinated modified branched olefin polymer as an active ingredient.

(5) The branched olefin polymer is 3-methylbutene-1
, 3-methylpentene-1,4,4-dimethylpentene-1, and 4,4-dimethylhexene-1, and 55% to 100% by weight of branched olefin component units of ifl or more, and the above 4. The coating composition according to item 4, which is an MtM olefin polymer and/or a branched olefin copolymer containing 0 to 45% by weight of olefin component units having 2 to 20 carbon atoms other than branched olefins.

(6) The fourth monomer, wherein the radically polymerizable monomer is an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride.
The coating composition described in Section 1.

(7) A branched olefin polymer with a melting point of 250°C or higher,
Obtained by graft polymerizing radically polymerizable monomers in the presence of a radical initiator and further reacting with chlorine, the content of radically polymerizable monomer units and the chlorine content are Q and 01li mass%, respectively. ~40% by weight, 10% by weight~7
An adhesive composition containing 0% by weight of a chlorinated modified branched olefin polymer as an active ingredient.

(8) The branched olefin polymer is 3-methylbutene-1
, 3-methylpentene-1,4,4-dimethylpentene-1, and 4,4-dimethylhexene-1.
~100% by weight, and olefin component units having 2 to 2 o of carbon atoms other than the branched chain olefins are O~45N! % of the branched olefin polymer and/or the branched olefin copolymer.

(9) The seventh method, wherein the radically polymerizable monomer is an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride.
Adhesive composition described in Section.

The configuration of the present invention will be explained in detail below.

The branched olefin polymer according to the present invention has a periodicity represented by a titanium-containing solid catalyst component, such as a solid component mainly containing titanium trichloride, or a solid component in which titanium tetrachloride is supported on a carrier such as magnesium chloride. A catalyst component of a metal compound of Groups I to III of the Periodic Table is combined with an organic compound of a metal of Groups I to III of the Periodic Table represented by organoaluminum compounds, and in some cases, an electron donor is added as a third component of the catalyst. Slurry polymerization in which polymerization is carried out in an inert solvent using a so-called Ziegler-Natsuter catalyst combined with
By bulk polymerization using the branched olefin itself as a solvent or gas phase polymerization performed in the gas phase mainly using the branched olefin gas, branched olefins are polymerized at 0°C to 200°C in the presence or absence of hydrogen. Atmospheric pressure (OKg/c 2G
)~50g/c pus under polymerization conditions of about 2G for 10 minutes~
It is a crystalline branched olefin polymer obtained by polymerizing for 20 hours, and among these, those having a melting point of 250° C. or higher are used in the present invention.

Specific examples of the branched olefin polymers having a melting point of 250°C or higher include 3-methylbutene-IJIL autopolymer (approximately 306°C), 3-methylpentene-111! l!
Polymer (melting point approximately 362°C), 3-ethylpentene-11
L monopolymer (melting point: 425°C), 4.4-dimethylpentene-1 homopolymer (melting point: about 391t: ), 4.
4-dimethylhexene-1 homopolymer (melting point approximately 350°C
), copolymers of branched olefins giving these homopolymers, and even copolymers of branched olefins with olefins having 2 to 20 carbon atoms other than branched olefins. It can be used if it contains 55% by weight or more of olefin component units, 45% by weight or more of olefin component units having 2 to 20 carbon atoms, and has a melting point of 250° C. or more.

If the melting point is less than 250°C, the improvement in heat resistance, which is the objective of the present invention, cannot be observed. Specific examples of olefins having 2 to 20 carbon atoms that can be copolymerized with branched olefins include straight chain olefins such as ethylene, propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1,
4-Methylhexene-1,5-methylhexene-1,4
Examples include branched chain olefins such as -ethylhexene-1, diolefins such as butadiene, isoprene, and chlorobrene, as well as vinylcyclohexane, allyltrimethylsilane, and styrene.

In addition, in the production method and composition of the present invention, in addition to the branched olefin polymer or copolymer having a temperature of 250°C or higher, other olefin polymers may be used in an amount that does not impair the effects of the present invention. For example, it is also possible to use a resin polymer such as polyethylene, polypropylene, 4-methylpentene-1 polymer, ethylene-propylene rubber, styrene-diene rubber, or a hydrogenated product thereof.

The method for producing a chlorinated modified branched olefin polymer of the present invention involves graft polymerizing a radically polymerizable monomer to the above-mentioned branched olefin polymer having a melting point of 250°C or higher,
Furthermore, the special feature is to react with chlorine.

In addition, in the production method of the present invention, either of the above two reactions, graft polymerization and chlorination, may be performed first, graft polymerization and chlorination may be performed simultaneously, and each reaction may be performed simultaneously. It is also possible to repeat the process more than once.

Hereinafter, an embodiment in which chlorination is performed after graft polymerization will be described, but the present invention is not limited to the following embodiment.

Modification methods for branched olefin polymers include various graft polymerization methods carried out in the presence of a radical initiator, such as suspending a branched olefin polymer in an appropriate medium and grafting a radically polymerizable monomer. A slurry graft polymerization method in which a branched chain olefin polymer is polymerized, a solution graft polymerization method in which a branched chain olefin polymer is dissolved in a solvent, a melt method in which a branched chain olefin polymer is melted under heating, and a branched chain olefin polymerization method in which a branched chain olefin polymer is dissolved in a solvent are used. A gas phase graft polymerization method in which a polymer is fluidized and suspended can be employed. In addition to the above methods, it is also possible to use a radiation graft polymerization method in which ionizing radiation is irradiated to cause a gas phase reaction.

As for the grafting reaction conditions, the reaction temperature is room temperature to 450°C.
, the pressure is from atmospheric pressure (OKg/cm2G) to 100g/cm2G
c*2G conditions, based on 100 parts by weight of the branched olefin polymer, radical initiators o, oos to lO, and 0.01 to 100 parts by weight of radically polymerizable monomers.
About 1 part by weight is used, and the reaction is usually carried out for 1 minute to 20 hours.

After the graft polymerization is completed, a modified branched chain olefin polymer can be obtained as it is or by removing it with acetone or the like. The resulting modified branched olefin polymer is subsequently chlorinated.

Chlorination of modified branched chain olefin polymers can be carried out by introducing chlorine gas in a dissolved or suspended state in the modified branched chain olefin polymer in the presence of a solvent such as benzene, xylene, toluene or tetrachloroethane. The reaction temperature was 30°C to 300°C and the pressure was atmospheric pressure ( OKg/cm2G
) to 100 g/C■2G conditions, usually 1 hour to 20
Allow time to react.

During the chlorination reaction, it is also possible to increase the reaction efficiency by using a radical initiator commonly used as a pentachlorination reaction catalyst, ultraviolet rays, or radiation.

After the chlorination reaction is completed, the chlorinated modified branched olefin polymer of the present invention can be obtained as it is or by removing it with methanol, steam, etc.

Thus, the content of radically polymerizable monomer units in the obtained chlorinated modified branched olefin polymer is 0.01% to 40% by weight, and the chlorinated content is 10% to 7% by weight.
It is necessary that the content be within the range of 0% by weight.

If the content of the radically polymerizable monomer component in the obtained chlorinated modified branched olefin polymer is less than 0.01% by weight, properties such as adhesiveness, solvent resistance, and compatibility with other resins may not be imparted. If the amount exceeds 40% by weight, the adhesion will actually decrease, and the water resistance originally possessed by the branched olefin polymer will also decrease.

In addition, if the chlorine content is less than 10% by weight, the solubility in the solvent used for coating compositions and adhesive compositions will decrease,
If it exceeds 70% by weight, heat resistance and adhesiveness will decrease.

Examples of the radical initiator used in the graft polymerization according to the production method of the present invention described above include methyl motyl ketone peroxide, methyl isobutyl ketone peroxide,
Ketone peroxides such as cyclohexanone peroxide, methyl cyclohexanone peroxide, 0-
Methylbenzoyl peroxide, bis-3,5,5-
Diacyl peroxides such as trimethylhexanoyl peroxide, lauroyl peroxide, pensoyl peroxide, 2,4,4-1-tumethylbenzene-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, etc. hydroperoxides, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-butyl peroxide, and other dialkyl peroxides; 1.1-di-t-butylperoxy-3),
5-trimethylcyclohexane, 1. Peroxy ketals such as tojitobutylbaroxycyclohexane, 2,2-di-rt-butylperoxy)-butane, t-butylperoxyisobutyrate, t-butylperoxyacetate, t-butylperoxybenzoate, etc. Particularly preferred are organic peroxides such as alkyl peresters.

Furthermore, the radically polymerizable monomer used in the present invention is a compound having at least one unsaturated bond in the molecule that can be radically polymerized or copolymerized, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid,
Unsaturated carboxylic acids such as fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, glutaconic acid, nadic acid, methyl nadic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, anhydride Unsaturated carboxylic acid anhydrides such as allylsuccinic acid, glutaconic anhydride, nadic anhydride, methyl nadic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, diethyl maleate, di-n-butyl maleate, diethyl fumarate , di-n-butyl fumarate, methyl acrylate, ethyl acrylate,
Butyl acrylate, hexyl acrylate, acrylic acid 2
- Ethylhexine, hebutyl acrylate, octyl acrylate, glycidyl acrylate, methylglycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methylglycidyl methacrylate, Unsaturated carboxylic acid esters and their derivatives such as diethylaminoethyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, and hydroxypropyl methacrylate, aromatic monomers such as styrene, α-methylstyrene, vinyltoluene, and hydroxystyrene. dienes such as 1,3-butadiene, isoprene, chlorobrene, ], 5-hexadiene, acrylonitrile, methacrylonitrile, acrylamide, N-methylolacrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, and vinyl Trimethoxysilane, vinyltriethoxysilane, vinyldimethylethoxysilane, vinyltriacetoxysilane, vinylmethyldiacetoxysilane, allyltriethoxysilane, allyltriethoxysilane, γ-methacryloxytrimethoxysilane, γ-methacryloxypropyltrimethoxy Examples include unsaturated organosilicon compounds such as silane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-acryloxypropylmethyldimethoxysilane, among which unsaturated carboxylic acids and/or unsaturated Saturated carboxylic acid anhydrides are preferably used.

In addition, these monomers are 1f! It is also possible to use not only one type but two or more types.

The chlorinated modified branched olefin polymer obtained by the production method of the present invention may be a known chlorinated modified branched olefin polymer, various thermoplastic resins, thermosetting resins, or plasticizers, if necessary. , stabilizers, pigments, viscosity control side, thixotropic improvers,
By adding additives such as anti-sagging agents, various adhesives, and even solvents, it can be widely used in many fields including coating compositions and adhesive compositions.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. The melting point of the branched olefin polymer or copolymer was measured using a DuPont Model 1090 Differential Scanning Calorimeter. After melting the sample in the device, it was slowly cooled to 20°C.
After holding the sample for 10 minutes, the temperature was increased at 20° C./min. In addition, when a plurality of melting heaks were measured, the highest value was adopted as the melting point. (IL position: t) Example 1 (1) Production of branched olefin polymer ■ Production of titanium-containing solid catalyst component n-hexane 6f1. , diethylaluminum monochloride ([1EAC 150 mol and diisoamyl ether 12.0 mol were mixed at 25°C for 1 minute and reacted at the same temperature for 5 minutes to form reaction product liquid (I) (diisoamyl ether/
A DEAC molar ratio of 24) was obtained. 40 moles of titanium tetrachloride was placed in a reactor that had been purged with nitrogen and heated to 35°C.The entire amount of the reaction product solution N) was kept there for 30 minutes, and then heated to 75°C.
The reaction was further carried out for 1 hour, cooled to room temperature, the supernatant liquid was removed, 20 times of n-hexane was added, and the supernatant liquid was removed by decantation. This operation was repeated 4 times to obtain a solid product (II).
) 1.9 kg was obtained.

The entire amount of (II) was suspended in 30j2 of n-hexane, 2DOg of diethylaluminium monochloride was added, and 1.0kg of propylene was added at 30°C and the reaction was carried out for 1 hour to obtain a polymerized solid product (11- A) was obtained (propylene reaction amount: 0.6 g) After the reaction, the supernatant liquid was removed, and the operation of adding n-hexane 301 and removing by decantation was repeated twice, and the above polymerization treatment was performed. 2.5 kg of solid product (II-A) was suspended in n-hexane 61, 3.5 kg of titanium tetrachloride was added at room temperature for about 1 minute, and the mixture was reacted at 80°C for 30 minutes.
Further, 1.6 kg of diisoamyl ether was added and the reaction was carried out at 80°C for 1 hour. After the reaction was completed, the supernatant liquid was removed by decantation, 40 It of n-hexane was added, and 10
After repeating the operation of stirring for 5 minutes, leaving to stand, and removing the supernatant liquid 5 times, the titanium trichloride composition (III) was dried under reduced pressure.
I got it. The titanium content in 1 g of the titanium trichloride composition (nl) was 192 mg.

■Polymerization of branched olefin In a stainless steel polymerization vessel with an internal volume of 200 iL and equipped with a stirrer, n-hexane + 0011. After adding 120 g of diethylaluminium monochlorite and 500 g of the titanium trichloride composition (III) obtained in step (1) above.

3.5 kg of 3-methylbutene-1 was added, and while stirring,
Polymerization was carried out at 40°C for 2 hours. After the reaction time had elapsed, 10 jl of methanol was added and the mixture was treated at 80°C for 1 hour. After the treatment, the polymer was neutralized with a 20% by weight aqueous sodium hydroxide solution and further washed three times with 5 of water each time at 40°C.

Subsequently, the polymer was separated into layers and dried to obtain 3.1 kg of crystalline 3-methylbutene-1 polymer. The melting point of the polymer was 306.3°C.

(2) Production of chlorinated modified branched olefin polymer The above (3-
After 1 kg of methylbutene-171 combination was added, 150 g of maleic anhydride and 5 g of dicumyl peroxide were added and stirred. The temperature was raised to 50° C. under stirring and held for 15 minutes. Subsequently, the reaction was carried out at 100°C for 1 hour, and then at 150°C for 2 hours. After the reaction was completed, the obtained powder was washed with acetone and further dried to obtain maleic anhydride-modified 3-methylbutene-1 Coalescence was obtained 6.Subsequently, 400 g of the tetrachloroethylene of 10) and the maleic anhydride-modified 3-methylbutene-■ polymer obtained in the above method were charged into a glass reactor equipped with a stirrer and purged with nitrogen. , pressure 2 kg/cm2G, temperature 1
A chlorination reaction was carried out at 50° C. for 7 hours with stirring by blowing chlorine gas while irradiating with light.

After the reaction is completed, the reaction solution is steam distilled to reduce the maleic anhydride content to 1.41% by weight and the chlorine content to 3%.
A 1% by weight chlorinated maleic anhydride-modified 3-methylbutene-1 polymer was obtained.

(3) Production of composition A solution obtained by adding 7 parts by weight of the chlorinated maleic anhydride-modified 3-methylbutene-1 polymer obtained in (2) above to 80 parts by weight of xylene was used as an epoxy paint (Kansai Paint Co., Ltd.). Made
A coating composition was obtained by adding and mixing 100 parts by weight (as solid content) of the product (trade name: Million No. 1^).

1.1.1-Trichloroethane steam-washed 3-methylbutene-1 polymer injection molded piece (vertical 1
0c+n, width 10 cm, thickness 0.5 am) by air spray so that the thickness was about 40 μm when dry. After coating, it was left at room temperature for 15 minutes, and then baked at 120° C. for 30 minutes. The obtained coated test piece was left in an air oven at 150°C for 2 hours, and after 1 hour had passed, it was immersed in regular gasoline at 25°C for 8 hours.

After immersion, the test piece was taken out and the appearance of the coating film was visually inspected, but no abnormalities such as shadowing or peeling were observed in the coating film, and the heat resistance and gasoline resistance were good.

Comparative Example 1 In Example 1 (2) and (31), except for using the chlorinated 3-methylbutene-1 polymer obtained by performing only the chlorination reaction without graft polymerization modification with maleic anhydride. A paint composition was obtained in the same manner, and when the composition was subjected to heat resistance and gasoline resistance tests, blistering and peeling were observed throughout the coating film.

Comparative Example 2 A maleic anhydride-modified 3-methylbutene-1 polymer obtained by performing only graft polymerization modification with maleic anhydride without performing a chlorination reaction in (2) and (3) of Example 1. An attempt was made to produce a coating composition in the same manner except that the maleic anhydride-modified 3-methylbutene-1 polymer was not dissolved in xylene, and a coating composition could not be obtained.

Example 2 (1) In (1) of Example 1, 10 g of 4,4-dimethylpentene-1 was added in place of 3-methylbutene-1.
, and 4,4-dimethylpentene-1-4,4-dimethylpentene-1 copolymer having a melting point of 3850° C. was obtained in the same manner except that g of 4,4-dimethylhexene-1 was used.

(2) In (2) of Example 1, 3-methylbutene-
The 4,4-dimethylpentene-1-4,4-dimethylpentene-1 copolymer obtained in (1) above may be used instead of the 1-polymer, and acrylic acid may be used instead of maleic anhydride for grafting. 4. Chlorinated acrylic acid modification with an acrylic acid content of 3.1% by weight and a chlorine content of 58% by weight in the same manner except that the polymerization modification reaction was carried out and the chlorination reaction time was 10 hours. A 4-dimethylpentene-1,-4,4-dimethylpentene-1 copolymer was obtained.

(3) Chlorinated acrylic acid-modified 4.4-dimethylpentene-1-4,4-dimethylpentene-1 copolymer 10 obtained in (2) above! part by weight in 100 parts by weight of xylene,
A brimer was obtained, and the brimer was converted into 3-methylbutene-
1 Polymer injection molded piece (length 10c11, width 2cm, thickness 0.5c11) was coated with a brush, and then epoxy paint (manufactured by Kansai Paint Co., Ltd., product name Million NO, lA) was applied to the test piece.
was applied by air spray to a thickness of about 40 μm when dry. After coating, heat resistance and gasoline resistance tests were conducted in the same manner as in Example 1 (3), but no abnormalities such as blistering or peeling were observed in the coating film, and the heat resistance and gasoline resistance were good. there were.

Example 3 (1) In (1) of Example 1, 3-methylbutene-
A 3-methylpentene-1 polymer having a melting point of 362.1 t was obtained in the same manner except that 3-methylpentene=1 was used instead of 1.

(2) +0I in a glass reactor with a stirrer purged with nitrogen.
L of tetrachlorethylene and 3- obtained in (1) above
After applying 400 g of methylpentene-1 polymer, the chlorination reaction was carried out for 5 hours under stirring by blowing in chlorine gas while irradiating light at a pressure of 2 g/cm'G and a temperature of 150°C. 0 After the reaction was completed. , by steam distilling the reaction solution,
Chlorinated 3-methylpentene-1f [combination was obtained.

Subsequently, 400 g of the chlorinated 3-methylpentene-+1 mixture obtained by the above method was placed in a nitrogen-substituted lambda glass reactor equipped with a stirrer, and then 80 g of n-butyl acrylate and tg of benzoyl peroxide were added and stirred. 4 under stirring
After raising the temperature to 0°C, the temperature was maintained for 15 minutes and then reacted at 90°C for 2 hours.

After the reaction, the obtained powder is washed with acetone and further dried to obtain n-butyl acrylate modified chlorinated 3-methylpentene with an n-butyl acrylate content of 15% by weight and a chlorine content of 18ffl%. -1 polymer was obtained.

(3) 7 parts by weight of the lobutyl acrylate modified chlorinated 3-methylpentene-1 polymer obtained in (2) above was added to 8 parts by weight of xylene.
0 parts by weight and the resulting solution was added to one-component urethane paint (manufactured by Kansai Paint Co., Ltd., product name: SO) DREX #
1200) were added and mixed to 100 parts by weight (as solid content) to obtain a coating composition.

1.1. ll-Lichloroethane steam-cleaned 3-methylbutene-IJI1 polymer injection molding I
ilOcm, horizontal 1Oc11. It was applied by air spray to a thickness of about 40 μm when dry. After application, heat resistance and gasoline resistance tests were conducted in the same manner as in Example 1 (3), but no abnormalities such as shadowing or peeling were observed in the coating film, and the heat resistance and gasoline resistance were good. Met.

Comparative Example 3 In the same manner as in (1) and (2) of Example 3, except that 4-methylpentene-1 was used instead of 3-methylpentene-1, n-butyl acrylate modified chlorinated 4-methyl acrylate was produced. A pentene-1 polymer was obtained. Subsequently, acrylic acid n
- Example 3 (3) except that the n-butyl acrylate modified chlorinated 4-methylpentene-1 polymer is used in place of the butyl modified chlorinated 3-methylpentene-1 polymer.
A coating composition was prepared in the same manner as above.

When the obtained coating composition was subjected to heat resistance and gasoline resistance tests in the same manner as in Example 3 (3), blistering and peeling were observed throughout the coating film.

Example 4 (1) In (11) of Example 1, 3-methylbutene-
The same procedure was used except that 0.5 kg of butene-1 was used in addition to 1, and the melting point was 2802 ° C. and the butene-1 content was 1.
A 3.0% by weight 3-methylbutene-1-butene-1 copolymer was obtained.

(2) Add 1g of 3-methylpentene-1-butene-1 copolymer 1 obtained in (1) above to a glass reactor equipped with a stirrer and purify with nitrogen, then add 80g of glycidyl methacrylate and 2g of benzoyl peroxide. It was added and stirred. After raising the temperature to 40°C with stirring, maintain the same temperature for 15 minutes, then raise the temperature to 90°C.
The reaction was carried out for 2 hours.

After the reaction, the obtained powder is washed with acetone and further dried to obtain glycidyl methacrylate modified 3-methylbutene-
A 1-butene-1 copolymer was obtained. Subsequently, 10 J2 of tetrachlorethylene and 400 g of the glycidyl methacrylate modified 3-methylbutene-1-butene-1 copolymer obtained in the above method were charged into a glass reactor equipped with a stirrer and the atmosphere was purged with nitrogen, and the pressure was 2 kg/1. cm”G, temperature 150
The chlorination reaction was carried out at 0.degree. C. for 6 hours under stirring by blowing in chlorine gas while irradiating with light.

After the reaction is completed, the reaction solution is steam distilled to obtain a chlorinated glycidyl methacrylate-modified 3-methylbutene-1-butene-1 copolymer having a glycidyl methacrylate content of 5.5% by weight and a chlorine content of 25% by weight. Obtained union.

(3) Chlorinated glycidyl methacrylate modified 3-methylbutene-1-butene-1 copolymer 10 obtained in (2) above
The weight part is xylene ■00! The solution was dissolved in several parts to obtain a brimer. The brimer was molded into a 3-methylbutene-1 polymer injection molded piece (10 cm long, 2 cm wide, 0.5 cm thick).
After applying with a brush on each end 2c of the two sheets, -
A molding urethane adhesive (trade name Cypinol 0F-21, manufactured by Saiten Kagaku Co., Ltd.) was applied with a brush.

Subsequently, the coated parts were overlapped and bonded together, and the obtained Test Piece 1 was dried in an air oven at 80°C for 30 minutes, and then left at 150°C for 2 hours.

Subsequently, it was further immersed in regular gasoline at 25° C. for 8 hours. After immersion, the shear strength was measured by pulling both ends of the non-adhesive side of the specimen at a shear rate of 20 I/min using a Tensilon type tensile tester at room temperature (20°C), and it was found to be 18.5 gf/c. It had good heat resistance and gasoline resistance.

Comparative Example 4 A 4-methylpentene-1-butene-1 copolymer (melting point 202. 5°C) was obtained. Using the 4-methylpentene-1-butene-1 copolymer, (2) of Example 4 will be carried out.
(A brimer was obtained in the same manner as in 31. The shear strength of the brimer was measured in the same manner as in Example 4 (3) and was found to be 2.2 Kgf/cIll'.

Example 5 (1) Same procedure as in Example 4 except that 0.2 g of propylene was used in place of butene-1 in (11), melting point was 287.0°C, propylene content was 6.2 wt. %
A 3-methylbutene-1-propylene copolymer was obtained.

(2) In (2) of Example 4, 3-methylbutene-
3- obtained in (1) above in place of the 1-butene-1 copolymer
using a methylbutene-1-propylene copolymer;
In addition, the maleic anhydride content was reduced to 0 in the same manner except that maleic anhydride was used instead of glycidyl methacrylate.
．． A chlorinated maleic anhydride-modified 3-methylbutene-1-propylene copolymer having a chlorine content of 6% by weight and a chlorine content of 27ji% was obtained.

(3) Chlorinated maleic anhydride modified 3- obtained in (2) above
Seven parts by weight of methylbutene-1-propylene copolymer were dissolved in 50 parts by weight of xylene. Apply the solution to a one-component urethane adhesive (manufactured by Saiten Chemical Co., Ltd., trade name Cypinol 0F-).
21) An adhesive composition was obtained by mixing with 100 parts by weight.

Injection molded piece made of 3-methylbutene-1 polymer (height 10cm)
, width 2 cm, thickness 0.5 cm) The adhesive composition obtained by the above method was applied with a brush to the 2 cm square end portion of each of the two sheets, and the applied parts were overlapped and bonded. The obtained adhesive test piece was dried in an air oven at 80°C for 30 minutes, and then left at 150°C for 2 hours.

Subsequently, it was further immersed in regular gasoline at 25° C. for 8 hours. After immersion, both ends of the non-adhesive side of the test piece were pulled at a shear rate of 20 mm/min using a Tensilon type tensile tester at room temperature (20°C), and the shear rate was measured; it was 19.5 Kgf 7 cm2, which was good. It had excellent heat resistance and gasoline resistance.

[Effects of the Invention] As is clear from the described examples, the coating composition and adhesive composition containing the chlorinated modified branched olefin polymer obtained by the method of the present invention can be used in combination with known chlorinated modified branched olefin polymers. It has significantly higher heat resistance than compositions containing olefin polymers.

Furthermore, even if a branched olefin polymer with a melting point of 250°C or higher is used, the resulting composition will have poor solvent resistance and solvent solubility if only chlorination or graft polymerization modification is performed, regardless of the method of the present invention. .

Therefore, coating compositions and adhesive compositions containing the chlorinated modified branched olefin polymer obtained by the method of the present invention are required to have high heat resistance and high solvent resistance, which have not been used in the past. It can be widely used in various fields.

that's all

Claims (9)

[Claims] (1) A branched olefin polymer with a melting point of 250°C or higher,
A radically polymerizable monomer is graft-polymerized in the presence of a radical initiator, and chlorine is further reacted to reduce the content of radically polymerizable monomer units and the chlorine content to 0.
．． A method for producing a chlorinated modified branched olefin polymer, characterized in that the amount is 01% to 40% by weight and 10% to 70% by weight. (2) The branched olefin polymer is 3-methylbutene-1
, 3-methylpentene-1, 4,4-dimethylpentene-1, and 4,4-dimethylhexene-1.
~100% by weight, and 0 to 45% by weight of olefin component units having 2 to 20 carbon atoms other than the branched olefins, the claim being a branched olefin polymer and/or a branched olefin copolymer. The manufacturing method according to item 1. (3) The production method according to claim 1, wherein the radically polymerizable monomer is an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride. (4) A branched olefin polymer with a melting point of 250°C or higher,
Obtained by graft polymerizing radically polymerizable monomers in the presence of a radical initiator and further reacting with chlorine, the content of radically polymerizable monomer units and the chlorine content are each 0.01% by weight. ~40% by weight, 10% by weight ~70
% by weight of a chlorinated modified branched olefin polymer as an active ingredient. (5) The branched olefin polymer is 3-methylbutene-1
, 3-methylpentene-1, 4,4-dimethylpentene-1, and 4,4-dimethylhexene-1.
~100% by weight, and 0 to 45% by weight of olefin component units having 2 to 20 carbon atoms other than the above branched olefins, which are branched olefin polymers and/or branched olefin copolymers Coating composition according to item 4. (6) The coating composition according to claim 4, wherein the radically polymerizable monomer is an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride. (7) A branched olefin polymer with a melting point of 250°C or higher,
Obtained by graft polymerizing radically polymerizable monomers in the presence of a radical initiator and further reacting with chlorine, the content of radically polymerizable monomer units and the chlorine content are each 0.01% by weight. ~40% by weight, 10% by weight ~70
% by weight of a chlorinated modified branched olefin polymer as an active ingredient. (8) The branched olefin polymer is 3-methylbutene-1
, 3-methylpentene-1, 4,4-dimethylpentene-1, and 4,4-dimethylhexene-1.
~100% by weight, and 0 to 45% by weight of olefin component units having 2 to 20 carbon atoms other than the above branched olefins, which are branched olefin polymers and/or branched olefin copolymers The adhesive composition according to item 7. (9) The adhesive composition according to claim 7, wherein the radically polymerizable monomer is an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride.