KR101773658B1 - Method of preparing abs resin having good heat resistance and abs resin having good heat resistance therefrom - Google Patents

Abstract

More particularly, the present invention relates to a process for producing a heat resistant ABS resin, which comprises polymerizing a mixed solution obtained by mixing a reaction solvent, an aromatic vinyl monomer, a vinylcyano monomer, a maleic anhydride monomer and a conjugated diene rubber; Introducing a primary amine after the polymerization to cause an imidation reaction; And finally polymerizing the imidization reaction followed by polymerization.
According to the present invention, there is provided an effect of providing a method of manufacturing a heat-resistant ABS resin excellent in heat resistance and thermal stability and reduced in occurrence of residues, and excellent in workability and retention stability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a heat-resistant ABS resin,

More particularly, the present invention relates to a method for producing a heat-resistant ABS resin having excellent heat resistance and thermal stability and reduced generation of residues, and to providing a heat-resistant ABS resin prepared therefrom .

Heat resistant acrylonitrile-butadiene-styrene (ABS) resin, which is generally excellent in impact resistance, processability, and chemical resistance, is widely used for parts for electric and electronic devices such as interior and exterior materials for automobiles, office equipment, home appliances, A high-performance heat-resistant resin having higher heat resistance is required.

Conventional heat-resistant ABS resin manufacturing methods include blending ABS resin prepared by emulsion polymerization and styrene-acrylonitrile with heat-resistant SAN resin in which monomers such as α-methylstyrene or n-phenylmaleimide are substituted, However, since there are many residues, there is a problem that the generation of gas occurs during injection molding and the stability of residence deteriorates. As described above, the process using the maleimide-based monomer, mainly phenylmaleimide, is troublesome in that the maleimide-based monomer is divided into several steps, and an additional process for dissolving the maleimide-based monomer in the solid state is required , Impact resistance and the like are not satisfactory, and the maleimide-based monomer is classified as a toxic substance, so that it is not easy to handle.

In another method, there is a method of producing heat-resistant ABS resin by continuous bulk polymerization by adding maleic anhydride as a heat-resistant monomer, but in this case, since the final ABS resin contains an unsaturated carboxylic acid, there is a problem that thermal stability is lowered.

Korean Patent Publication No. 2009-0029537 (published on March 23, 2009)

It is an object of the present invention to provide a method for producing a heat-resistant ABS resin excellent in heat resistance and thermal stability and reduced in occurrence of residues, and having excellent processability and stability of stay.

The present invention also aims to provide a heat-resistant ABS resin produced by the above-mentioned method.

These and other objects of the present disclosure can be achieved by all of the present invention described below.

In order to attain the above object, the present invention provides a method for producing a rubber composition, comprising the steps of: polymerizing a mixed solution obtained by mixing a reaction solvent, an aromatic vinyl monomer, a vinylcyanide monomer, a maleic anhydride monomer and a conjugated diene rubber; Introducing a primary amine after the polymerization to cause an imidation reaction; And finally polymerizing the imidization reaction followed by polymerization.

In addition, the present invention provides a heat-resistant ABS resin excellent in heat resistance and thermal stability produced by the above-described production method and having reduced occurrence of residue, and having excellent processability and retention stability.

As described above, according to the present invention, the maleic anhydride monomer, which is a heat resistant monomer, is replaced with thermally stable maleimide through an imidization reaction with a primary amine, so that heat resistance and thermal stability are excellent, And a heat-resistant ABS resin produced by the above-described method.

Hereinafter, the present invention will be described in detail.

The process for producing the heat resistant ABS resin according to the present invention comprises the steps of: polymerizing a mixed solution obtained by mixing a reaction solvent, an aromatic vinyl monomer, a vinylcyanide monomer, a maleic anhydride monomer and a conjugated diene rubber; Introducing a primary amine after the polymerization to cause an imidation reaction; And a final polymerization step after the imidization reaction. The heat-resistant ABS resin prepared by the above-mentioned method has excellent heat resistance and thermal stability, and has reduced residue generation, and thus has excellent processability and stability.

The mixed solution is prepared by mixing 10 to 40% by weight of a reaction solvent, 30 to 65% by weight of an aromatic vinyl monomer, 1 to 25% by weight of a vinyl cyan monomer, 1 to 20% by weight of a maleic anhydride monomer, and 1 to 20 %.

The reaction solvent is, for example, 15 to 35% by weight or 20 to 30% by weight, and the viscosity is easily controlled within the above range.

The reaction solvent may be at least one selected from the group consisting of toluene, ethylbenzene, xylene, methyl ethyl ketone, and xylene.

Another example of the aromatic vinyl monomer may be 35 to 60% by weight or 43 to 53% by weight, and the impact strength is excellent within the above range.

The aromatic vinyl-based monomer may be at least one member selected from the group consisting of styrene, alpha-methylstyrene, o-ethylstyrene, p-ethylstyrene, and 3-4-dichlorostyrene.

Another example of the vinyl cyano monomer is 5 to 20% by weight or 10 to 15% by weight, and the heat resistance is excellent within the above range.

The vinyl cyano based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.

As another example, the maleic anhydride monomer has an effect of 3 to 15% by weight, or 4 to 12% by weight, and excellent in heat resistance and residence stability within the above range.

The maleic anhydride monomer may be at least one member selected from the group consisting of maleic anhydride, maleic acid, maleic monoester and maleic diester.

As another example, the conjugated diene rubber may be 3 to 15% by weight or 5 to 11% by weight, and the impact strength is excellent within the above range.

The conjugated diene rubber may be at least one selected from the group consisting of polybutadiene rubber, polyisoprene rubber, styrene-butadiene copolymer rubber and acrylonitrile-butadiene copolymer rubber.

The primary amine can be added in an amount of 1 to 1.2 times, or 1 to 1.1 times, based on the weight of the maleic anhydride monomer, and has excellent heat stability and processability within the above range.

The primary amine may be at least one selected from the group consisting of methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline, toluidine, chlorophenylamine and bromophenylamine It is aniline.

The polymerization may be, for example, bulk polymerization, preferably continuous bulk polymerization.

The polymerization is effected in an amount of 0.005 to 0.15 parts by weight, 0.01 to 0.10 parts by weight, or 0.03 to 0.07 parts by weight, for example, and an excellent balance of polymerization and physical properties within the above range.

The initiator may be selected from the group consisting of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, lauroyl peroxide, benzoyl peroxide, cyclohexanone peroxide, At least one selected from the group consisting of

Polymerizing the mixed solution in a reactor at 90 to 100 < 0 >C; Secondary polymerization in a reactor at 120 to 140 캜; A step of introducing a primary amine and carrying out an imidization reaction at 120 to 200 ° C; And a final polymerization in a reactor at a temperature of 155 to 165 ° C. In this case, there is an effect that the heat resistance and the thermal stability are excellent and the generation of residues is reduced.

Removing the unreacted monomers and the solvent in a devolatilizing tank under a high-temperature vacuum after the final polymerization step, and then preparing a pellet.

As another example of the imidization substitution reaction, the reaction is excellent at 130 to 170 ° C or 145 to 155 ° C, and the primary amine is not decomposed.

The reactor may be a continuous stirred tank reactor (CSTR), a plug flow reactor, or a multi-stage reactor. In particular, a continuous stirred tank reactor is preferably used.

The vacuum of the devolatilizing tank may be, for example, 25 Torr or less, or 10 to 25 Torr. In this case, the residual monomer content in the resin is low and the thermal stability is improved.

The temperature of the devolatilizing tank may be, for example, 200 to 250 ° C or 220 to 240 ° C, and the unreacted monomer and the reaction solvent may be easily removed within the above range.

The present invention provides a heat-resistant ABS resin produced by the above-mentioned method for producing a heat-resistant ABS resin.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example 1

8% by weight of styrene-butadiene rubber (styrene content: 40% by weight and butadiene content: 60% by weight) was added to a mixture of 25% by weight of toluene, 49.6% by weight of styrene and 5% by weight of maleic anhydride as a reaction solvent, , 0.05 part by weight of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (t-butylperoxy) -3,3,5-trimethyl cyclohexane as an initiator To prepare a polymerization solution. The polymerized solution was firstly polymerized at a temperature of 95 ° C in a first reactor while being charged into a 26L reactor at a rate of 12 L / hr. Second polymerization was carried out at a temperature of 130 ° C in a second reactor. , An aromatic vinyl monomer, a vinylcyanide monomer, a maleic anhydride monomer, and a conjugated diene rubber, 5 parts by weight of aniline, which is the same amount as that of maleic anhydride, was fed at a flow rate of 0.6 L / hr, and 150 Lt; RTI ID = 0.0 > C. ≪ / RTI > After the final polymerization was sufficiently carried out at 160 ° C in the fourth reactor, unreacted monomers and solvent were removed at a vacuum degree of 25 Torr or less in a volatilization bath at 200 to 250 ° C when the polymerization conversion rate reached about 80%, and then the pelletized resin And the physical properties thereof were measured.

Examples 2 to 3 and Comparative Examples 1 to 2

The pelletized resin was prepared in the same manner as in Example 1 except that the components and contents in the following Table 1 were used in Example 1, and the physical properties were measured.

Comparative Example 3

30 parts by weight of PMI-SAN resin (PAS 1460, NISPON SHOKUBAI PAS 1460, PMI content 35%, styrene content 50% by weight and acrylonitrile content 7% by weight), SAN resin (styrene content 73% by weight and acrylonitrile content 27% ), 27 parts by weight of an ABS powder (butadiene content 60% by weight, styrene content 30% by weight and acrylonitrile content 10% by weight) and 0.2 parts by weight of IR-1076 as an antioxidant were fed into an extruder To prepare a resin in the form of pellets, and the physical properties thereof were measured.

 [Test Example]

The properties of the specimens prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.

Impact strength (1/4 ", kgf · cm / cm): measured according to ASTM D256 method (Izod Impact).

Heat resistance (HDT, ° C): Measured according to the ASTM D648 method.

* Retention stability (ΔE): LAB value, which is the color value of the specimen, was measured using a Hunter Lab colorimeter at 210 ° C direct injection and at 25 ° C for 15 minutes. ? E is an arithmetic mean value before and after retention, and the closer to 0, the better the retention stability.

[Equation 1]

* T-VOC (Total Volatile Organic Compound, g / gmol) was analyzed using Gel Chromatograph (G / C).

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 SM (% by weight) 49.6 47.6 45.6 49.6 45.6 - AN (% by weight) 12.4 11.9 11.4 12.4 11.4 - MAH (% by weight) 5 7.5 10 5 10 - SBR (% by weight) 8 8 8 8 8 - TLN (% by weight) 25 25 25 25 25 - Aniline (parts by weight) 5 7.5 10 0 0 - Aniline input amount (L / hr) 0.6 0.9 1.2 0 0 - Impact strength (1/4 ", 23 ° C) 21.2 20.4 18.7 21.3 19 23.7 Heat resistance (℃) 100 104 110 98 107 102 Stability (ΔE) 2.3 2.4 2.6 3.5 5.8 3.2 T-VOC (g / gmol) 65 58 50 68 56 108

As shown in Table 1, in Examples 1 to 3 of the present invention, it was possible to confirm the effect of heat resistance, stability of stay and T-VOC while maintaining the impact strength.

On the other hand, in Comparative Examples 1 and 2 in which aniline was not added, the heat resistance and especially the retention stability were deteriorated. In Comparative Example 3 conducted by the conventional method of producing a heat-resistant ABS resin, it was confirmed that T-VOC was rapidly increased and a large amount of toxic volatile compounds were generated in the human body.

Claims (14)

A mixture of 20 to 30% by weight of a reaction solvent, 43 to 53% by weight of an aromatic vinyl monomer, 10 to 15% by weight of a vinylcyanide monomer, 7.5 to 10% by weight of a maleic anhydride monomer and 5 to 11% by weight of a conjugated diene rubber Polymerizing the mixed solution;
Adding the primary amine in the polymerization to 7.5 to 10 parts by weight based on 100 parts by weight of the reaction solvent, the aromatic vinyl monomer, the vinyl cyan monomer, the maleic anhydride monomer, and the conjugated diene rubber; And
Wherein the reaction solvent is at least one selected from the group consisting of toluene, ethylbenzene, and xylene. The method of claim 1, wherein the reaction solvent is at least one selected from the group consisting of toluene, ethylbenzene and xylene.
delete delete The method according to claim 1,
Wherein the aromatic vinyl-based monomer is at least one selected from the group consisting of styrene, alpha-methylstyrene, o-ethylstyrene, p-ethylstyrene, and 3-4-dichlorostyrene.
The method according to claim 1,
Wherein the vinyl cyano monomer is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.
The method according to claim 1,
Wherein the maleic anhydride monomer is at least one member selected from the group consisting of maleic anhydride, maleic acid, maleic monoester and maleic diester. A method for producing an ABS resin.
The method according to claim 1,
Wherein the conjugated diene rubber is at least one selected from the group consisting of a polybutadiene rubber, a polyisoprene rubber, a styrene-butadiene copolymer rubber, and an acrylonitrile-butadiene copolymer rubber.
The method according to claim 1,
The primary amine is at least one member selected from the group consisting of methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline, toluidine, chlorophenylamine and bromophenylamine By weight based on the total weight of the thermosetting resin.
delete The method according to claim 1,
Wherein the polymerization is bulk polymerization.
The method according to claim 1,
Wherein the polymerization is carried out in an amount of 0.005 to 0.15 part by weight based on the initiator.
The method according to claim 1,
The mixed solution is subjected to a primary polymerization in a reactor at 90 to 100 ° C; Secondary polymerization in a reactor at 120 to 140 캜; A step of introducing a primary amine and carrying out an imidization reaction at 120 to 200 ° C; And 155 to 165 ° C in a reactor.
The method according to claim 1,
Further comprising the step of removing unreacted monomers and a solvent in a devolatilizing tank under a high-temperature vacuum after the final polymerization step to prepare pellets.
14. A heat-resistant ABS resin produced by any one of claims 1, 4 to 8, or 10 to 13.