KR101838163B1 - A thermoplastic resin having excellent heat resistance and mechanical properties, and a method for manufacturing the same - Google Patents

Abstract

According to an embodiment of the present invention, provided are a thermoplastic resin and a manufacturing method thereof. The thermoplastic resin is made by copolymerizing a monomer mixture with a copolymer wherein the monomer mixture includes a rubber component, an N-substitution maleimide monomer, a heat-resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer and the copolymer is made of an N-substitution maleimide monomer, a heat-resistant aromatic vinyl monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer. Therefore, the manufacturing method can simplify continuous polymerization processes.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermoplastic resin having excellent heat resistance and mechanical properties and a method for producing the thermoplastic resin.

The present invention relates to a thermoplastic resin having excellent heat resistance and mechanical properties, and a method for producing the same.

In general, acrylonitrile-butadiene-styrene (ABS) copolymer resins are excellent in impact resistance, chemical resistance, chemical resistance and mechanical strength, and are easy to be molded. Parts, and general goods. However, ABS resin has a limit to be used for applications requiring high heat resistance due to low heat resistance.

In order to increase the heat resistance of the ABS resin, a method of replacing a part of components constituting the ABS resin with a heat-resistant copolymer containing a styrene monomer having excellent heat resistance, an imide monomer or the like, or adding an inorganic substance has been proposed.

Among them, addition of an inorganic substance has an effect of improving the heat resistance, but it has a problem that the mechanical properties such as impact strength, flexural strength, tensile strength and the like are deteriorated because the compatibility with the polymer resin and the dispersibility are deteriorated. The imide monomer also has an excellent effect of improving the heat resistance, but since the miscibility with the SAN constituting the matrix of the ABS resin is lowered, the mechanical properties are lowered and the color properties such as the yellow color, whiteness degree and heat discoloration of the ABS resin are significantly There is a problem of deterioration.

In the case of using a styrene-based monomer having excellent heat resistance, the heat resistance improvement effect is relatively weak but the balance of physical properties is good compared with the above-mentioned other methods, and thus it is widely used commercially. Of these, α-methyl styrene (AMS) has been widely used commercially because of its excellent balance of physical properties with respect to price, and various studies are being conducted on a method for producing a heat-resistant copolymer using alpha methyl styrene.

Generally, the most widely used method for improving the heat resistance of the ABS resin is a melt extrusion method using a heat-resistant copolymer resin. In this method, a heat-resistant copolymer resin is prepared by using alpha methyl styrene (AMS), or a heat-resistant copolymer resin is prepared by using N-phenyl maleimide (PMI) ) And grafted rubber and other additives prepared so as to improve compatibility with each other.

The continuous polymerization method using the PMI-based monomer and the butadiene rubber has an advantage that a product having excellent heat resistance can be produced through a single process. However, due to the copolymerization rate ratio of the PMI-based monomer and the styrene monomer, And the matrix composition of the latter stage of the continuous polymerization may be different from each other, so that the miscibility may be lowered and the mechanical properties such as impact strength may be deteriorated. As a method for solving this problem, there has been proposed a method of correcting the composition while adding a PMI monomer in accordance with the degree of polymerization of each of the polymerization reactors connected in series, but the process is complicated and difficult.

On the other hand, the use of a liquid AMS monomer is advantageous in that the raw material can be easily handled in the polymerization process and the raw material cost is lower than the PMI monomer in powder form. However, due to the self-depolymerization characteristic of the AMS monomer, It is difficult to balance heat resistance and mechanical properties by using AMS-based monomer and rubber at the same time.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems of the prior art, and an object of the present invention is to provide a thermoplastic resin composition which can simultaneously achieve both heat resistance and mechanical properties by simultaneously applying PMI- and AMS- And a method for producing the same.

An aspect of the present invention relates to a mixture comprising a rubber component, an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer; And a copolymer composed of an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer.

In one embodiment, 1 to 10 parts by weight of the copolymer may be copolymerized with 100 parts by weight of the mixture.

In one embodiment, the rubber component may comprise butadiene rubber and styrene-butadiene rubber.

In one embodiment, the butadiene rubber may be 25 to 70 cps at 25 ° C in a solution prepared by dissolving the butadiene rubber in 5 wt% of styrene.

In one embodiment, the mixture comprises 5 to 15 wt% of butadiene rubber, 1 to 5 wt% of styrene-butadiene rubber, 1 to 10 wt% of N-substituted maleimide monomer, 15 to 35 wt% of heat resistant aromatic vinyl monomer, 25 to 45% by weight of a vinyl monomer, and 15 to 25% by weight of an unsaturated nitrile monomer.

In one embodiment, the copolymer comprises 5 to 60 wt% of an N-substituted maleimide monomer, 10 to 70 wt% of a heat resistant aromatic vinyl monomer, 5 to 50 wt% of an unsaturated nitrile monomer, and 3 to 50 wt% of an aromatic vinyl monomer, ≪ / RTI >

In one embodiment, the N-substituted maleimide monomer is selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- But are not limited to, butyl maleimide, N-isobutyl maleimide, Nt-butyl maleimide, N-cyclohexylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, Maleic anhydride, maleimide, N-lauryl maleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N- And mixtures thereof.

In one embodiment, the heat-resistant aromatic vinyl monomer may be selected from the group consisting of? -Methylstyrene,? -Ethylstyrene, methyl? -Methylstyrene, and a mixture of two or more thereof.

In one embodiment, the aromatic vinyl monomer is selected from the group consisting of styrene,? -Methylstyrene vinyltoluene, t-butylstyrene, halogen substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, And mixtures thereof.

In one embodiment, the unsaturated nitrile monomer is selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and mixtures of two or more thereof .

(I) a mixture comprising a rubber component, an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer, and (ii) Preparing a solution by dissolving a copolymer comprising an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer; (b) introducing the solution into a first reactor to produce a first polymer having a conversion of the mixture of 20 to 35% by weight; (c) introducing the first polymer into a second reactor to produce a second polymer having a conversion of the mixture of 35 to 50% by weight; (d) introducing the second polymer into a third reactor to produce a third polymer having a conversion of the mixture of 50 to 70% by weight; And (e) introducing the third polymer into a fourth reactor to produce a fourth polymer having a conversion of 70 to 90% by weight of the mixture.

In one embodiment, the solution may comprise from 1 to 10 parts by weight of the copolymer, based on 100 parts by weight of the mixture.

In one embodiment, the rubber component may comprise butadiene rubber and styrene-butadiene rubber.

In one embodiment, the butadiene rubber may be 25 to 70 cps at 25 ° C in a solution prepared by dissolving the butadiene rubber in 5 wt% of styrene.

In one embodiment, the mixture comprises 5 to 15 wt% of butadiene rubber, 1 to 5 wt% of styrene-butadiene rubber, 1 to 10 wt% of N-substituted maleimide monomer, 15 to 35 wt% of heat resistant aromatic vinyl monomer, 25 to 45% by weight of a vinyl monomer, and 15 to 25% by weight of an unsaturated nitrile monomer.

In one embodiment, the copolymer comprises 5 to 60 wt% of an N-substituted maleimide monomer, 10 to 70 wt% of a heat resistant aromatic vinyl monomer, 5 to 50 wt% of an unsaturated nitrile monomer, and 3 to 50 wt% of an aromatic vinyl monomer, ≪ / RTI >

In one embodiment, 0.01 to 0.3 parts by weight of a radical initiator, 0.005 to 0.2 parts by weight of a polyfunctional vinyl compound, and 0.01 to 0.5 parts by weight of a molecular weight modifier are added to the first reactor in 100 parts by weight of the mixture in the step (b) More parts can be added.

In one embodiment, the step (b) to (e) the reaction temperature respectively Tb, Tc, Td, and Te in the phase, and T _b <T _c <T _d <T _e, T _e is 145-165 Lt; 0 &gt; C.

In one embodiment, the step (b) to (e), respectively, the reaction time in step t _b, t _c, t _d, and t _e, t _b> t _c> t _d> t _e a, t _e May be 0.1 to 1 hour.

In one embodiment, the step (f) may further include the step of putting the fourth polymer into a devolatilizing apparatus to remove unreacted materials.

According to one aspect of the present invention, there is provided a process for producing a rubber composition comprising a mixture comprising a rubber component, an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an aromatic vinyl monomer and an unsaturated nitrile monomer in the presence of an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, Nitrile monomer, and aromatic vinyl monomer, the PMI-based monomer and the AMS-based monomer can be simultaneously applied during the continuous polymerization of the ABS resin, so that the heat resistance and the mechanical properties can be balanced.

According to another aspect of the present invention, there is provided a rubber composition comprising a mixture comprising a rubber component, an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer, A solution prepared by dissolving a copolymer composed of a monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer in an organic solvent is successively reacted in a first reactor and second to fourth reactors connected in series in the downstream thereof to simplify and simplify the continuous polymerization process can do.

It should be understood that the effects of the present invention are not limited to the effects described above, but include all effects that can be deduced from the description of the invention or the composition of the invention set forth in the claims.

1 shows FT-IR analysis results of the thermoplastic resin pellets according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" to another part, it includes not only "directly connected" but also "indirectly connected" . Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

Thermoplastic resin

An aspect of the present invention relates to a mixture comprising a rubber component, an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer; And a copolymer composed of an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer.

The weight average molecular weight of the thermoplastic resin may be 100,000 to 180,000, preferably 120,000 to 160,000. If the weight average molecular weight of the thermoplastic resin is less than 100,000, the mechanical properties may deteriorate. If the weight average molecular weight is more than 180,000, the melt viscosity may increase sharply and the workability may be deteriorated. The thermoplastic resin had an Izod impact strength (kg · cm / cm, 3.2 mm notched) of 20 to 30 as measured by ASTM D-256 and a melt index (200 ° C., 21.6 kg ) Is 5.0 to 6.5, and the softening point (5 kg, 50 ° C / hr) of the vicat measured by ASTM D-1525 may be 110 to 120 ° C.

(1) Mixture

(1-1) Rubber component

The rubber component may include butadiene rubber and styrene-butadiene rubber.

The butadiene rubber may have a viscosity of 25 to 70 cps at 25 DEG C in a solution prepared by dissolving styrene in 5 wt% of the butadiene rubber. When the solution viscosity of the butadiene rubber exceeds 70 cps, it is difficult to control the particle diameter of the rubber.

The content of the butadiene rubber in the mixture may be 5 to 15% by weight. If the content of the butadiene rubber is less than 5% by weight, mechanical properties including impact strength may be deteriorated. If the content is more than 15% by weight, it is difficult to control the particle diameter of the rubber due to high viscosity, and the heat resistance may be significantly lowered.

The styrene-butadiene rubber may be a copolymer comprising 20 to 50% by weight of styrene and 50 to 80% by weight of butadiene. If the content of styrene is less than 20% by weight, the heat resistance and mechanical properties can not be balanced. If the content of styrene is more than 50% by weight, the content of rubber in the thermoplastic resin may be lowered.

The butadiene may be selected from the group consisting of 1,3 butadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl- But may be 1,3-butadiene, but is not limited thereto.

The styrene may be at least one selected from the group consisting of styrene,? -Methylstyrene,? -Ethylstyrene, o-methylstyrene, p-styrene, m-methylstyrene,? -Methylstyrene vinyltoluene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, and mixtures of two or more thereof, preferably styrene, but is not limited thereto.

The content of the styrene-butadiene rubber in the mixture may be 1 to 5% by weight. If the content of the styrene-butadiene rubber is less than 1% by weight, it is difficult to control the particle size of the rubber and the mechanical properties thereof. If the content of the styrene-butadiene rubber exceeds 5% by weight, the impact resistance may be lowered.

(1-2) N-substituted maleimide monomer

The N-substituted maleimide monomer is one component of the above-mentioned mixture, and at the same time, is a monomer constituting the copolymer and can improve the heat resistance of the thermoplastic resin.

First, the content of the N-substituted maleimide monomer in the mixture may be 1 to 10% by weight, and preferably 3 to 10% by weight. When the content of the N-substituted maleimide monomer is less than 1% by weight, the compatibility with the copolymer is lowered and the heat resistance and mechanical properties can not be balanced. If the content is more than 10% by weight, It is difficult to control the particle size and the mechanical properties thereof and the molecular weight may be lowered.

The content of the N-substituted maleimide monomer in the copolymer may be 5 to 60% by weight. When the content of the N-substituted maleimide monomer is within the above range, the increase in melt viscosity and embrittlement can be suppressed while preventing the decrease in heat resistance and thermal stability of the copolymer, thereby improving the compatibility with the mixture and the kneading property .

The N-substituted maleimide monomer contained as one component and one monomer respectively in the mixture and the copolymer may be the same or different. However, it is preferable to use the same as the N-substituted maleimide monomer in each of these in consideration of the compatibility and the compatibility of the copolymer and the copolymer.

The N-substituted maleimide monomer is selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, But are not limited to, isobutyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-benzylmaleimide, and a mixture of two or more thereof, in the group consisting of maleimide, N-hydroxyphenylmaleimide, And may be selected, preferably N-phenylmaleimide, but is not limited thereto.

(1-3) Heat-resistant aromatic vinyl monomers

The heat-resistant aromatic vinyl monomer is one component of the above-mentioned mixture, and is a monomer constituting the copolymer, facilitating the control of the polymerization rate of the mixture and the copolymer, and improving the heat resistance of the thermoplastic resin.

First, the content of the heat-resistant aromatic vinyl monomer in the mixture may be 15 to 35% by weight. If the content of the heat resistant aromatic vinyl monomer is less than 15% by weight, heat resistance may be deteriorated. If the content of the heat resistant aromatic vinyl monomer is more than 35% by weight, the polymerization rate may be slowed to lower productivity, The molecular weight is remarkably lowered and the heat resistance and mechanical properties can not be balanced.

The content of the heat-resistant aromatic vinyl monomer in the copolymer may be 10 to 70% by weight. If the content of the heat-resistant aromatic vinyl monomer is less than 10% by weight, heat resistance may be deteriorated. If the content is more than 70% by weight, the polymerization rate may become unstable, and thermal stability and color tone may be deteriorated.

The heat-resistant aromatic vinyl monomer contained as one component and one monomer respectively in the mixture and the copolymer may be the same or different. However, it is preferable to use the same as the heat-resistant aromatic vinyl monomer in each of these in consideration of the compatibility and the kneadability of the mixture and the copolymer.

The heat-resistant aromatic vinyl monomer may be selected from the group consisting of? -Methylstyrene,? -Ethylstyrene, methyl? -Methylstyrene, and a mixture of two or more thereof, preferably? -Methylstyrene, But is not limited thereto.

(1-4) An aromatic vinyl monomer

The aromatic vinyl monomer may be a monomer of the above-mentioned mixture and constituting the copolymer.

First, the content of the aromatic vinyl monomer in the mixture may be 25 to 45% by weight, preferably 30 to 40% by weight. If the content of the aromatic vinyl monomer is out of the above range, the compatibility of the mixture with the copolymer is lowered, and the heat resistance and mechanical properties of the thermoplastic resin can not be balanced.

The content of the aromatic vinyl monomer in the copolymer may be 3 to 50% by weight. When the content of the aromatic vinyl monomer is in the above range, the melt viscosity of the copolymer can be kept low to improve the compatibility with the mixture and the kneadability, thereby improving the thermoplastic resin and the thermal stability and heat resistance have.

The aromatic vinyl monomer contained as one component and one monomer respectively in the mixture and the copolymer may be the same or different. However, in consideration of the compatibility and the kneading property of the mixture and the copolymer, it is preferable to use the same as the aromatic vinyl monomer in each of them.

Wherein the aromatic vinyl monomer is at least one selected from the group consisting of styrene,? -Methylstyrene vinyltoluene, t-butylstyrene, halogen substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, ethylstyrene, And may be selected. Preferably, it may be styrene, but is not limited thereto.

(1-5) Unsaturated Nitrile Monomer

The unsaturated nitrile monomer may be a monomer of the above-mentioned mixture and a monomer constituting the copolymer.

First, the content of the unsaturated nitrile monomer in the mixture may be 15 to 25% by weight in consideration of the heat resistance and mechanical properties of the thermoplastic resin and the compatibility of the mixture and the copolymer.

The content of the unsaturated nitrile monomer in the copolymer may be 5 to 50% by weight. If the content of the unsaturated nitrile monomer is less than 5% by weight, the polymerization rate becomes unstable and it is difficult to control the polymerization reaction. If the content of the unsaturated nitrile monomer is more than 50% by weight, it is difficult to control the heat generation during polymerization.

The unsaturated nitrile monomer contained as one component and one monomer respectively in the mixture and the copolymer may be the same or different. However, it is preferable to use the same unsaturated nitrile monomer in each of these in consideration of the compatibility and the compatibility of the copolymer and the copolymer.

The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and mixtures of two or more thereof, , Acrylonitrile, but is not limited thereto.

(2) Copolymer

The thermoplastic resin is preferably a copolymer comprising a rubber component, an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer, wherein the mixture comprises two or more monomers, preferably four monomers &Lt; / RTI &gt;

The copolymer may be composed of an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer. The kind, function, content and the like of the monomer constituting the copolymer are as described above.

For example, the copolymer may comprise 5 to 60% by weight of an N-substituted maleimide monomer, 10 to 70% by weight of an? -Alkylstyrene monomer, 5 to 50% by weight of an unsaturated nitrile monomer, and 3 to 50% by weight of an aromatic vinyl monomer. And may be a block copolymer having a weight average molecular weight (Mw) of 7 to 300,000 and a glass transition temperature of 150 to 200 ° C so as to have a low melt viscosity.

Particularly, the copolymer is excellent in heat resistance and thermal stability, but has an N-substituted maleimide monomer which raises the viscosity of the resin, and an α-olefin copolymer having a relatively low heat resistance and thermal stability as compared with the N-substituted maleimide monomer, By using less expensive N-substituted maleimide monomer, it is possible to lower the melt viscosity and reduce the manufacturing cost. Further, the problem of lowering the heat resistance due to the weight loss of the N-substituted maleimide monomer is supplemented by an appropriate amount of the? -Alkylstyrene monomer, and the unsaturated nitrile monomer is used as a solvent for the solid N-substituted maleimide monomer, And can be applied to continuous bulk polymerization. By applying an aromatic vinyl monomer having excellent processability and coloring property, it is possible to lower the melt viscosity of the copolymer and improve the compatibility with other resins or other monomers and the kneadability.

The melt viscosity of the copolymer may be 10-200 Pa · s considering heat resistance, compatibility with other resins or other monomers, and kneadability.

1 to 10 parts by weight, preferably 1 to 7 parts by weight, of the copolymer may be copolymerized with respect to 100 parts by weight of the mixture. If the content of the copolymer copolymerized with the mixture is less than 1 part by weight, the effect of improving the heat resistance is insufficient. If the content is more than 10 parts by weight, the mechanical properties including impact strength may be deteriorated.

On the other hand, the thermoplastic resin may further include, if necessary, one additive selected from a certain amount of a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, a heat stabilizer, a dye, a pigment and a mixture of two or more thereof. The additive may be added during the polymerization reaction in each step to be described later, and may be added at the time of processing the thermoplastic resin as the final product, but the addition method or timing is not particularly limited.

Method for producing thermoplastic resin

(I) a mixture comprising a rubber component, an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer, and (ii) Preparing a solution by dissolving a copolymer comprising an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer; (b) introducing the solution into a first reactor to produce a first polymer having a conversion of the mixture of 20 to 35% by weight; (c) introducing the first polymer into a second reactor to produce a second polymer having a conversion of the mixture of 35 to 50% by weight; (d) introducing the second polymer into a third reactor to produce a third polymer having a conversion of the mixture of 50 to 70% by weight; And (e) introducing the third polymer into a fourth reactor to produce a fourth polymer having a conversion of 70 to 90% by weight of the mixture.

(A) a mixture comprising (i) a rubber component, an N-substituted maleimide monomer, a heat resistant aromatic vinyl monomer, an aromatic vinyl monomer, and an unsaturated nitrile monomer, and (ii) A solution composed of a monomeric monomer, a heat-resistant aromatic vinyl monomer, an unsaturated nitrile monomer, and an aromatic vinyl monomer may be dissolved to prepare a solution as a reactant for the subsequent continuous bulk polymerization reaction.

The organic solvent may be an aromatic compound such as ethylbenzene, benzene, toluene or xylene, methyl ethyl ketone, acetone, n-hexane, chloroform, cyclohexane or the like, but is not limited thereto. The amount of the organic solvent may be appropriately adjusted in consideration of the viscosity of the reaction system, but it may be adjusted to a range of 5 to 30 parts by weight based on 100 parts by weight of the mixture. If the amount of the organic solvent is less than 5 parts by weight, the viscosity of the reaction system may increase sharply. If the amount exceeds 30 parts by weight, the effective reaction volume of the reaction system may decrease, or the volume of the solution may increase, It can be complicated.

In addition, the rubber component, monomer, copolymer component, composition, and action effect that can be used in the preparation of the solution in the step (a) are as described above.

In the step (b), a continuous bulk polymerization reaction of the solution and the copolymer is initiated in the presence of a radical initiator, a polyfunctional vinyl compound, and a molecular weight modifier in a first reactor, and the first polymer And the temperature T _a of the first reactor can be kept relatively low as compared with the second to fourth reactors connected to the subsequent stage. For example, the temperature T _a of the first reactor may be 90-130 ° C. If the temperature T _a of the first reactor is out of the range, the conversion of the mixture may deviate from the range.

The radical initiator may be a monofunctional initiator, a polyfunctional initiator, or a mixture thereof.

The monofunctional initiator may be selected from the group consisting of t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5, Butyl peroxy-3,5,5-trimethyl hexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-bis (m- Butyl peroxy isopropyl monocarbonate, 2,5-dimethyl-2,5-bis (m-toluoyl peroxy) hexane, t-butyl peroxy isopropyl monocarbonate, T-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane (2,5- Dimethyl-2,5-bis (benzoyl peroxy) hexane, t-butyl peroxyacetate, 2,2-bis (t-butylperoxy) butyl peroxy butane, t-butyl peroxybenzoate, 1,1-di (t-amyl peroxide) Amylperoxy-cyclohexane, t-amyl peroxyacetate, t-amyl peroxy-2-ethylhexylcarbonate, 1,1- ethylhexyl carbonate, t-butylperoxy 2-ethylhexyl carbonate, and mixtures of two or more thereof.

Examples of the multifunctional initiator such as a bifunctional initiator include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (1,1- 3,3,5-trimethyl cyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane ), 1,1-di (t-amylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-di (t- (T-butylperoxy) butane, butyl 4,4-di (t-butylperoxy) valerate, and mixtures of two or more thereof And preferably 1,1-bis (t-butylperoxy) cyclohexane. However, the present invention is not limited thereto.

The amount of the radical initiator may be 0.01 to 0.3 parts by weight, preferably 0.02 to 0.1 parts by weight based on 100 parts by weight of the mixture. If the amount of the radical initiator added is less than 0.01 part by weight, the required polymerization rate and conversion can not be achieved, and the heat resistance, mechanical properties and productivity may be deteriorated. If the amount exceeds 0.3 parts by weight, It is difficult to do.

The polyfunctional vinyl compound may be a compound having three or more unsaturated hydrocarbons or a mixture thereof.

The trifunctional vinyl compound may be pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, or a mixture of two or more thereof, but is not limited thereto. The tetrafunctional vinyl compound may be, but is not limited to, di (trimethylolpropane) tetraacrylate, pentaerythritol tetraacrylate, or a mixture thereof. The pentafunctional vinyl compound may be dipentaerythritol pentaacrylate, and the hexafunctional vinyl compound may be dipentaerythritol hexaacrylate.

The amount of the polyfunctional vinyl compound to be added may be 0.005 to 0.2, preferably 0.01 to 0.1 part by weight based on 100 parts by weight of the mixture. If the amount of the polyfunctional vinyl compound is less than 0.005 parts by weight, the effect of improving the molecular weight is weak and the heat resistance and mechanical properties can not be balanced. If the amount is more than 0.2 parts by weight, polymerization reaction becomes unstable and unnecessary gel may be generated .

The molecular weight modifier may be at least one selected from the group consisting of n-dodecylmercaptan, n-amyl mercaptan, t-butyl mercaptan, t-dodecylmercaptan, n-hexylmercaptan, n-octylmercaptan, And mixtures thereof, preferably t-dodecylmercaptan, but is not limited thereto. The amount of the molecular weight controlling agent may be 0.01 to 0.5 parts by weight based on 100 parts by weight of the mixture.

In the step (c), the first polymer obtained in the first reactor is transferred to a second reactor and further subjected to continuous bulk polymerization to obtain a second polymer having a conversion of 35 to 50% by weight of the mixture. It is necessary to apply sufficient heat to achieve the conversion rate of the mixture within the above range so that the temperature T _b of the second reactor can be raised compared to the temperature T _a of the first reactor. For example, the temperature T _b of the second reactor may be 125-145 ° C. If the temperature T _b of the second reactor is out of the range, the conversion of the mixture may deviate from the range.

In the step (d), the second polymer obtained in the second reactor is transferred to the third reactor, and further subjected to continuous bulk polymerization to obtain a third polymer having a conversion of 50 to 70% by weight. The temperature T _c of the third reactor may be increased as compared with the temperature T _b of the second reactor since sufficient heat must be applied to achieve the conversion of the mixture in the above range. For example, the temperature T _c of the third reactor may be 135-155 ° C. If the temperature T _c of the third reactor is out of the range, the conversion of the mixture may deviate from the above range.

In the step (e), the third polymer obtained in the third reactor is transferred to a fourth reactor and further subjected to a continuous bulk polymerization reaction to produce a fourth polymer having a conversion of 70 to 90% by weight. When the reaction between the solution and the copolymer proceeds to a certain level or more, for example, the conversion of the mixture in the solution is in the range of 50 to 70% by weight, unreacted rubber components, monomers, The temperature T _e of the fourth reactor can be increased compared to the temperature T _d of the third reactor. For example, the temperature T _e of the fourth reactor may be 145-165 ° C. If the temperature T _e of the fourth reactor is out of the range, the conversion of the mixture may deviate from the range.

If the conversion of the mixture in the fourth polymer is less than 70% by weight, the melt viscosity of the fourth polymer is lowered and the transfer becomes difficult. When the conversion is higher than 90% by weight, the melt viscosity may excessively increase and the transfer may be difficult.

The first to fourth reactors may be stirred tank reactors, and each reactor may further include an additive for controlling the viscosity, composition, etc. of the first to fourth polymerizers, or a monomer feed line.

Meanwhile, the reaction times in the steps (b) to (e) may be t _b , t _c , t _d , and t _e , and t _b > t _c > t _d > t _e . In the case where the reaction temperature in the steps (b) to (e) sequentially increases, the continuous bulk polymerization reaction of the mixture and the copolymer is performed by sequentially shortening the reaction time in the steps (b) to (e) By buffering and controlling the reaction rate appropriately, the conversion of the polymerized product obtained in each step can be achieved, and the heat resistance and impact strength of the thermoplastic resin as the final product can be balanced.

For example, the t _b, t _c, t _d and t _e are respectively 1-4 hours, 1-2 hours, 0.5 to 1.5 hours, and 0.5 and the t _b> from 1.0 time range t _c> t _d > _e .

The method for producing a thermoplastic resin may further comprise the step of (f) introducing the fourth polymer into a devolatilizer to remove unreacted materials.

The devolatilizer or devolatilizer may separate the fourth polymer and the non-reactant. The defrosting unit may include one or more unit devices. One unit device may be connected to a subsequent unit device or an extruder. For example, the fourth polymer may be transferred to the second unit device after passing through the first unit device, or may be transferred to the extruder directly, and the fourth polymer material passed through the second unit device may be transferred to the third unit device, It can be transferred directly to the extruder. That is, the unit device provided at the last stage may be connected by an extruder. The depressurization device can be operated under reduced pressure in the range of 0 to 760 mmHg for easy separation of unreacted materials.

In addition, the unreacted material recovered in the devolatilizing apparatus may be condensed, the composition may be analyzed by a GC (Gas Chromatography) apparatus, and then introduced into the upper portion of the first reactor. Recycling of the unreacted material may be terminated when the production of the thermoplastic resin is terminated Can be repeated.

Hereinafter, embodiments of the present invention will be described in detail.

Example 1

12 parts by weight of a polybutadiene rubber (A) having a viscosity of 35 cps at 25 占 폚 and having a viscosity of 5% by weight based on styrene, a styrene-polybutadiene copolymer 2 (B) having a styrene content of 31.5% and a linear type (SBSB) (N-phenylmaleimide,? -Methylstyrene, styrene, acrylonitrile) ultrahigh heat-resisting air (G-1) having a glass transition temperature of 173 DEG C, (D) 25 parts by weight of? -Methylstyrene, (E) 34 parts by weight of styrene and (F) 22 parts by weight of acrylonitrile were dissolved in 20 parts by weight of (H) ethylbenzene to prepare a solution. (J) 0.05 part by weight of 1,1-bis (t-butylperoxy) cyclohexane, (J) 0.03 part by weight of di (trimethylolpropane) tetraacrylate, Was reacted at 110 DEG C for 2.5 hours while continuously feeding the same into the first reactor.

The product of the first reactor was continuously introduced into the second reactor using a metering pump and reacted at 140 ° C for 1.5 hours. The product of the second reactor was continuously introduced into the third reactor using a metering pump and reacted at 150 DEG C for 1 hour. The product of the third reactor was continuously introduced into the fourth reactor using a metering pump and reacted at 160 DEG C for 0.5 hour.

After passing through the four reactors, the polymer was put in a devolatilizing tank to remove unreacted monomers, residual volatile components and organic solvents, and resin pellets were prepared.

Example 2

(G-1) Except that the charging amount of the four-component system (N-phenylmaleimide,? -Methylstyrene, styrene, acrylonitrile) ultra high temperature resistant copolymer having a glass transition temperature of 173 ° C was changed to 6 parts by weight The resin pellets were prepared in the same manner as in Example 1.

Example 3

(C) N-phenylmaleimide and (E) styrene were changed to 7 parts by weight and 32 parts by weight, respectively, to prepare resin pellets.

Comparative Example 1

(G-1) The same as Example 1, except that a four-component system (N-phenylmaleimide,? -Methylstyrene, styrene, acrylonitrile) ultra high temperature resistant copolymer having a glass transition temperature of 173 ° C was not charged. Resin pellets were prepared.

Comparative Example 2

(C) The resin pellets were prepared in the same manner as in Example 1 except that N-phenylmaleimide was not added and (D) the amount of? -Methylstyrene was changed to 30 parts by weight.

Comparative Example 3

(N-phenylmaleimide,? -Methylstyrene, styrene, acrylonitrile) ultrahigh heat-resistant copolymer (C) having a glass transition temperature of 173 ° C (N-phenylmaleimide) D) Resin pellets were prepared in the same manner as in Example 1 except that the amount of? -Methylstyrene was changed to 30 parts by weight.

Comparative Example 4

(G-1) A glass transition temperature of 173 deg. C (G-2) was added without adding a four-component system (N-phenylmaleimide,? -Methylstyrene, styrene, acrylonitrile) Resin pellets were prepared in the same manner as in Example 1, except that 3 parts by weight of a mid-aromatic vinyl copolymer (MS-NI PMI 40%: Denka) was added.

Comparative Example 5

(G-1) A glass transition temperature of 173 deg. C (G-2) was added without adding a four-component system (N-phenylmaleimide,? -Methylstyrene, styrene, acrylonitrile) Resin pellets were prepared in the same manner as in Example 1, except that 6 parts by weight of mid-aromatic vinyl copolymer (MS-NI PMI 40%: Denka) was added.

Comparative Example 6

(N-phenylmaleimide,? -Methylstyrene, styrene, acrylonitrile) ultrahigh heat-resistant copolymer having a glass transition temperature of 173 DEG C and (C) N-phenylmaleimide and (G- (D-2), 3 parts by weight of an N-substituted maleimide-aromatic vinyl copolymer (MS-NI PMI 40%: manufactured by Denka) was added, and the amount of α-methylstyrene was changed to 30 parts by weight , Resin pellets were prepared in the same manner as in Example 1 above.

Comparative Example 7

(C) The amount of the N-phenylmaleimide was changed to 15 parts by weight, and (D) the amount of the? -Methylstyrene was changed to 15 parts by weight. The resin pellets were prepared in the same manner as in Example 1.

Comparative Example 8

(D) A resin pellet was prepared in the same manner as in Example 1, except that the amount of? -Methylstyrene was changed to 10 parts by weight and the amount of styrene (E) was changed to 49 parts by weight.

Comparative Example 9

(D) A resin pellet was prepared in the same manner as in Example 1 except that the amount of? -Methylstyrene was changed to 45 parts by weight and the amount of styrene (E) was changed to 14 parts by weight.

The amount of each substance used in the examples and comparative examples is shown in Table 1 below.

division (A) (B) (C) (D) (E) (F) (G-1) (G-2) (H) (I) (J) (K) Example 1 12 2 5 25 34 22 3 - 20 0.05 0.03 0.03 Example 2 12 2 5 25 34 22 6 - 20 0.05 0.03 0.03 Example 3 12 2 7 25 32 22 3 - 20 0.05 0.03 0.03 Comparative Example 1 12 2 5 25 34 22 - - 20 0.05 0.03 0.03 Comparative Example 2 12 2 30 34 22 3 - 20 0.05 0.03 0.03 Comparative Example 3 12 2 30 34 22 - - 20 0.05 0.03 0.03 Comparative Example 4 12 2 5 25 34 22 - 3 20 0.05 0.03 0.03 Comparative Example 5 12 2 5 25 34 22 - 6 20 0.05 0.03 0.03 Comparative Example 6 12 2 30 34 22 - 3 20 0.05 0.03 0.03 Comparative Example 7 12 2 15 15 34 22 3 - 20 0.05 0.03 0.03 Comparative Example 8 12 2 5 10 49 22 3 - 20 0.05 0.03 0.03 Comparative Example 9 12 2 5 45 14 22 3 - 20 0.05 0.03 0.03

(Unit: parts by weight)

Experimental Example 1: FT-IR analysis

("Total"), a precipitate obtained by dissolving it in acetone and centrifuging ("acetone insoluble component"), and a solution in which acetone was removed Min ") is shown in FIG.

Referring to FIG. 1, a first acrylonitrile, acrylic polymer in (2237.421cm ^-1), N- phenylmaleimide (1712.715cm ^-1), styrene (1600.248cm ^-1), α- methyl styrene (1473.502cm ^-1) , And butadiene (966.753 cm &lt;&quot; ¹ &gt;).

On the other hand, when the polymer is dissolved in acetone and centrifuged, a solution phase and a precipitate are obtained. The solution phase has a four-component system (N-phenylmaleimide,? -Methylstyrene, styrene, acrylonitrile ) Ultra high heat resistant copolymer, and the precipitate is composed of other rubber components, grafted monomers and the like.

Referring back to Fig. 1, peaks corresponding to N-phenylmaleimide and a-methylstyrene, which are components contributing to heat resistance, were observed in both the solution phase and the precipitate.

These results indicate that, in addition to the four component system (N-phenylmaleimide,? -Methylstyrene, styrene, acrylonitrile) ultrahigh heat-resistant copolymer, the rubber component used as a reactant, N-phenylmaleimide and? .

The rubber component in which N-phenylmaleimide and? -Methylstyrene are grafted can improve the compatibility and miscibility with the four-component ultrahigh heat-resisting copolymer, so that the heat resistance and the mechanical properties of the thermoplastic resin co- For example, the impact strength can be balanced.

Experimental Example 2: Evaluation of physical properties

The resin pellets prepared in Examples and Comparative Examples were injection-molded to prepare specimens, and physical properties of the specimens were measured. The results are shown in Table 2 below. The method of measuring the physical properties is as follows.

- Weight average molecular weight: Eluate was analyzed by GPC (Gel Permeation Chromatography) using THF (Tetrahydrofuran) relative to standard PS (Standard Polystyrene) samples.

-Izod Impact strength: Measured according to ASTM D-256

- Tensile strength: Measured according to ASTM D-638

- Melt index: measured according to ASTM D-1238

-Vicat softening point: measured according to ASTM D-1525

division Weight average
Molecular Weight Impact strength
(kg · cm / cm, 3.2 mm notched) Impact strength
(kg · cm / cm, 6.4 mm notched) The tensile strength
(kgf / cm ² ) Melt Index
(g / 10 min, 200 DEG C, 21.6 kg) Vicat Flash Point
(5 kg, 50 DEG C / hr) Example 1 14.5 26.4 21.5 502 6.1 114.2 Example 2 14.4 25.3 20.7 490 5.8 115.1 Example 3 14.2 24.8 20.1 496 5.2 117.0 Comparative Example 1 14.6 20.1 16.3 475 6.2 112.8 Comparative Example 2 14.1 23.2 18.6 480 5.3 105.7 Comparative Example 3 14.2 25.9 21.0 485 8.9 101.6 Comparative Example 4 14.4 17.4 13.8 470 6.0 114.4 Comparative Example 5 14.5 15.6 12.1 450 5.1 116.2 Comparative Example 6 14.1 13.8 10.8 430 5.2 105.9 Comparative Example 7 12.7 5.3 4.5 380 3.6 121.3 Comparative Example 8 16.8 8.6 6.7 400 3.0 110.1 Comparative Example 9 11.4 14.6 12.1 440 7.2 109.7

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (20)

A mixture comprising a rubber component, an N-substituted maleimide monomer, a first aromatic vinyl monomer, a second aromatic vinyl monomer different from the first aromatic vinyl monomer, and an unsaturated nitrile monomer; And
A copolymer comprising a first aromatic vinyl monomer, an N-substituted maleimide monomer, a first aromatic vinyl monomer, an unsaturated nitrile monomer, and a second aromatic vinyl monomer different from the first aromatic vinyl monomer. The method according to claim 1,
1 to 10 parts by weight of the copolymer is copolymerized with 100 parts by weight of the mixture. The method according to claim 1,
Wherein the rubber component comprises a butadiene rubber and a styrene-butadiene rubber. The method of claim 3,
Wherein the butadiene rubber has a viscosity of 25 to 70 cps at 25 캜 in a solution prepared by dissolving styrene in 5% by weight of styrene. The method of claim 3,
Wherein the mixture comprises 5 to 15 wt% of butadiene rubber, 1 to 5 wt% of styrene-butadiene rubber, 1 to 10 wt% of N-substituted maleimide monomer, 15 to 35 wt% of first aromatic vinyl monomer, 25 to 25 wt% of second aromatic vinyl monomer 25 To 45% by weight of an unsaturated nitrile monomer, and 15 to 25% by weight of an unsaturated nitrile monomer. The method according to claim 1,
Wherein the copolymer comprises 5 to 60% by weight of an N-substituted maleimide monomer, 10 to 70% by weight of a first aromatic vinyl monomer, 5 to 50% by weight of an unsaturated nitrile monomer, and 3 to 50% by weight of a second aromatic vinyl monomer. Thermoplastic resin. The method according to claim 1,
Wherein the N-substituted maleimide monomer is at least one selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- But are not limited to, isobutyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-benzylmaleimide, and a mixture of two or more thereof, in the group consisting of maleimide, N-hydroxyphenylmaleimide, Selected thermoplastic resin. The method according to claim 1,
Wherein the first aromatic vinyl monomer is one selected from the group consisting of? -Methylstyrene,? -Ethylstyrene, methyl? -Methylstyrene, and a mixture of two or more thereof. The method according to claim 1,
Wherein the second aromatic vinyl monomer is selected from the group consisting of styrene,? -Methylstyrene vinyltoluene, t-butylstyrene, halogen-substituted styrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, ethylstyrene, Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; The method according to claim 1,
Wherein the unsaturated nitrile monomer is one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and mixtures of two or more thereof. (a) mixing an organic solvent with (i) a mixture comprising a rubber component, an N-substituted maleimide monomer, a first aromatic vinyl monomer, a second aromatic vinyl monomer different from the first aromatic vinyl monomer, and an unsaturated nitrile monomer, and (ii) preparing a solution by dissolving a copolymer of an N-substituted maleimide monomer, a first aromatic vinyl monomer, an unsaturated nitrile monomer, and a second aromatic vinyl monomer different from the first aromatic vinyl monomer;
(b) introducing the solution into a first reactor to produce a first polymer having a conversion of the mixture of 20 to 35% by weight;
(c) introducing the first polymer into a second reactor to produce a second polymer having a conversion of the mixture of 35 to 50% by weight;
(d) introducing the second polymer into a third reactor to produce a third polymer having a conversion of the mixture of 50 to 70% by weight; And
(e) introducing the third polymer into a fourth reactor to produce a fourth polymer having a conversion of the mixture of 70 to 90% by weight. 12. The method of claim 11,
Wherein the solution contains 1 to 10 parts by weight of the copolymer relative to 100 parts by weight of the mixture. 12. The method of claim 11,
Wherein the rubber component comprises a butadiene rubber and a styrene-butadiene rubber. 14. The method of claim 13,
Wherein the butadiene rubber is prepared by dissolving styrene in 5 wt% of the butadiene rubber and has a viscosity of 25 to 70 cps at 25 캜. 14. The method of claim 13,
Wherein the mixture comprises 5 to 15 wt% of butadiene rubber, 1 to 5 wt% of styrene-butadiene rubber, 1 to 10 wt% of N-substituted maleimide monomer, 15 to 35 wt% of first aromatic vinyl monomer, 25 to 25 wt% of second aromatic vinyl monomer 25 To 45% by weight of an unsaturated nitrile monomer, and 15 to 25% by weight of an unsaturated nitrile monomer. 12. The method of claim 11,
Wherein the copolymer comprises 5 to 60% by weight of an N-substituted maleimide monomer, 10 to 70% by weight of a first aromatic vinyl monomer, 5 to 50% by weight of an unsaturated nitrile monomer, and 3 to 50% by weight of a second aromatic vinyl monomer. A method for producing a thermoplastic resin. 12. The method of claim 11,
Wherein 0.01 to 0.3 parts by weight of a radical initiator, 0.005 to 0.2 parts by weight of a polyfunctional vinyl compound and 0.01 to 0.5 parts by weight of a molecular weight modifier are further added to the first reactor in 100 parts by weight of the mixture in the step (b) A method for producing a resin. 12. The method of claim 11,
Wherein the reaction temperatures in the steps (b) to (e) are respectively Tb, Tc, Td, and Te,
And _{T b <T c <T d} <T e,
T _e is from 145 to 165 ° C. 12. The method of claim 11,
The reaction times in the steps (b) to (e) are respectively t _b , t _c , t _d , and t _e ,
t _b > t _c > t _d > t _e ,
and t _e is 0.1 to 1 hour. 12. The method of claim 11,
(f) introducing the fourth polymer into a devolatilizing apparatus to remove unreacted materials.

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