JPS60115609A - Production of polymer - Google Patents

Abstract

PURPOSE:To produce a particulate polymer of excellent heat resistance economically, by polymerizing a specified acrylic monomer in the presence of a polymer of this monomer and/or a different polymer. CONSTITUTION:Tricyclo[5,2,1,0<2>,<6>]dec-8-yl(meth)acrylate monomer is polymerized in the presence of a polymer of its own and/or a different polymer (e.g., polystyrene or polyphenylene ether) to produce a (co)polymer containing 5- 100wt% units of the above monomer. A desirable polymerization process is a suspension polymerization process and the resin particles thus obtained are used as a material for extrusion or producing foams, and can form moldings of excellent heat resistance.

Description

[Detailed description of the invention] The present invention relates to a method for producing a polymer with excellent heat resistance.

Conventionally, polyethylene resins have been widely used as resins for molding materials and foaming materials, but their heat distortion temperature is low, making them unsuitable for use in applications requiring heat resistance.

Therefore, we took advantage of the moldability of polystyrene resin.

For example, in order to obtain a resin that has side heat properties.

It is possible to mix high-density polyethylene or crystalline polypropylene, but these have many problems such as difficulty in mixing with polystyrene and reduced moldability. Dimensions. In addition to these resins, styrene.

A maleic anhydride copolymer has been proposed (Japanese Unexamined Patent Publication No. 1983
39186), when this copolymer is produced by suspension polymerization, a very complicated suspension polymerization process is required due to the unique reactivity of maleic anhydride. It is pointed out in Japanese Patent Publication No. 47-49831 that it requires a large amount of use and is not economical. In addition, methyl methacrylate is the main component and α-methylstyrene is the minor hv component, and a vinyl compound as the third component is used in combination to take advantage of the low reactivity of α-methylstyrene to carry out suspension polymerization at a high temperature of 95 to 130°C for about 20 minutes. Although this method is proposed in Japanese Publication No. 182334 of Time, it is not economical because the polymerization temperature is high and a long suspension polymerization process is required.

The first object of the present invention is to solve these problems and to produce a polymer with excellent heat resistance.

The second objective is to produce such a polymer in particulate form by a suspension polymerization method.

That is, 9 the present invention provides tricyclo[5,2 methacrylate]
, 1,0'.6]dec-8-yl, tricyclo(5,2,1,0''.6]dec-8-yl acrylate and other polymerizable monomers. Polymerization of one monomer or in the presence of another polymer, and tricyclo[5,2 methacrylate]
,1,0'・6]dec-8-yl and/acrylic acid toIJcyclo[5,2,1,0''・0]dec-8-yl
The present invention relates to a method for producing a polymer, characterized in that the blending ratio of F is 5 to 100 F by weight.

In the present invention, other polymerizable monomers include:

Examples include unsaturated fatty acid esters, aromatic vinyl compounds, vinyl cyanide compounds, and N-substituted maleimides. Examples of unsaturated fatty acid esters include mef acrylate, ethyl 7-acrylate, and butyl acrylate.

Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, acrylic acid cycloalkyl esters such as cyclohexyl acrylate, acrylic acid aromatic esters such as phenyl acrylate and benzyl acrylate, acrylic acid esters such as glycidyl acrylate, methacrylic acid Methyl, ethyl methacrylate, propyl methacrylate,
Methacrylic acid alkyl esters such as butyl methacrylate, hexyl methacrylate, and 2-ethylhexyl methacrylate, methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, methacrylic acid aromatic esters such as phenyl methacrylate and benzyl methacrylate, glycidyl methacrylate, etc. methacrylic acid esters, etc.

Examples of aromatic vinyl compounds include styrene, α-substituted styrenes such as α-methylstyrene and α-ethylstyrene, and nuclear-substituted styrenes such as chlorostyrene, vinyltoluene, and t-butylstyrene. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. N-substituted maleimides include N-methylmaleimide, N-ethylmaleimide, and N-isopropylmaleimide.

Aliphatic N-substituted maleimides such as N-butylmaleimide and N-laurylmaleimide; alicyclic N-substituted maleimides such as N-cyclohexylmaleimide;

Examples include aromatic N-substituted maleimides such as N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmale-4mide, and N-methoxyphenylmaleimide. In addition, vinyl acetate, α-methylethylene, diethyl maleate, etc. can also be used.

The polymer of the above monomer is polyethylene.

Also includes polypropylene printing.

In the present invention, other polymers include polyphenylene oxide and polyethylene terephthalate.

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There are polymers that cannot be obtained by vinyl monopolymerization, such as 11-carbon polymers and lH polyesters.

As a method for producing the polymer of the present invention, known methods such as radical vertical polymerization and ionic polymerization can be applied. For example, it can be produced by methods such as bulk polymerization, solution polymerization, and suspension polymerization in the presence of a polymerization initiator. Polymerization methods are preferred. In this case, the monomers mentioned above are polymerized in the presence of other polymers, but even if these polymers are dissolved in the #monomers, they cannot be impregnated with the monomers. You can leave it there.

Examples of initiators used in polymerization include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, and 1,1-di-t-butyl. Organic peroxides such as peroxy-3,3,5-trimethylcyclohexane, azobis-
Azo compounds such as 4-notoxy-2,4-dimethylvaleronitrile, azopisicuhexanone-1-carbonitrile, azodibenzoyl, water-soluble catalysts such as potassium persulfate, ammonium persulfate, and peroxides or peroxides. Any catalyst that can be used in normal radical polymerization, such as a redox catalyst using a combination of a sulfate and a reducing agent, can be used. The amount of polymerization catalyst is 0.01 to 1 based on the total amount of monomers.
It is preferable to use it within a range of 0 weight ratio. Mercaptan compounds, thioglycol, carbon tetrabromide as polymerization regulators.

α-methylstyrene dimer or the like is added as necessary to adjust the molecular weight.

The polymerization temperature is preferably selected appropriately between 0 and 200°C, particularly preferably 50 and 120°C.

Solvents for solution polymerization include benzene, toluene,
Xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dichloroethylene, etc. can be used.

Suspension polymerization is carried out in an aqueous medium, with the addition of suspending agents and, if necessary, suspension aids. Examples of suspending agents include water-soluble polymers such as polyvinyl alcohol, methylcellulose, and polyacrylamide, and sparingly soluble inorganic substances such as calcium phosphate and magnesium pyrophosphate. It is preferable to use the slightly soluble inorganic material in an amount of 0.05 to 0.5% by weight based on the total amount of monomers.

Examples of the am auxiliary agent include anionic surfactants such as sodium dodecylbenzenesulfonate, and when a sparingly soluble inorganic substance is used as a suspending agent, it is preferable to use them together. Suspension aid: 0.001 to 0.02 per 1 of total monomers
It is preferable to use a weight factor.

Tricyclo[5] methacrylate used in the present invention
,2,1,0''·6]dec-8-yl Futakeacrylic acid tricyclo[5,2,1°ol·6]dec-8-yl is a commonly known method for the synthesis of methacrylic acid esters or acrylic acid esters. obtained using the method.

For example, by adding H2O to dicyclopentadiene to form dicyclopentenyl alcohol, and then performing a catalytic hydrogenation reaction, tricyclo[5,2,1,0''...]decar-8-o is obtained.This alcohol and methacryl It can be obtained by a condensation reaction with an acid, acrylic acid, methacrylic acid chloride, acrylic acid chloride, or a transesterification reaction with methyl methacrylate or methyl acrylate.

The polymer obtained by the present invention can be applied to expandable thermoplastic resin particles, injection molding materials, extrusion molding materials, and the like.

When the polymer obtained according to the present invention is used, various additives 9 such as pigments and flame retardants are added to improve moldability and impart flame retardancy.

Known additives such as antioxidants, plasticizers, and antistatic agents may also be included.

The resin particles obtained from the present invention can be used as a heat-resistant thermoplastic resin for extrusion, injection, etc., and can also be used as a foam raw material.

Next, nine examples of the present invention will be shown.

Example 1 41! Place 15 liters of ion-exchanged water in an autoclave with rotating stirring.
009 polyvinyl alcohol (W-2 manufactured by Denki Kagaku Kogyo ■)
4) 4.59 and polyfren particles (0.6~0.8m
(diameter) 5009, and while stirring, lower the temperature in the system to 8.
The temperature was raised to 0°C. Tricyclo methacrylate [5,2,1
,0''-')dec-8-yl 5009] 25g each
It was dropped three times at 0 minute intervals. Next, the remaining monomer Kl, 1
-di-t-butylperoxy3,3.5-)limethylcyclohexane 2.679.

0.59 of t-butylperbenzony) was dissolved and added in the same manner 30 minutes after the third addition of the solution. After continuing the reaction at the same temperature for an additional 3 hours, the temperature was raised to 120°C in 60 minutes, and stirring was continued at this temperature for 3 hours thereafter. Thereafter, the mixture was cooled to 30''C to obtain polymer particles.

Table 1 shows the average diameter and glass transition temperature.

Example 2 Polyphenylene ether 5009 [engineering plastic 1IuPPO] was used instead of 500 g of polystyrene particles used in Example 1, and the average diameter and glass transition temperature of polymer particles obtained are shown in Table 1.

Example 3 4I! In an autoclave with a rotary stirrer, methacrylic acid II'/Rio C5,2,1,0"l') Teka-8
- Prepare 500g of pv and 250g of styrene, 1 oyster
While stirring, polyphenylene ether (PP0 manufactured by Engineering Plastics) 2509 was added and completely dissolved in 2 hours while purging with nitrogen gas.

Benzoyl peroxide after complete dissolution 2.39. After dissolving 1.5 g of t-butyl perbenzoate, the stirring was stopped and 20009 ion-exchanged water was added, then the stirring was restarted and 59.9 g of tricalcium phosphate was added. Sodium dodecylbenzenesulfonate O, s% solution i6g.

Suspension polymerization was started by adding 0.759 g of sodium sulfate.

Thereafter, polymer particles were produced in the same manner as in Example 1]7. Table 1 shows the average diameter and glass transition temperature.

Comparative Example 1 In Example 3, tricyclomethacrylate [5°2,
i, O'.6] Polymer particles were obtained in the same manner as in Example 3, except that polyphenylene ether 2509 was dissolved in styrene monomer 7509 without using theca-8-yl. Table 1 shows the average diameter and glass transition temperature.

According to the present invention, a resin with excellent heat resistance can be obtained. Further, in the present invention, even if suspension polymerization is employed as a polymerization method, it can be carried out stably without any particular problems.

Claims (1)

[Claims] 1. Tricyclo methacrylate [5,2,1,o''・6
] Dec-8yl, tricycloC5,2,1, acrylate
o9.6] In the presence of a polymer of at least one monomer selected from the group consisting of deca-8yl and other polymerizable monomers or other polymers, the monomer is polymerized, and tricyclomethacrylate is [5,2,1,,0'l':1
Dec-8-yl and/or tricyclo[
5,21,0'・6] The blending ratio of dec-8-yl is 5 to 1
A method for producing a polymer, characterized in that it is made into a 0.00-weight polymer. 2. A method for producing a polymer according to claim 1, wherein the polymerization is carried out by suspension polymerization.