KR0145842B1 - Thermoplastic resin composition - Google Patents

Abstract

The present invention provides a thermoplastic resin composition and a method for producing the same, which comprises (A) a functional resin obtained by adding a functional monomer to an aromatic vinyl compound-vinyl cyanide compound copolymer in an amount of 0.1-30% by weight; (B) a functional ethylene-propylene copolymer rubber obtained by adding a monomer containing a poor reactive group to an ethylene-propylene copolymer in an amount of 0.1-10% by weight; (C) ethylene-propylene-diene copolymer rubbers; And (D) an aromatic vinyl compound-vinyl cyanide compound copolymer, prepared by melt extruding them, and having excellent physical properties such as weather resistance and impact resistance.

Description

Thermoplastic resin composition

The present invention relates to a thermoplastic resin composition, and more particularly, to an aromatic vinyl compound-vinyl cyanide compound copolymer, a functional resin in which a monomer containing an epoxy or maleic anhydride is added, and a functional ethylene-propylene in which a monomer containing a reactive group is added. (Ethylene-Propylene, hereinafter referred to as EPM) Rubber and ethylene-propylene-diene terpolymer (hereinafter referred to as EPM), which is produced by polymerization by extrusion method, characterized by weather resistance and impact resistance, etc. It relates to a thermoplastic resin composition having excellent physical properties.

ABS resin, a styrene resin, is a high-performance plastic based on acrylonitrile, butadiene and styrene. Is fulfilling. However, ABS resin has a double bond in the main chain of the rubber butadiene, so when aging outdoors due to heat, light, etc., the physical properties are degraded, so additional treatment is required for outdoor use such as automobile exterior materials. There are three additional treatment methods for this purpose: a secondary processing method of painting with paint, a method of adding a light stabilizer to ABS, and a method of replacing butadiene rubber with a rubber having no double bond. On the other hand, in order to fundamentally improve the weather resistance of ABS resin, the resin which substituted butadiene which is poor in weather resistance among the components of ABS resin by acrylic rubber or EPDM rubber is developed and marketed.

Background Art Conventionally, development of a graft copolymer having excellent impact resistance and weather resistance by graft copolymerization of styrene or acrylonitrile to EPDM rubber has excellent weather resistance. Emulsion polymerization method (US Pat. No. 3,435,096) is usually adopted as the production method, and only solution polymerization method (US Pat. No. 3,538,190) is known. However, these known techniques require a long time of polymerization and have a big disadvantage of using a polar solvent to dissolve the EPDM rubber in the case of emulsion polymerization and solution polymerization. In order to reduce the amount of the polar solvent, a method of obtaining a resin having good physical properties while reducing the amount of the polar solvent by adding a mixed solvent to the polar solvent (Japanese Patent Publication No. 52-30995) has been published. The production is now decreasing gradually.

Under these circumstances, the inventors studied extensively for the purpose of providing ABS resins having enhanced weather resistance and impact strength without using polar solvents that are harmful to the environment, and as a result, aromatic vinyl compound-vinyl cyanide compounds containing functional monomers. Extruder using an ethylene-propylene rubber (functional EPM rubber) and an ethylene-propylene-diene copolymer (EPDM rubber) containing a functional copolymer with a reactive monomer and an aromatic vinyl compound-vinyl cyanide compound copolymer, if necessary It has been found that the above object can be achieved by polymerizing through extrusion reaction in the present invention, and have completed the present invention.

That is, an object of the present invention is to provide a thermoplastic resin composition having excellent physical properties such as weather resistance and impact resistance at low cost through a simple production process.

In order to achieve the above object, the present invention

(A) 10-90% by weight of a functional resin obtained by adding a functional monomer in an amount of 0.1-30% by weight to the aromatic vinyl compound-vinyl cyanide compound copolymer;

(B) 1-50% by weight of a functional ethylene-propylene copolymer rubber obtained by adding a monomer containing a reactive group to the ethylene-propylene copolymer in an amount of 0.1-10% by weight;

(C) 1-50% by weight of ethylene-propylene-diene copolymer rubber; And

(D) A thermoplastic resin composition comprising 0-40% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer.

The invention also

(A) 10-90% by weight of a functional resin obtained by adding a functional monomer in an amount of 0.1-30% by weight to the aromatic vinyl compound-vinyl cyanide compound copolymer;

(B) 1-50% by weight of a functional ethylene-propylene copolymer rubber obtained by adding a monomer containing a reactive group to the ethylene-propylene copolymer in an amount of 0.1-10% by weight;

(C) 1-50% by weight of ethylene-propylene-diene copolymer rubber; And

(D) 0-40% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer is melt-extruded for 30 seconds or more at a temperature of 170-250 ° C. and an extrusion rate of 50-400 rpm to provide a method for producing a thermoplastic resin composition. do.

Other objects, features and applications of the present invention will become apparent to those skilled in the art from the following detailed description.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition of the present invention is 10-90% by weight of a functional resin (functional resin (A)) obtained by adding a functional monomer to an aromatic vinyl compound-vinyl cyanide compound copolymer in an amount of 0.1-30% by weight, preferably 65-85% by weight; 1-50% by weight of a functional ethylene-propylene copolymer rubber (functional EPM rubber (B)) obtained by adding a monomer containing an ethylene-propylene copolymer reactive group in an amount of 0.1-10% by weight; Preferably 7-20% by weight ethylene-propylene-diene copolymer rubber (EPDM rubber (C)) 1-50% by weight, preferably 5-20% by weight; And 0-40% by weight of aromatic vinyl compound-vinyl cyanide compound copolymer (copolymer (D)), preferably 0-10% by weight.

According to the present invention, a thermoplastic resin having excellent physical properties such as weather resistance and impact resistance at low cost without using a polar solvent by graft polymerizing the extrusion reaction under the specific conditions in the above (A)-(D) components in an extruder The composition can be prepared.

In the aromatic vinyl compound and the vinyl cyanide compound used in the (A) and (D) components of the resin composition of the present invention, examples of the aromatic vinyl compound include styrene, alphamethylstyrene, ortho and paramethylstyrene, dimethylstyrene, chloromethylstyrene, Dichlorostyrene, bromostyrene, dibromostyrene and tribromostyrene may be used alone or in combination of two or more thereof, and the content in the entire copolymer may be in the range of 10-80 wt%. In addition, representative materials of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, or alpha clonitrile, and account for 5 to 40% by weight of the total copolymer and may be used alone or in combination.

If the content of the aromatic vinyl compound and the vinyl cyanide compound is outside the above range, there is a problem that a uniform resin is not produced, which is not preferable. In order to impart functionality to the copolymer of such an aromatic vinyl compound and a vinyl cyanide compound and to prepare a functional resin (A) having compatibility with the functionalized EPM rubber, a functional monomer should be added during the production of this copolymer. Functional monomers that can be used in the present invention for this purpose include monomers containing an epoxy group or maleic anhydride, double monomers containing epoxy groups itaconic acid mono glycidyl ester, butene tricarboxylic acid mono glycidyl ester , Butene tricarboxylic acid diglycidyl ester, vinyl glycidyl ester, glycidyl acrylate, glycidyl methacrylate, glycidyl methyl methacrylate, styrene paraglycidyl ether, 4-epoxy-1 -Pentene or paraglycidyl styrene, and monomers containing maleic anhydride include maleic acid, fumaric acid, itaconic acid, maleic anhydride or itaconic anhydride. These functional monomers make up 0.1-30% by weight of the functional resin (A). If the functional monomer exceeds 30% by weight, the flow of the resin is reduced, there is a problem in processing is not good.

EPM functional rubber (B) used in the present invention should be graft reaction in the functional resin (A) and the extruder, which is necessary for the functionalization operation, for the functionalization of EPM rubber for the production of ethylene-propylene copolymer The functional EPM rubber (B) is obtained by reacting the monomer containing the reactive group and the catalyst at the time together on the extruder.

As the monomer containing a reactive group that can be used for this purpose, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride or itaconic anhydride can be used, and the amount thereof is 0.1-10% by weight of the EPM rubber composition. If it is less than 0.1% by weight, it is difficult to cause sufficient reaction. If it exceeds 10% by weight, severe crosslinking reaction occurs, which is not preferable because of processing problems.

In the preparation of such functional EPM rubber (B), a catalyst may be used to increase the graft efficiency, but isopropyl peroxydicarbonate, cumene hydroxy peroxide, dicumylperoxide, benzoyl peroxide, tertiary butyl benzoate, etc. It may be used in an amount of 0.01-2.0% by weight of the total EPM rubber composition.

In the resin composition of the present invention, the EPDM rubber (C) is a diene compound, for example, dicyclopentadiene, 1,4-hexadiene (1, 4) as a third component in a binary system of ethylene and propylene. -Hexadiene), 1,3-cyclooctadiene, 1,4-pentadiene (1,4-Pentadiene), 5-ethylidene-2-norbornene (5-Ethylidiene-2-Norbonene ) And so on. The molar ratio of ethylene and propylene in the ethylene-propylene rubber in the rubber (C) is in the range of 5: 1 to 2: 1, and it is also possible to use two or more kinds of different rubbers as described below.

For example, one or two blend moles of EPDM, polybutadiene, polyisoprene, and styrene-butadiene rubber can be used as the (C) component.

The functional EPM rubber, EPDM rubber, and functional resin thus prepared occupy 10-50 weight, 10-50 weight percent, and 10-90 weight percent, respectively, of the total thermoplastic resin composition, the functional EPM rubber and EPDM rubber content, respectively If it is less than 10% by weight, there is a problem that the impact property is lowered, if it exceeds 50% by weight, there is a problem that the heat resistance is lowered. If the functional resin (A) content is less than 10% by weight, there is a problem that the physical properties are lowered. If it exceeds 90% by weight, there is a problem in processing due to severe crosslinking reaction, which is not preferable.

In addition, in the present invention, a copolymer of an aromatic vinyl compound containing no functional monomer and a vinyl cyanide compound, that is, a copolymer (D) may be added in a range of 0 to 40% by weight, because the properties of the resin can be controlled. Meanwhile, the functional EPM rubber (B), the EPDM rubber (C), the functional resin (A) and the copolymer (D) having the above characteristics are graft-reacted with each other through a single or twin screw extruder to impart compatibility. To prepare a thermoplastic resin excellent in impact resistance, the specific method is described as follows.

First, the above-mentioned functional EPM rubber, EPDM rubber and functional resin are introduced into the twin screw extruder equipped with a kneading block at each ratio at a time. At this time, the compatibility between resins can be controlled by changing the time and temperature at which the resin stays in the extruder. The retention time is increased, so that the interfacial adhesion is increased, and the reactivity increases with increasing temperature, thereby increasing the compatibility.

In the present invention, the graft reaction between resins should be made at 170-250 ° C. for at least 30 seconds to achieve good compatibility. If the temperature is less than 170 ℃ is not accompanied by a chemical reaction that affects the compatibility between the resins have a problem that the compatibility is lowered and the resin is deformed or discolored when it exceeds 250 ℃.

The extrusion speed of the extruder can be adjusted to 50-400rpm to control the residence time of the resin in the extruder, thereby controlling the chemical reaction.

Therefore, the thermoplastic resin manufacturing method of the present invention as described above is manufactured through the reaction extrusion in the extruder using a functional EPM rubber, EPDM rubber and a functional resin, do not use a polar solvent at all, and easy to control the final physical properties, There are several advantages, such as the elimination of complex processes that have been performed in the manufacturing process.

Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.

[Production Example 1]

Preparation of Functional EPM Rubber (B)

100 parts by weight of ethylene-propylene rubber, 1.0 part by weight of acrylic acid and 0.05 part by weight of dicumyl peroxide as a catalyst were combined and melt-extruded using a 40 mm twin screw extruder with a kneading block to obtain a functional EPM rubber. At this time, the compression speed was 300rpm and the extrusion temperature was 240 ℃.

[Production Example 2]

Preparation of Functional Resin (A)

75 parts by weight of styrene monomer, 25 parts by weight of acrylonitrile, 10.0 parts by weight of paraglycidyl styrene and 0.4 parts by weight of tertiary butylhydro peroxide, a radical polymerization initiator, were added to a high-pressure reactor equipped with a stirrer at a temperature of 80 ° C. After heating for 3 hours to polymerize for 3 hours, 150 parts by weight of ion-exchanged water and 1.0 part by weight of tricalcium phosphate as a suspending agent were added to disperse the contents, and then heated to 90 ° C to proceed polymerization for 5 hours. After the temperature was raised to ℃, the polymerization was completed for 2 hours to give a bead-like functional resin of 0.5-1.0mm in diameter through the process of dehydration, drying.

[Example 1-9]

The functional EPM rubber of Preparation Example 1, the functional resin of Preparation Example 2, and EPDM rubber were blended in the combination component ratios illustrated in the following table, followed by melt extrusion using a 40 mm twin screw extruder.

The residence time and temperature to control the compatibility during melt extrusion were controlled by changing the rpm of the extruder and the temperature of the kneading block. The overall physical properties were measured after fabrication using the 4 oz. Specimen injection machine and the injection temperature was set to 240 ℃. The results are shown in Table 1 below.

Comparative Example 1-5

In the same manner as in the above example, the composition ratio illustrated in Table 1 was used, but instead of the functional EPM rubber, a copolymer of ethylene-propylene rubber itself or EPDM rubber and an unfunctionalized aromatic vinyl compound and a vinyl cyanide compound was used as it was. The results are shown in Table 1 below.

[Comparative Example 6-9]

Specimens were prepared using the composition ratios illustrated in Table 2 in the same manner as in Example, and the notched impact strength and heat deflection temperature were measured. The results are shown in Table 2 below.

Claims (8)

(A) 10-90% by weight of a functional resin obtained by adding a functional monomer in an amount of 0.1-30% by weight to the aromatic vinyl compound-vinyl cyanide compound copolymer; (B) 1-50% by weight of a functional ethylene-propylene copolymer rubber obtained by adding a monomer containing a reactive group to the ethylene-propylene copolymer in an amount of 0.1-10% by weight; (C) 1-50% by weight of ethylene-propylene-diene copolymer rubber; And (D) 0-40% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer. (A) 65-85% of the functional resin obtained by adding the functional monomer to the aromatic vinyl compound-vinyl cyanide compound copolymer in an amount of 0.1-30% by weight; (B) 7-20% by weight of a functional ethylene-propylene copolymer rubber obtained by adding a monomer containing an ethylene-propylene copolymer reactive group in an amount of 0.1-10% by weight; (C) 5-20% by weight of ethylene-propylene-diene copolymer rubber; And (D) 0-10% by weight of an aromatic vinyl compound-vinyl cyanide compound copolymer. The functional monomer of the functional resin (A) is a monomer containing an epoxy group or a monomer containing a maleic anhydride group, and occupies 0.1 to 30% by weight of the resin (A). Thermoplastic resin composition. 4. The monomer according to claim 1 or 3, wherein the monomer containing an epoxy group is an itaconic acid mono glycidyl ester, butene tricarboxylic acid monoglycidyl ester, butene tricarboxylic acid diglycidyl ester, vinylglycidyl ester, At least one of glycidyl acrylate, glycidyl methacrylate, glycidyl methylmethacrylate, styrene paraglyceryl ether, 4-epoxy-1 pentene or paraglycidyl styrene. Thermoplastic resin composition. The thermoplastic resin composition according to claim 1 or 3, wherein the monomer containing maleic anhydride group is one or two or more of maleic acid, fumaric acid, itaconic acid, maleic anhydride or itaconic anhydride. The monomer containing a reactive group in the functional ethylene-propylene rubber (B) is acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride or itaconic anhydride, and the amount thereof is The thermoplastic resin composition, characterized in that 0.1 to 10% by weight based on the weight of the rubber (B). The diene in component (C) according to claim 1 or 2, wherein the diene in component (C) is dicyclopentadiene, 1,4-hexadiene, 1.3-cyclooctadiene, 1,5-hexadiene, 1,7-octadiene, 1 , 4-pentadiene, or 5-ethylidene-2 norbornene. (A) 10-90% by weight of a functional resin obtained by adding an aromatic vinyl compound-vinyl cyanide compound copolymer functional monomer in an amount of 0.1-30% by weight; (B) 1-50% by weight of a functional ethylene-propylene copolymer rubber obtained by adding a monomer containing a reactive group to the ethylene-propylene copolymer in an amount of 0.1-10% by weight; (C) 1-50% by weight of ethylene-propylene-diene copolymer rubber; And (D) 0-40% by weight of the aromatic vinyl compound-vinyl cyanide compound copolymer is melt-extruded for 30 seconds or more at a temperature of 170-250 ° C. and an extrusion rate of 50-400 rpm.