JPS5815508A - Production of ethylene copolymer - Google Patents

Abstract

PURPOSE:To obtain a copolymer having both excellent properties of PE and a property as a bonding agent and being useful as a high-molecular plasticizer for PVC, a wax blending agent, a laminate, etc., by copolymerizing ethylene with a cyclic monomer containing a vinylidene group and a heterocyclic ring. CONSTITUTION:An ethylene copolymer containing 5-99.5wt% component (i), 95-0.5wt% component (ii) and below 50wt%, based on the total monomer weight, component (iii) is prepared by copolymerizing ethylene (i) with a cyclic monomer (ii) of formulaIor II, wherein A is an organic group (e.g., diketene, alpha-methyleneoxetane) and, if necessary, other copolymerizable ethylenically unsaturated monomers (iii) (e.g., propylene) in the presence of a free radical-generating catalyst (e.g., dicumyl peroxide).

Description

Detailed Description of the Invention The present invention provides a method for copolymerizing ethylene with a cyclic monomer having a vinylidene group and a heterocycle, and optionally with another ethylenically unsaturated monomer that can be copolymerized with at least one of the monomers. This invention relates to a method for producing a novel ethylene copolymer obtained by polymerization.

The ethylene copolymer obtained by the method of the present invention retains the excellent properties of polyethylene, such as excellent processability, low-temperature embrittlement, and chemical resistance, and has properties as a binder, and furthermore, it has the properties of a polyolefin. ,PVC.

It can be blended with polyamides, cellulose derivatives, vinylidene halide copolymers, polystyrene-acrylic copolymers, polyesters, polyurethanes, etc., and can provide useful resin compositions.

An object of the present invention is to provide a novel method for producing ethylene copolymers.

That is, the present invention uses ethylene, a cyclic monomer having a vinylidene group and a heterocycle represented by the general formula A (representing an organic group), and optionally other ethylene monomers copolymerizable with at least one of the above monomers. The present invention provides a method for producing an ethylene copolymer, which comprises copolymerizing saturated monomers using a free radical catalyst.

The cyclic monomer having a vinyline group and a heterocycle used for copolymerization with ethylene in the method of the present invention is a vinylidene group and a heterocycle monomer represented by (wherein A represents an organic group) .

Specifically, diketene, α-methylene oxetane, 2-methylenetetrahydrofuran, 2-methylene-1,8-dioxolane, 2-methylene-1,8-dioxane, α-
Methylene phthalane.

2-methylene-1゜4゜6, an unsaturated orthoester
-Dryoxasbiro[4,4':]nonane.

Examples include 8-methylene-1,5,7,11-tetraoxaspiro (5,51 undecane, alkylene oxide derivatives, etc.) Among these, diketene, α-methylene oxetane.

2-methylenetetrahydrofuran, 2-methylene-1.
8-dioxolane, 2-methylene-1°8-dioxane, etc. are preferably used.

The copolymerization ratio of ethylene and a cyclic monomer having a vinylidene group and a heterocycle is generally 5 to 99.5% by weight of ethylene;
Preferably 50-99% by weight and the cyclic monomer 95-00
Copolymerization is carried out at 5% by weight, preferably from 50 to 1% by weight.

If the proportion of the cyclic monomer exceeds 95% by weight, the compatibility with polyolefins, innes, etc. becomes poor;
If the amount is less than 5% by weight, it will not substantially contribute as a binder or blending agent, so it is preferably copolymerized within the above range.

In addition, in the method of the present invention, other ethylenically unsaturated monomers that are copolymerizable with at least one of the above monomers can be copolymerized, and examples of such monomers include the following: be able to. Olefins such as propylene, butene-1, decene-1 and octadecene-1; aromatic vinyls such as styrene and α-methylstyrene; vinyl esters containing 2 to 6 carbon atoms in the saturated carboxylic acid component, e.g. Vinyl lactate, vinylprobionate, vinyl benzoate, etc.;
Methyl, ethyl, propyl, butyl-92-ethylhexyl, cyclohexyl, dodecyl, octadecyl, glycidyl, etc. esters of acrylic and methacrylic acids containing 8 carbon atoms; maleic anhydride maleic acid mono- and maleic acid di-esters containing 1 to 18 carbon atoms in the saturated alcohol component, such as methyl-, ethyl-, butyl-, cyclohexyl-22-ethylhexyl-, dodecyl-, Monoesters and diesters such as octadecyl; vinyl chloride; vinyl ethers, such as vinyl methyl ether, vinyl ethyl ether; N-vinyl lactams, such as N-vinyl pyrrolidone or N-vinyl caprolactam; acrylic acid amide compounds; secondary vinyl carboxylic acids Amide: N-vinyl-N-alkyl-carboxylic acid amide, etc. Of the ethylenically unsaturated monomers mentioned above, vinyl acetate and acrylic esters are particularly advantageously used. The copolymerization ratio of these other ethylenically unsaturated monomers is 50% by weight in the total copolymer.
The amount shall be as follows.

The free radical catalyst used in the present invention refers to a catalyst that generates free radicals under the polymerization conditions employed,
It includes compounds having oxygen or a 10-0- bond or a -N-N- bond. Such catalysts include oxygen,
Water peroxide aralkyl group and derivatives thereof, allyl group, alkyl group, etc., Y is allyl group and derivatives thereof.

Aralkyl group, alkyl group, hydrogen, etc., X,! :Y may be the same or different. ) are particularly effective. For example, X-0
-0-Y type catalysts include diethyl 4-ruoxide, tert-butyl hydroperoxide, di-tert-butyl hydroperoxide,
There are butyl peroxide, para-menthane hydroyl oxide, diisopropylbenzene hydro 4 oxide, cumyl hydro oxide, dicumyl oxide, benzoyl hydrozyl oxide, etc. As x-1-o-o-y type catalysts, tert-butyl Zeroxybenzoate, tertiary-butylperoxyisobutyrate, tertiary-butylperoxyacetate, tertiary-butylperoxy-2-ethylhexanoate, tertiary-butylperoxycaprylate, cumyl peroxy 2-ethylhexanoate, tertiary-butylperoxy-2-ethylhexanoate -Butylyloxybivalate, cumylyloxy male valate, and other solvents include capryl peroxide, acetyl oxide, 2-ethylhexanoyl oxyto, male baryl oxide, and x-o-'6-o-o -y type catalysts include isooctylyloxymonocarbonate, isoamyl(9)R-ruoxymonocarbonate, isopropylyloxymonocarbonate, and the like.

Examples include isopropyloxydicarbonate, isoamyloxydicarbonate.

Examples include isooctylyloxydicarbonate and isopropylyloxydicarbonate, and mixtures of these peroxides are also effective.

Examples of the azo compound include azobisisobutyronitrile, azobis-2,2-diphenylacetonitrile, and mixtures thereof. The catalyst concentration in the charge can vary from 1% to 1% based on the total weight of all monomers, preferably a peroxide catalyst,
For azo catalysts it can vary from 0.0005 to 0.2% by weight and for oxygen catalysts from 0.002 to 0.01% by weight. This copolymerization reaction can be carried out in the presence of a diluent (10) in order to control the temperature uniformly throughout the reaction mixture, but a diluent is not essential. Suitable diluents include water, alcohols such as methanol and tert-butanol, etc. Futan.

Hydrocarbons such as isooctane, cyclohexane, methylcyclohexane, toluene, and benzene.

These include chlorobenzene, butyl acetate, and mixtures thereof. This copolymerization reaction can be carried out at a pressure of 500 to 4,000 atmospheres, but the preferred pressure is 1.00 atmospheres.
0 to a, o o o atmospheric pressure.

The temperature can generally be 40 to 800°C, but the preferred temperature is 70 to 280°C.

If the pressure is less than 500 atmospheres or the temperature is less than 40°C, the polymerization reaction rate and conversion rate will be significantly lowered, and a large amount of catalyst will be required, which is industrially disadvantageous. Also, high pressure of 4,000 atmospheres or more or temperature 8
Polymerization becomes difficult at high temperatures above 00°C.
You can't expect safe driving. Any batch, semi-continuous or continuous polymerization method is effective as the method according to the present invention. In particular, when produced in a continuous manner, the composition of the copolymer is nearly uniform and a high performance product can be obtained, which is preferable.

The copolymers of the present invention have unique properties that make them highly useful alone or in combination with other polymeric or non-polymeric materials, e.g. by mixing to produce compositions. Become. That is, the ethylene copolymer obtained by the method of the present invention contains, for example, 1 to 20% by weight of the cyclic monomer of the present invention and 0% of the ethylenically unsaturated monomer.
The copolymer containing ~80% by weight is more transparent and flexible than conventional polyethylene, and also has the excellent properties of polyethylene, such as excellent processability, low-temperature embrittlement, and chemical resistance. It can be used in a wider range of applications than conventional polyethylene films and molded products. When used as a laminate, it has high peel strength and can be usefully used.

Furthermore, as the amount of the cyclic monomer of the present invention increases, the degree of crystallinity decreases, exhibiting elastomer properties not seen in polyethylene, and can be used for special purposes such as wax blending agents, toys, sports equipment, etc. can. What is more interesting is that the copolymer of the present invention has good compatibility with polyolefins, polyvinyl chloride, etc., and can be blended to provide useful resin compositions. It is particularly useful as a polymeric plasticizer that forms a uniform resin composition with polyvinyl chloride and imparts plasticity to polyvinyl chloride. For use as a composition with polyvinyl chloride, for example, the cyclic monomer of the present invention may be contained in an amount of 5 to 25% by weight, and the ethylenically unsaturated monomer may be contained in an amount of 10 to 25% by weight.
The intrinsic viscosity determined as a 80% by weight tetralin solution at a total temperature of 185°C is 0.8-2, and the OdQ/f (or melt index (7/10 min)) is approximately 500-0.
01) ethylene copolymer to polyvinyl chloride.
By adding 0 parts by weight, a flexible polyvinyl chloride composition can be obtained.

Stabilizers, pigments, fillers and other additives can be mixed with the ethylene copolymer used in the method of the present invention, if necessary. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. After repeatedly substituting ethylene with oxygen-free ethylene, the pressure was reduced and 15 units of ditertiary-butylyl oxide and 1.5 m of diketene were added to this container.
Charge Q and 10 mλ of acetone. After that, ethylene was introduced to an appropriate pressure, the internal stirrer was started, and the temperature of the container was 152°C, the pressure was 1,500K, and the pressure was 1,500K.
The reaction was started with cd. After 28 minutes the pressure is 1.1 o
It fell to ob/i. The container was cooled and the pressure was released to obtain a copolymer of ethylene and diketene 141. From the results of elemental analysis, it was found that this product contained 10% by weight of diketene. After forming it into a film, the infrared absorption spectrum was measured (results showed the presence of a characteristic absorption value of 4 (1785 ff") of ester carbonyl and the existence of a compound due to the β-position cleavage of diketene. Also, it was determined as a tetralin solution at 185 ° C. Intrinsic viscosity is 0.75d2/
It was 1.

A 1 gm thick sheet produced by hot press molding was significantly more transparent than polyethylene.

Examples 2 to 6 In the same manner as in Example 1, the type and amount of the cyclic monomer and/or ethylenically unsaturated monomer having a vinylidene group and heterocycle to be copolymerized with ethylene, the catalyst, and the reaction conditions were changed. An ethylene copolymer was obtained. As catalysts, ditertiary butyl zuroxide, caprylic zuroxide, and azobisisobutyl nitrile were used. Table 1 shows the reaction conditions and properties of the copolymer obtained.

Examples 7-8 Free-radical catalysts were continuously produced under the production conditions of Table 2 using a temperature-controlled 5ON stainless steel reactor equipped with suitable inlets and outlets and an agitator. While supplying (Note 4) TBEH: Tertiary butylyloxy-2-ethylhexanoate (Note 5) Measured in accordance with JIS K-6760.

Next, reference example (ζ) will specifically explain the usefulness of the copolymer obtained by the method of the present invention.

Reference Example 1 70 parts of ethylene-vinyl acetate-diketene copolymer obtained in Example 2 and calcium stearate +
1-5 parts, 11 stearate: 1.5 parts, epoxidized soybean oil, 0 parts and polyvinyl chloride 100 parts<polymerization degree 1
100) was kneaded for 7 minutes on a hot roll heated to 150°C, and then molded at 170°C for 5 minutes to a thickness of 2f.
A sheet of 1 was created.

A flexible transparent sheet was obtained. On the other hand, ethylene-vinyl acetate copolymer (evacy 1-@720
10 (vinyl acetate 25% by weight, melt index 8), manufactured by Sumitomo Chemical Co., Ltd.) to obtain a composition with polyvinyl chloride, and then press molding (18
) The 2M thick sheet produced was milky white and opaque.

Reference-Example 2 Chromate treated 180mX18QtlXQ,
(20 parts by weight of the ethylene-2-methylene-1,8-dioxolane-ethyl acrylate copolymer obtained in Example 4 and polyethylene (Sumikasen''G3) were placed on a 3fl iron plate.
A resin composition prepared by mixing 80 parts by weight of 01 (manufactured by Sumitomo Chemical Industries, Ltd.) was placed, and after preheating at 200°C for 15 minutes,
It was pressed at a pressure of 100 Kp/d and then cooled with a cooling press to obtain a laminate with a resin composition layer having a thickness of 111t1t. When the 180° angular strength was measured at a temperature of 20°C and a tensile speed of 591,117 m, it was 6.41 r.
//d.

The tensile strength of polyethylene alone without the copolymer was 2.11)/d.

Reference Example 8 1.0% by weight of the ethylene copolymer powder obtained in Example 7 and glass m fiber (diameter 10p + length 6mg, E glass) 80
% by weight, and then mixed with powder of stereoregular polypropylene (manufactured by Sumitomo Kagaku Kogyo Co., Ltd., Sumitomo Noblen W5017) with an intrinsic viscosity of 1.8, using an 80 MMφ extruder. After extrusion at a resin temperature of 240°C, it was granulated.

The granules were molded using a 5-ounce screw type injection molding machine at a resin temperature of 270°C and a mold temperature of 50°C.

As a result of forming each test piece under the conditions of screw back pressure 10 K, /cd and measuring each physical property, the heating deformation temperature was 142
The C1 tensile yield strength was 761%=/d and the flexural strength was 81411 p/d.

The physical properties of the composition without the polymer were measured, and the results were as follows: heating deformation temperature: 115°C; tensile yield strength: 4904°C.
/i and bending strength were 670 b/d. The heating deformation temperature is ASTM D64'8-56 (maximum fiber stress 18.6.1 given/lG, tensile strength is A8TM'P6
88 Shiro 4T1 bending strength was measured in accordance with each test method of ASTM D790-68.

Procedural amendment (spontaneous) l, Indication of the case 1982 Patent Application No. 11418'52, Name of the invention Process for producing ethylene copolymer3, Person making the amendment Relationship with the case Patent applicant address Higashi, Osaka City 5-15 Kitahama, Ward Name (
209) Sumitomo Chemical Co., Ltd. Representative Hijikata
Take 4, Agent Address: 5-15 Kitahama, Higashi-ku, Osaka City "Detailed Description of the Invention" column 6 of the specification to be amended Contents of the amendment (1) Page 8 of the specification, line 6 "-N- N-J as f-N=N
-” is corrected.

(2) In Example 2 of Table 1 on page 16, lines 114 and 4j of the weight of copolymer are corrected to rlO, 4J.

(3) Np Table 1 Copolymer weight row r15 of Example 5
．． 'I' krlO, correct it to 'I'.

that's all (2 complete)

Claims (6)

[Claims] (1) A cyclic monomer having ethylene and a vinylidene group represented by the general formula (wherein A represents an organic group) and a heterocycle, optionally copolymerizable with at least 10,000 of the above monomers. A method for producing an ethylene copolymer, comprising copolymerizing ethylenically unsaturated monomers using a free radical catalyst. (2) The method for producing an ethylene copolymer according to claim 1, wherein the reaction pressure is 500 to 4000 atm and the reaction temperature is 40 to 800°C. (3) The copolymerization ratio of ethylene and a cyclic monomer having a vinylidene group and a heterocycle is 5 to 9995% by weight (1) and 95 to 0.5% by weight. A method for producing an ethylene copolymer according to items 1 and 2. (4) The copolymerization ratio of ethylene and a cyclic monomer having a vinylidene group and a heterocycle is 5 to 99.5% by weight and 95 to 95% by weight.
0.5% by weight, and at least 100 parts by weight based on 100 parts by weight of the total monomers.
3. A method for producing an ethylene copolymer according to claims 1 to 2, which comprises copolymerizing the seed with another ethylenically unsaturated monomer copolymerizable with the seed. (5) The cyclic monomer having a vinylidene group and a heterocycle is diketene, α-methylene oxetane, 2-methylenetetrahydrofuran, 2-methylene-1,8-dioxolane, 2-methylene-1,8-dioxane, α-methylene Phthalan. 2-methylene-1,4,6-dryoxaspiro C4',
4 ] nonane, 8-methylene-1,5°7.11-tetraoxaspiro[5,5) undecane and f 0 ) selected from the group consisting of alkylene oxide derivatives, characterized in that it is at least one type of monomer. A method for producing an ethylene copolymer according to claims 1 to 4. (6) The cyclic monomer having a vinylidene group and a heterocycle was selected from diketene, α-methylene oxetane, 2-methylenetetrahydrofuran, 2-methylene-1,8-dioxolane, and α-methylene-1,8-dioxane. The method for producing an ethylene copolymer according to claims 1 to 5, characterized in that the ethylene copolymer is at least one type of monomer.