JPS612753A - Novel high polymer composition - Google Patents

Abstract

PURPOSE:To titled composition, obtained by incorporating a terpolymer of styrene, unsaturated peroxycarbonate and diester of fumaric acid in a polymer having a specific solubility parameter, and having improved dispersibility and strength of the polymer. CONSTITUTION:A novel high polymer composition obtained by incorporating (A) a copolymer prepared by copolymerizing three components of 99-50pts.wt., preferably 99-70pts.wt. styrene with 20-0.1pts.wt., preferably 10-0.1pts.wt. unsaturated peroxycarbonate expressed by formula I (R1 and R2 are H, 1-12C alkyl group or 3-12C cycloalkyl group), preferably having 100-250 deg.C temperature at 1min half-life, e.g. tert-butyl peroxyallyl carbonate, and 50-1pt.wt., preferably 30-1pt.wt. diester of fumaric acid expressed by formula II (R3 and R4 are 1-12C alkyl group or 3-12C cycloalkyl group), e.g. dimethyl maleate, with (B) a polymer having 7-11 solubility parameter, e.g. polyethylene or polypropylene.

Description

Detailed Description of the Invention <Industrial Field of Application> The present invention involves blending a terpolymer obtained by copolymerizing styrene, unsaturated peroxycarbonate, and fumaric acid diester into a polymer having a solubility parameter of 7 to 11. The present invention relates to a polymer composition comprising:

<Prior art and its problems> Polystyrene is generally used not only as a thermoplastic resin, but also as a processing aid and polymer modifier, taking advantage of its high processability. ing.

However, polystyrene can be used as a processing aid, such as the latter.
When used as a polymer modifier, for example, U, S, P 3
383435 (1968) with polyphenylene oxide, West German Patent No. 46,542 (1966)
Although it has been shown that blends with polymers that are compatible with polystyrene, such as the blend with SBR rubber in the specification of No. It has poor compatibility with lubricating resins such as methyl, or with rubbers such as butadiene rubber and acrylonitrile-butadiene rubber. Therefore, there is a problem in that many of these blends result in compositions in which the physical properties of both components are significantly deteriorated.

Therefore, when blending polystyrene with a polymer that is incompatible with polystyrene, it has been necessary to perform operations such as adding a common compatible polymer. For example, polystyrene/polyethylene/graft copolymer (J, App
l, Polymer Scc 17°2597.279
1 (1973)), polystyrene/rubber/block or graft copolymers (West German Patent No. 2,342,219 (1975)), and the like. Other methods include copolymerizing styrene with acrylonitrile or methyl methacrylate segments for the purpose of improving the compatibility of polyvinyl chloride/styrene polymers, or modifying blend resins as seen in methods of chlorinating polystyrene. However, in either case, there are disadvantages in that a third polymer is required and extensive modification of the blend is unavoidable.

Structure of the Present Invention As a result of intensive studies to improve these conventional drawbacks, the present inventors copolymerized a mixed composition of a specific proportion of styrene, an unsaturated peroxycarbonate described below, and a specific fumaric acid diester. It has been found that a polymer composition obtained by blending the resulting copolymer with a polymer having a polymer solubility parameter of 7 to 11 has significantly improved polymer dispersibility and reduced strength. As a result, the present invention was completed.

That is, the gist of the present invention is 99 to 50 parts by weight of styrene, 20 to 0.1 parts by weight of an unsaturated peroxycarbonate represented by the following general formula (1), and 50 to 1 part by weight of a fumaric acid diester represented by the following general formula (2). This is a polymer composition prepared by blending a copolymer obtained by copolymerizing a part with a polymer having a solubility parameter of 7 to 11.

(In the formula, R and R2 represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms, and R8 and R4 represent an alkyl group having 1 to 12 carbon atoms or an alkyl group having 3 to 12 carbon atoms. 12 cycloalkyl groups, and these may be the same.) The styrenic terpolymer in the present invention is copolymerizable with 99 to 50 parts by weight, more preferably 99 to 70 parts by weight of styrene. 20-0.1 parts by weight, more preferably 10-0.1 parts by weight of unsaturated peroxycarbonate, which is an organic peroxide having It is a copolymerization of components.

The unsaturated peroxycarbonate used in the present invention and which is a copolymerizable peroxide represented by formula (1) has a half-life of 1 minute at a temperature of 100°C or higher and 250°C.
Compounds with ``C or less are preferable, for example, t-
Examples include butylperoxyallyl carbonate, t-butylperoxymethacrylic carbonate, t-butylperoxyturbate, t-hexylperoxyallyl carbonate, and the like.

Further, the fumaric acid diester used in the present invention and represented by the general formula (2) is a compound that has characteristics that can improve the drawback of lack of copolymerizability of styrene and unsaturated peroxycarbonate and maintain the physical properties of polystyrene. Specifically, dimethyl maleate, diethyl fumarate, diisopropyl fumarate, di-t-butyl fumarate, di5ec
-butyl fumarate, dicyclobentyl fumarate, dicyclohexyl fumarate, methyl-isopropyl fumarate, methyl t-butyl fumarate, etc., but at least one of the alkyl chains of R3 and R4 in formula (2) , preferably has a bulky branched structure.

Furthermore, the styrenic terpolymer of the present invention can be easily synthesized by radical polymerization such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. using a general radical polymerization initiator.

Polymers with a solubility parameter of 7 to 11 used in the present invention include resins such as polyethylene, polypropylene, polystyrene, polyvinyl acetate, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polyester, polyphenylene oxide, or polybutadiene, Examples include diene rubbers such as natural rubber, SBR, polychloroprene, and NBR.

In addition, the solubility parameter of the styrenic terpolymer is 7~
11 can be blended in any composition ratio, but when using the styrenic terpolymer as a processing aid or polymer modifier, the solubility parameter is 7. It is preferable to use 0.1 part by weight of 100 parts by weight based on 100 parts by weight of polymer having a solubility parameter of 7 to 11, and the resulting polymer composition has better processability, Adhesion, strength, heat resistance, hardness, etc. are improved.

On the other hand, when the styrenic terpolymer is used mainly or as a polymer composite composition having a solubility parameter of 7 to 11 with the styrenic terpolymer, 100% of the styrenic terpolymer by weight %, preferably 100 parts to 0.1 parts by weight of a polymer with a solubility parameter of 7 to 1], and the resulting polymer composition has better strength, heat resistance, and impact resistance than polystyrene alone. Improvements will be made.
In addition, in the present invention, the composition is a composition of the styrenic ternary copolymer pair and a polymer having a solubility parameter of 7 to 11, but in addition to these, organic peroxides, fillers, flame retardants,
A mold release agent, a heat stabilizer, a pigment, and in the case of diene rubber, a vulcanizing agent and a vulcanization accelerator may be added.

For blending the polymer composition of the present invention, common blending machines such as extruders, injection molding machines, roll mixers, Banbury mixers, kneaders, etc. can be used. In this case, the temperature at the time of cross-talk is set to a solubility parameter of 7 because the styrene terpolymer has excellent melt blendability over a wide temperature range of 130 to 300°C.
~ ] The usual processing temperature for the polymer of 1 can be selected at will.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Examples 1-2 Styrene, t-butyl peroxyallyl carbonate (
BPAC) and dicyclohexylphalate (Da)I
Each of F) was mixed with radical initiator di-2-ethylhexyl peroxydicarbonate (trade name: Perloyl OPP, manufactured by NOF Corporation) with the charged weight composition shown in Table 1.
was added, and the resulting mixed composition was polymerized for 48 hours at a polymerization temperature of 40° C. by a normal suspension polymerization method to obtain a styrenic terpolymer.

Next, each of the obtained styrenic terpolymer 20
g and low density polyethylene solubility parameter (8,1) 8
0 g was blended in a plastomill at 160° C. for 10 minutes under a nitrogen stream. Each of the obtained compositions was pressed with a press at a temperature of 150°C to a thickness of lll11.
I made it into a sheet. Each seam) was punched out with a dumbbell, and the physical properties were tested using a tensile tester to determine the tensile strength (k).
g/c+it) and elongation at break (m) were determined, and the obtained results are shown in Table 1.

Comparative Example 1 Polystyrene], Og and 40 g of low density polyethylene were blended according to Examples - 2, the obtained blended composition was pressed to form a sheet, the obtained sheet was further punched with a dumbbell, and then the obtained punched The physical properties were tested using a tensile test, and the results are shown in Table 1.

Comparative Example 2 A sheet was pressed under the same conditions as Examples 1 and 2 except that 50 g of low-density polyethylene was used as the resin, and the obtained sheet was further punched with a dumbbell, and the physical properties of the obtained punched body were tested. The results are shown in Table 1.

Example 3 10 g of the same styrenic terpolymer used in Example 1
Butadiene rubber (BR8,4) of the following compound
ong and additives in the following amounts, and the resulting mixture was blended at 150°C for 10 minutes using a roll mixer.

Butadiene rubber (BR) 100 g Zinc oxide 5 g Stearic acid
2g11AF black 13
60g Diana Process Oil 5g
Robo #600 1g Coumaron resin 5g Furthermore, 2g of sulfur and 1.2g of vulcanization accelerator DM were added to the obtained blend and blended at 60°C for 7 minutes using a roll kneader. Then, the obtained polymer composition was pressed (vulcanized) at 150°C for 20 minutes.
A sheet having a thickness of 2Ill111 was obtained. The obtained sheet with a thickness of 2IIIl was punched into a dumbbell shape,
It was used for physical property measurements. As for physical property tests, in addition to a tensile test according to Example 1, surface hardness and aging tests (observing changes in physical properties after treatment in air at 120'C for 72 hours) were conducted, and the obtained results are shown in Table 2. . Also, as a comparative example, the results of the same treatment as above using polystyrene instead of the styrene terpolymer are also listed.

Comparative Example 3 The same starting material used in Example 3 was treated in accordance with Example 3, except that polystyrene was used instead of the styrenic terpolymer in Example 3, and the resulting composition was used in Example 3. Table 2 shows the results obtained by conducting a physical property test according to 3.

Comparative Example 4 Butadiene rubber (BR) alone was treated according to Example 3, and the physical properties were tested according to Example 3. The results are shown in Table 2.

Table 1 Sachi pulling speed 1m/win Table 2

Claims (1)

Scope of Claims: 99 to 50 parts by weight of styrene, 20 to 0.1 parts by weight of an unsaturated peroxycarbonate represented by the following general formula (1), and 50 parts by weight of a fumaric acid diester represented by the following general formula (2).
A polymer composition made by blending a copolymer obtained by copolymerizing ~1 part by weight with a polymer whose solubility parameter is 7 to 11 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...
(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) (In the formula, R_1 and R_2 are hydrogen atoms or carbon atoms 1 to 1
2 represents an alkyl group or a cycloalkyl group having 3 to 12 carbon atoms, and R_3 and R_4 represent an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, and these may be the same. . )