TW201323448A - Rubber-modified styrene-based resin, manufacturing method thereof, and molded product made therefrom - Google Patents

Abstract

A rubber-modified styrene-based resin comprises: a continuous phase formed by 70 wt% to 85 wt% of the copolymer (A); and a dispersion phase formed by 15 wt% to 30 wt% of rubber particles (B), wherein the copolymer (A) comprises the styrene-maleic anhydride-based copolymer (A1) and the styrene-acrylonitrile copolymer (A2); the rubber particles (B) comprises rubber particles (B1) containing an occlusion structure and rubber particles (B2) containing a non-occlusion structure, the weight ratio of A1 to A2 is in the range of 0.15 to 0.55, and the weight ratio of B1 to B2 is in the range of 0.1 to 2.5. The resin comprises a better softening point and fluidity, and has the excellent impact strength under a low temperature, such that it provides the excellent operational convenience under high temperature as well as low temperature in the subsequent processes.

Description

Rubber modified styrene resin, preparation method thereof and molded article obtained by using same

The invention relates to a material suitable for preparing plastic molded articles such as electrical equipment, office equipment, automobile parts and household articles, in particular to a rubber modified styrene resin. The present invention also provides a method of preparing the rubber-modified styrene-based resin, and a molded article comprising the rubber-modified styrene-based resin.

Most of the components contained in plastic molded articles for electrical equipment, household goods, and the like are rubber-modified styrene resins, polycarbonate resins (Polycarbonate Resin), and the like. Among them, the rubber modified styrene resin, such as Acrylonitrile-Butadiene-Styrene Resin (ABS), is widely used in electrical appliances, electronic and automotive parts, mainly It has a good evaluation of the formability, physical properties and mechanical properties, especially the good appearance and gloss of the molded article.

However, as the quality requirements of users continue to increase, there is still a need for improvement in impact strength and heat resistance of rubber-modified styrene-based resins, and in order to improve the appearance of gates for injection molding products, With fully automated production, it is gradually formed by pin gates. Because of the extremely small pores, the resin melt with high viscosity does not easily flow through the pores. Therefore, Improve the fluidity requirements of rubber-modified styrene resin, and increase the injection molding temperature to avoid reducing the efficiency of production; therefore, how to make rubber modified styrene resin have good impact strength, heat resistance, tensile strength, The balance of physical properties such as liquidity is a subject of great improvement in this field.

Most of the conventional improvement methods are to improve the physical properties (especially the thermal properties or mechanical properties required for the forming process) by adding different reinforcing materials to enhance the application value of the rubber modified styrene resin. Currently, the reinforcing material comprises a rubber graft copolymer (such as styrene-acrylonitrile-diene rubber) or a maleic imine copolymer (such as a styrene-acrylonitrile-maleimide copolymer, etc.).

However, in the above-mentioned rubber-modified styrene-based resin modified by the addition of a reinforcing material, since the polarity of the maleimide copolymer and the polarity of the rubber-modified styrene resin are quite different, the rubber is The compatibility between the modified styrene resin and the reinforcing material tends to be poor, resulting in uneven mixing and easy deterioration of mechanical properties such as impact strength or bending strength. Further, the molded article having poor compatibility is not excellent in mechanical properties in a low-temperature operating environment.

In view of the above, there is still a need to develop a rubber-modified styrenic resin having preferred thermal properties (such as fluidity or softening point temperature) and mechanical properties while allowing the resin to be obtained between thermal properties and low temperature mechanical properties. Balanced to meet the needs of the industry for molded products with a wide range of temperature differences.

Accordingly, a first object of the present invention is to provide a rubber-modified styrenic resin having a preferred softening point and impact strength.

Therefore, the rubber-modified styrene resin of the present invention comprises: 70% by weight to 85% by weight of the continuous phase formed by the copolymer (A); and 15% by weight to 30% by weight of the rubber particles (B) a dispersed phase, wherein the copolymer (A) comprises a styrene-maleic anhydride-based copolymer (A ₁ ) and a styrene-acrylonitrile copolymer (A ₂ ); the rubber particles (B) include a occluding structure The rubber particles (B ₁ ) and the rubber particles (B ₂ ) having a non-occlusive structure, and the weight ratio of A ₁ to A ₂ is in the range of 0.15 to 0.55, and the weight ratio of B ₁ to B ₂ is in the range of 0.1 to 2.5.

A second object of the present invention is to provide a molded article of a rubber-modified styrene resin.

Then, the molded article of the rubber-modified styrene-based resin of the present invention is obtained by subjecting a rubber-modified styrene-based resin as described above to a kneading process.

A third object of the present invention is to provide a process for preparing a rubber-modified styrene-based resin.

Therefore, the method for preparing a rubber-modified styrene-based resin of the present invention comprises a bulk polymerization rubber comprising from 5% by weight to 20% by weight of the emulsion-polymerized rubber graft copolymer (I) and from 15% by weight to 85% by weight. Mixing the mixture of the copolymer (II), 10% by weight to 35% by weight of the styrene-maleic anhydride copolymer (A ₁ ) and 0% by weight to 45% by weight of the solution-polymerized ethylene-based copolymer (III) Made by.

The effect of the present invention is that the weight ratio of A ₁ to A _{2 and} the weight ratio of B ₁ to B ₂ of the present invention can make the rubber modified styrene resin have better softening point and fluidity. At the same time, it has good impact strength at low temperature operation, and has good operation convenience for subsequent processing processes at high temperature or low temperature, and transmits styrene-maleic anhydride copolymer (A ₁ ) and has The synergistic effect generated between the rubber particles (B ₁ ) of the occlusion structure further balances the thermal properties and the low-temperature mechanical properties of the rubber-modified styrenic resin of the present invention.

The rubber-modified styrene resin of the present invention comprises: 70% by weight to 85% by weight of the continuous phase formed by the copolymer (A); and 15% by weight to 30% by weight of the dispersed phase of the rubber particles (B). Wherein the copolymer (A) comprises a styrene-maleic anhydride-based copolymer (A ₁ ) and a styrene-acrylonitrile copolymer (A ₂ ); the rubber particles (B) comprise rubber particles having a occluding structure ( B ₁ ) and rubber particles (B ₂ ) having a non-occluded structure, and the weight ratio of A ₁ to A ₂ is in the range of 0.15 to 0.55, and the weight ratio of B ₁ to B ₂ is in the range of 0.1 to 2.5.

Preferably, the copolymer (A) comprises 12% by weight to 47% by weight of the styrene-maleic anhydride-based copolymer (A ₁ ), based on 100% by weight of the total of the copolymer (A), and 53 The styrene-acrylonitrile-based copolymer (A ₂ ) is % by weight to 88% by weight.

Preferably, the styrene-maleic anhydride copolymer (A ₁ ) comprises from 45% by weight to 54.5 % by weight of styrene monomer units, and from 45% by weight to 54.5 % by weight of unsaturated bismuth quinone dicarboxylate. A monomer unit, and 0.5% by weight to 10% by weight of an unsaturated dicarboxylic anhydride monomer unit.

Preferably, the styrene-acrylonitrile-based copolymer (A ₂ ) comprises 65% by weight to 76% by weight of a styrene-based monomer unit, and 24% by weight to 35% by weight of an acrylonitrile-based monomer unit.

Preferably, the rubber particles (B) comprise 15% by weight to 75% by weight of rubber particles (B ₁ ) having a occluding structure, and 25% by weight, based on 100% by weight of the total amount of the rubber particles (B). ～85% by weight of rubber particles (B ₂ ) having a non-occluded structure.

The rubber particles (B ₁ ) having a absorbing structure include one or several styrene copolymers, a first rubber body coated with a styrene copolymer, and a first graft copolymer grafted onto the rubber body. And the rubber particles (B ₂ ) having a non-occluded structure include a second rubber body and the second graft copolymer grafted onto the rubber body. The first rubber body and the second rubber body may be the same or different, and the first graft copolymer and the second graft copolymer may be the same or different. The styrene-based copolymer, the first graft copolymer or the second graft copolymer respectively comprises a styrene-based monomer and an acrylonitrile-based monomer, and optionally other copolymerizable vinyl-based monomers are added. The mixture of the bodies is formed by polymerization, and the monomers are used as described in the above-mentioned bulk polymeric rubber graft copolymer (II). The first rubber body or the second rubber body is respectively formed of a rubber component, and the rubber component is the rubber component used in the block polymer rubber graft copolymer (II) described below.

In an embodiment of the present invention, the rubber-modified styrene resin comprises: 70% by weight to 85% by weight of the continuous phase formed by the copolymer (A); and 15% by weight to 30% by weight of the rubber particles (B) The dispersed phase formed, wherein the copolymer (A) comprises 12% by weight to 47% by weight of the styrene-maleic anhydride-based copolymer (A ₁ ), and 53% by weight to 88% by weight of the styrene-propylene a nitrile-based copolymer (A ₂ ); the rubber particles (B) comprising rubber particles (B ₁ ) having a occluding structure, and rubber particles (B ₂ ) having a non-occlusive structure; the styrene-maleic anhydride system The copolymer (A ₁ ) is composed of 45% by weight to 54.5 % by weight of styrene monomer units, 45% by weight to 54.5 % by weight of unsaturated bismuth quinone iodide monomer units, and 0.5% by weight to 10% by weight. The composition of the weight % unsaturated dicarboxylic anhydride monomer unit; the styrene-acrylonitrile copolymer (A ₂ ) is from 65% by weight to 76% by weight of the styrene monomer unit, and 24% by weight to 35 weight % by weight of the acrylonitrile monomer unit; and the weight ratio of A ₁ to A ₂ is in the range of 0.15 to 0.55, and the weight ratio of B ₁ to B ₂ is in the range of 0.1 to 2.5.

In an embodiment of the present invention, the rubber-modified styrene resin comprises: 70% by weight to 85% by weight of the continuous phase formed by the copolymer (A); and 15% by weight to 30% by weight of the rubber particles (B) The dispersed phase formed, wherein the copolymer (A) comprises 12% by weight to 47% by weight of the styrene-maleic anhydride-based copolymer (A ₁ ), and 53% by weight to 88% by weight of the styrene-propylene a nitrile-based copolymer (A ₂ ); the rubber particles (B) comprising 15% by weight to 75% by weight of rubber particles (B ₁ ) having a occluding structure, and 25% by weight to 85% by weight of a non-occluded structure Rubber particles (B ₂ ); the styrene-maleic anhydride copolymer (A ₁ ) is composed of 45% by weight to 54.5 % by weight of styrene monomer units, and 45% by weight to 54.5 % by weight of unsaturated two a carboxylic acid quinone imine monomer unit, and 0.5% by weight to 10% by weight of an unsaturated dicarboxylic anhydride monomer unit; the styrene-acrylonitrile copolymer (A ₂ ) is from 65% by weight to 76% by weight % styrene monomer unit, and 24% by weight to 35% by weight of the acrylonitrile monomer unit; and the weight ratio of A ₁ to A ₂ is in the range of 0.2 to 0.51.

Preferably, the first graft copolymer in the rubber particles (B ₁ ) having the occluding structure has an average thickness ranging from 90 ~300 And the second graft copolymer in the rubber particles (B ₂ ) having the non-occluded structure has an average thickness ranging from 30 ~160 . More preferably, the first graft copolymer in the rubber particles (B ₁ ) having the occluding structure has an average thickness ranging from 100 ~300 And the second graft copolymer in the rubber particles (B ₂ ) having the non-occluded structure has an average thickness ranging from 40 ～140 . The thickness of the graft copolymer may depend on the temperature of the polymerization reaction, the residence time, the rubber properties [such as molecular weight, polymeric composition, or microstructure of 1,2-vinyl (vinyl) content, etc.), chain transfer agent and solvent. The type, amount, type of initiator, reactor design, stirring speed, and specific operating conditions before and after the reverse rotation are regulated. Before and after the reverse rotation occurs, when the solution or the bulk polymerization is carried out, the solution phase (rubber particles) and the solute phase (copolymer) may reversely rotate, that is, the original solution phase is converted into the solute phase, and The original solute phase is converted to a solution phase.

When the first graft copolymer in the rubber particles (B ₁ ) having the occluding structure has an average thickness range of less than 90 When the rubber modified styrene resin has poor impact strength; when the average thickness of the second graft copolymer in the rubber particles (B ₂ ) having the non-occlusive structure is less than 30 Or higher than 160 In this case, the rubber-modified styrene-based resin has poor impact strength and poor fluidity.

Preferably, the rubber particles (B ₁ ) having the occluding structure have a weight average particle diameter ranging from 0.1 μm to 10 μm, and the rubber particles (B ₂ ) having the non-occlusive structure have a weight average particle diameter ranging from 0.05. Mm ~ 0.8μm. More preferably, the rubber particles (B ₁ ) having the occluding structure have a weight average particle diameter ranging from 0.2 μm to 7 μm, and the rubber particles (B ₂ ) having the non-occlusive structure have a weight average particle diameter ranging from 0.06. Mm ~ 0.6μm.

The method for preparing a rubber-modified styrene resin according to the present invention is a graft copolymerization of a bulk polymer rubber comprising 5% by weight to 20% by weight of an emulsion polymerized rubber graft copolymer (I) and 15% by weight to 85% by weight. Mixture of the product (II), 10% by weight to 35% by weight of the styrene-maleic anhydride copolymer (A ₁ ) and 0% by weight to 45% by weight of the solution polymerized ethylene copolymer (III) Got it.

The method for preparing a rubber-modified styrene resin according to the present invention further comprises a processing process after the kneading.

Preferably, in the method for preparing a rubber-modified styrene resin according to the present invention, the emulsion-polymerized rubber graft copolymer (I), the bulk polymer rubber graft copolymer (II), and the solution-polymerized ethylene-based copolymer (III) a monomer component comprising a styrene-based monomer comprising 50% by weight to 90% by weight, and 10% by weight to 50% by weight of an acrylonitrile-based monomer, respectively, is obtained by polymerization. Since the copolymer has the same composition, it is easier to mix, and then the impact resistance of the rubber-modified styrene resin is improved. More preferably, the emulsion polymerized rubber graft copolymer (I), the bulk polymer rubber graft copolymer (II) and the solution polymerized ethylene copolymer (III) each comprise from 58% by weight to 80% by weight. The styrene monomer and the monomer component of 20% by weight to 42% by weight of the acrylonitrile monomer are obtained by polymerization.

Preferably, the weight percentage of the acrylonitrile monomer in the monomer component used in the bulk polymeric rubber graft copolymer (II) or the solution polymerization ethylene copolymer (III) is smaller than that of the emulsion polymerization rubber graft The weight percentage of the acrylonitrile-based monomer in the monomer component used in the copolymer (I) is such that the styrene-maleic anhydride-based copolymer (A ₁ ) having no acrylonitrile-based monomer unit is in the emulsion-polymerized rubber. The dispersion in the graft copolymer (I) is uniform, and the thermal properties and low-temperature mechanical properties of the rubber-modified styrene resin of the present invention are further improved and balanced.

Hereinafter, the emulsion rubber graft copolymer (I), the bulk polymer rubber graft copolymer (II), the styrene-maleic anhydride copolymer (A ₁ ), and the solution polymerized ethylene copolymer (III) will be polymerized one by one. Detailed instructions:

[Solution Polymerization Vinyl Copolymer (III)]

The solution-polymerized ethylene-based copolymer (III) comprises a styrene-based monomer (i-1) and an acrylonitrile-based monomer (i-2), and optionally other copolymerizable vinylic monomers. The first monomer component of (i-3) is obtained by solution polymerization. The solution-polymerized ethylene-based copolymer (III) obtained contains a styrene-acrylonitrile-based copolymer (A ₂ ).

The styrene monomer (i-1) may be used singly or in combination, and the styrene monomer (i-1) includes, but is not limited to, styrene, α-methylstyrene, p-tert-butylbenzene. Ethylene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, α-methyl-p-methylstyrene, Or brominated styrene and the like. Preferably, the styrenic monomer (i-1) is selected from the group consisting of styrene, α-methylstyrene, or the like. Preferably, the content of the styrene monomer (i-1) is 50% by weight based on 100% by weight of the total of (i-1), (i-2), and (i-3). 90% by weight; more preferably, 55% by weight to 85% by weight; still more preferably, 58% by weight to 80% by weight.

The acrylonitrile-based monomer (i-2) may be used singly or in combination, and the acrylonitrile-based monomer (i-2) may include, but not limited to, acrylonitrile or α-methacrylonitrile. Preferably, the acrylonitrile-based monomer (i-2) is acrylonitrile. Preferably, the content of the acrylonitrile-based monomer (i-2) is 10% by weight based on 100% by weight of the total of (i-1), (i-2), and (i-3). 50% by weight; more preferably, 15% by weight to 45% by weight; still more preferably 20% by weight to 42% by weight.

The other copolymerizable vinyl monomer (i-3) may be used singly or in combination, and the other copolymerizable vinyl monomer (i-3) includes, but is not limited to, an acrylic monomer, a methacrylic acid system. A monomer, an acrylate monomer, or a methacrylate monomer. Preferably, the content of the other copolymerizable vinyl monomer (i-3) is in the range of 100% by weight based on the total amount of (i-1), (i-2), (i-3) 0% by weight to 40% by weight; more preferably 1% by weight to 34% by weight; still more preferably 3% by weight to 30% by weight.

The acrylic monomer includes, but is not limited to, acrylic acid or the like. The methacrylic monomer includes, but is not limited to, methacrylic acid or the like. The acrylate monomer includes, but is not limited to, methyl acrylate, ethyl acrylate, isopropyl acrylate, or butyl acrylate. Preferably, the acrylate monomer is butyl acrylate.

The methacrylate monomer includes, but is not limited to, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, and Cyclohexyl acrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate ), ethylene dimethacrylate, or neopentyl dimethacrylate. Preferably, the methacrylate monomer is selected from methyl methacrylate or butyl methacrylate.

In the solution polymerization, a polymerization initiator may be optionally added. The polymerization initiator is selected from a monofunctional polymerization initiator, a polyfunctional polymerization initiator, or a combination thereof. The monofunctional polymerization initiator may be used singly or in combination, and the monofunctional polymerization initiator includes, but is not limited to, benzoyl peroxide, dicumyl peroxide, T-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxybenzoate T-butyl-peroxy benzoate), bis-2-ethylhexyl peroxy dicarbonate, tert-butyl peroxy isopropyl carbonate BPIC), cyclohexanone peroxide, 2,2'-azo-bis-isobutyronitrile (AIBN), 1,1'-azobicyclo 1,1'-azo-biscyclohexane-1-carbonitrile, or 2,2'-azo-bis-2-methylbutyronitrile (2,2'-azo-bis-2 -methyl butyronitrile) and so on. Among them, benzammonium peroxide and 2,2'-azo-bis-isobutyronitrile are preferred.

The polyfunctional polymerization initiator may be used singly or in combination, and the polyfunctional polymerization initiator includes, but is not limited to, 1,1-bis-tert-butylperoxycyclohexane (1,1-bis-t) -butyl peroxy cyclohexane (TX-22), 1,1-bis-tert-butylperoxide-3,3,5-trimethylcyclohexane (1,1-bis-t-butylperoxy-3,3 ,5-trimethyl cyclohexane, abbreviated as TX-29A), 2,5-dimethyl-2,5-bis-(2-ethylperoxyhexane)hexane [2,5-dimethyl-2,5-bis -(2-ethylhexanoxy peroxy)hexane], 4-(t-butylperoxycarbonyl)-3-hexyl-6-[7-(t-butylperoxycarbonyl)heptyl]cyclohexane {4-( T-butyl peroxy carbonyl)-3-hexyl-6-[7-(t-butyl peroxy carbonyl)heptyl] cyclohexane}, di-t-butyl-diperoxyazelate , 2,5-Dimethyl-2,5-bis(benzoquinone peroxy)hexane, 2,5-dimethyl-2,5-bis-(benzoyl peroxy)hexane, di-t-butyl Di-t-butyl peroxy-hexahydro-terephthalate (BPHTH), or 2,2-bis(4,4-di-t-butylperoxy)cyclohexylpropane [2,2-bis-(4,4-di-t-butyl peroxy)cyclohexyl propane, Jane PX-12] and the like.

In the solution polymerization, a chain transfer agent may be optionally added. The chain transfer agent may be used singly or in combination, and the chain transfer agent includes, but is not limited to, n-dodecyl mercaptan (NDM), stearyl mercaptan, and third. - t-dodecyl mercaptan (TDM), n-propyl mercaptan, n-octyl mercaptan, tri-octyl mercaptan, tri-decyl mercaptan, or antimony Terpinolene and the like.

Preferably, the solution polymerization reaction has an operating temperature in the range of from 70 ° C to 140 ° C; more preferably, the solution polymerization has an operating temperature in the range of from 90 ° C to 130 ° C.

[Styrene-Maleic Anhydride Copolymer (A ₁ )]

Preferably, the styrene-maleic anhydride copolymer (A ₁ ) comprises 45% by weight to 54.5 % by weight of styrene monomer units, and 45% by weight to 54.5 % by weight of unsaturated dicarboxylic acid quinones. An amine monomer unit and 0.5% by weight to 10% by weight of an unsaturated dicarboxylic anhydride monomer unit.

_One of the processes for preparing the styrene-maleic anhydride-based copolymer (A ₁ ) may be one comprising a styrene monomer, an unsaturated dicarboxylic acid quinone imide monomer, and an unsaturated dicarboxylic anhydride monomer. The second monomer component is obtained by copolymerization. Further, the styrene-maleic anhydride-based copolymer (A ₁ ) may be prepared by copolymerization of a monomer component including a styrene monomer and an unsaturated dicarboxylic anhydride monomer. An intermediate product, which is further reacted with ammonia or a primary amine to carry out a hydrazine imidization reaction, wherein the unsaturated dicarboxylic anhydride monomer unit on the intermediate product forms an unsaturated dicarboxylic acid with ammonia or a primary amine. A quinone imine monomer unit.

The kind of the styrene-based monomer is the same as the styrene-based monomer (i-1) in the solution-polymerized ethylene-based copolymer (III) described above, and therefore will not be described again.

The unsaturated dicarboxylic acid quinone imine monomer may be used singly or in combination, and the unsaturated dicarboxylic acid quinone imide monomer includes, but is not limited to, maleic imine, nitrogen-methyl maleimide , nitrogen-isopropyl maleimide, nitrogen-butyl maleimide, nitrogen-hexyl maleimide, nitrogen-octyl maleimide, nitrogen-dichakimide Amine, nitrogen-cyclohexylmaleimide, nitrogen-phenylmaleimide, nitrogen-2,3-tolyl maleimide, nitrogen-2,4-tolyl maleimide, Nitrogen-2,3-ethylphenylmaleimide, nitrogen-2,4-ethylphenylmaleimide, nitrogen-2,3-butylmaleimide, nitrogen-2,4 - Butyl phenyl maleimide, nitrogen-2,6-tolyl maleimide, nitrogen-2,3-chlorophenylmaleimide, nitrogen-2,4-chlorophenylmalay Yttrium imine, nitrogen-2,3-bromophenylmaleimide, or nitrogen-2,4-bromophenylmaleimide. Preferably, the maleimide monomer is nitrogen-phenyl maleimide.

The unsaturated dicarboxylic anhydride-based monomer may be used singly or in combination, and the unsaturated dicarboxylic anhydride-based monomer includes, but is not limited to, maleic anhydride, itaconic anhydride, citraconic anhydride, aconite (aconic) Anhydride, etc. Preferably, the unsaturated dicarboxylic anhydride monomer is maleic anhydride.

[Bulk polymer rubber graft copolymer (II)]

The bulk polymeric rubber graft copolymer (II) is obtained by bulk or solution polymerization of a third component, wherein the third component comprises 100 parts by weight of the third monomer component and 5 Parts by weight to 30 parts by weight of the rubber component. The third monomer component comprises 50% by weight to 90% by weight of the styrene-based monomer and 10% by weight to 50% by weight of the acrylonitrile-based monomer, and optionally added 0% by weight to 40% by weight of the other monomer A copolymerizable vinyl monomer.

Preferably, the third monomer component comprises 58% by weight to 80% by weight of the styrene monomer and 20% by weight to 42% by weight of the acrylonitrile monomer, and the selective addition is 0% by weight to 40%. % by weight of other copolymerizable vinylic monomers.

In the bulk polymerization reaction, an additive may be optionally added, and the additive includes, but is not limited to, a solvent, a polymerization initiator or a chain transfer agent, and the like. The obtained bulk polymer rubber graft copolymer (II) contains a styrene-acrylonitrile-based copolymer (A ₂ ) and rubber particles (B ₁ ) having a occluding structure.

Preferably, the rubber component is selected from a diene rubber, a polyacrylate rubber, or a polyoxyalkylene rubber.

The diene rubber may be used singly or in combination, and the diene rubber includes but is not limited to butadiene rubber, isoprene rubber, chloroprene rubber, and ethylene-propylene-diene terpolymer rubber. (ethylene propylene diene terpolymer, abbreviated as EPDM), styrene-diene rubber, or acrylonitrile-diene rubber. Wherein, the butadiene rubber comprises, but is not limited to, a high cis (Hi-Cis) content of butadiene rubber and a low cis (Low-Cis) content of butadiene rubber. The typical weight composition of cis (Cis)/vinyl (Vinyl) in the high cis content butadiene rubber is (94 to 98 wt%) / (1 to 5 wt%), and the rest of the composition is trans. (Trans) structure, and Mooney viscosity is between 20 and 120, and the molecular weight range is preferably from 100,000 to 800,000. The typical weight composition of cis/vinyl in the low cis content butadiene rubber ranges from (20 to 40 wt%) / (1 to 20 wt%), the balance is trans structure, and the Mooney viscosity is From 20 to 120, the molecular weight range is preferably from 100,000 to 800,000. The styrene-diene rubber includes, but is not limited to, styrene-butadiene rubber, styrene-isoprene rubber, and the like, and the styrene-diene rubber may be a block copolymer or a random copolymer. (random) or star type, wherein the styrene-butadiene rubber has a weight ratio of styrene to butadiene ranging from 5:95 to 80:20, and the molecular weight range is preferably 50,000 to 600,000. Preferably, the styrene-diene rubber is a styrene-butadiene rubber.

The styrene-based monomer, the acrylonitrile-based monomer, the other copolymerizable vinyl-based monomer, the polymerization initiator, and the chain transfer agent are as described above in the preparation of the styrene-based system in the solution-polymerized ethylene-based copolymer (III). The type of the monomer (i-1), the acrylonitrile monomer (i-2), the other copolymerizable vinyl monomer (i-3), the polymerization initiator, and the chain transfer agent will not be described again.

Preferably, the polymerization initiator is contained in an amount of 0.01 by weight based on 100 parts by weight of the total of the rubber component, the styrene monomer, the acrylonitrile monomer, and the other copolymerizable vinyl monomer. Parts to 10 parts by weight.

Preferably, the chain transfer agent is contained in an amount of 0.001 parts by weight based on 100 parts by weight of the total of the rubber component, the styrene monomer, the acrylonitrile monomer, and the other copolymerizable vinyl monomer. ~1 parts by weight.

The bulk polymeric rubber graft copolymer (II) is prepared by continuously feeding the starting materials of the rubber component, the styrene monomer, the acrylonitrile monomer, and other copolymerizable vinyl monomers. After entering the reactor, after the reaction reaches the desired conversion rate, the solution after the reaction is continuously taken out from the reaction device, and introduced into a devolatilizer, and the unreacted starting material and reaction are carried out by the devolatilizer. After the volatile component produced is removed, the bulk polymeric rubber graft copolymer (II) of the present invention can be obtained or further granulated. In general, the devolatilizer can use a vacuum degassing tank device or a degasser. The unreacted starting material or volatile component removed by the devolatilizer is optionally recovered by a condenser, and if necessary, the water in the recovered liquid can be removed and used as a starting material.

The reactor includes, but is not limited to, a plug flow reactor (PFR), a continuous stirred-tank reactor (CSTR), or a reactor containing a static mixer (Static reactor) )Wait. The number of the reactors may be one, or two or more, preferably three or more, in combination. When more than two reactors are used, the first reactor is preferably a fully mixed reactor (CSTR).

Preferably, the reactor is operated at a temperature in the range of from 80 ° C to 200 ° C; more preferably, the reactor is operated at a temperature in the range of from 90 ° C to 160 ° C. Preferably, the operating pressure of the reactor ranges from 1 kg/cm ² to 5 kg/cm ² .

[Emulsified Polymer Rubber Graft Copolymer (I)]

The emulsion-polymerized rubber graft copolymer (I) is a fourth monomer component comprising 45% by weight to 85% by weight of a rubber emulsion (solids) and 15% by weight to 55% by weight of a functional monomer component. Obtained by graft polymerization, wherein the functional monomer component comprises 50% by weight to 90% by weight of a styrene monomer, 10% by weight to 50% by weight of an acrylic monomer, and 0 weight % to 40% by weight of other copolymerizable monomers.

Preferably, the functional monomer component comprises 58% by weight to 80% by weight of a styrene monomer, 20% by weight to 42% by weight of an acrylonitrile monomer, and 0% by weight to 40% by weight of others. The monomer can be copolymerized.

In the graft polymerization, an additive may be optionally added, and the additive includes, but is not limited to, a coagulant, an emulsifier, a polymerization initiator, or a chain transfer agent. After the graft polymerization, the selective step can be further carried out by coagulation, dehydration, drying and the like. The obtained emulsion-polymerized rubber graft copolymer (I) contains a styrene-acrylonitrile-based copolymer (A ₂ ) and rubber particles (B ₂ ) having a non-ociratory structure. After the graft polymerization reaction, the content of the styrene-acrylonitrile-based copolymer (A ₂ ) is 10% by weight or less based on 100% by weight of the total amount of the emulsion-polymerized rubber graft copolymer (I).

The rubber emulsion is obtained by an emulsion polymerization method from 60% by weight to 100% by weight of the rubber component and 0% by weight to 40% by weight of the other copolymerizable monomer, or further subjected to the fertilizer treatment after the emulsion polymerization reaction. The rubber component is the rubber component of the above-mentioned bulk polymeric rubber graft copolymer (II). The other copolymerizable monomer includes, but is not limited to, a styrene monomer, an acrylonitrile monomer, an acrylate monomer, or a methacrylate monomer. The rubber emulsion includes, but is not limited to, polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-methyl methacrylate copolymer, or isoprene- Butyl acrylate copolymer and the like.

The hypertrophy treatment can be carried out by a general method of freezing fat, mechanical fat or additive hypertrophy. The additive used in the additive hypertrophy method includes, but is not limited to, (1) an acidic substance: acetic anhydride, hydrogen chloride or sulfuric acid, etc.; (2) a salt-based substance: sodium chloride, potassium chloride or calcium chloride; (3) A polymer aggregating agent containing a carboxylic acid group: a (meth)acrylic acid-(meth)acrylate copolymer (such as a methacrylic acid-butyl acrylate copolymer, a methacrylic acid-ethyl acrylate copolymer) or the like.

For example, the method for producing a diene rubber emulsion can be polymerized by an emulsion polymerization method using a diene monomer (for example, butadiene), or 50% by weight to 100% by weight of a diene monomer and 0% by weight. The monomer such as styrene and/or acrylonitrile of 50% by weight is polymerized by an emulsion polymerization method to obtain a diene rubber emulsion having a weight average particle diameter of 0.05 μm to 0.8 μm. A small particle size diene rubber emulsion having a weight average particle diameter of 0.05 μm to 0.18 μm may be obtained by an emulsion polymerization method, and then subjected to a fertilizer treatment to increase the weight of the small particle size diene rubber emulsion. A large particle size diene rubber emulsion having an average particle diameter of 0.2 μm to 0.8 μm.

The styrene monomer, the acrylonitrile monomer, the other copolymerizable vinyl monomer, the polymerization initiator, and the chain transfer agent in the functional monomer component are prepared as described above to prepare a solution polymerization ethylene copolymer. Styrene monomer (i-1), acrylonitrile monomer (i-2), other copolymerizable vinyl monomer (i-3), polymerization initiator, chain transfer agent in (III) The type, or the unsaturated dicarboxylic acid quinone imine monomer and the unsaturated dicarboxylic anhydride monomer in the styrene-maleic anhydride copolymer (A ₁ ) are prepared as described above, and therefore will not be described again.

Preferably, the additive is contained in an amount ranging from 0.01 part by weight to 5 parts by weight based on 100 parts by total of the total of the rubber emulsion and the functional monomer component; more preferably, the additive is contained in an amount of 0.1 part by weight. Parts to 3 parts by weight. Wherein, the coagulating agent may be used singly or in combination, and the coagulating agent includes but is not limited to sulfuric acid, acetic acid, sodium sulfate, potassium sulfate, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, pyrosulfite, coke Sulfate, hydrosulfite, formaldehydesulfoxylate, thiosulfate, sulfoxylate, calcium chloride, magnesium chloride, magnesium sulfate, or aluminum sulfate. Preferably, the coagulating agent is selected from the group consisting of sodium hydrogen sulfite, sodium metabisulfite, sodium dithionite, or sodium formaldehyde sulfoxylate.

The preparation method of the rubber modified styrene resin can be carried out by a general mixing method, and the mixture is placed in a stirrer to be stirred, uniformly mixed, and if necessary, an additive or a polymer can be added to obtain the rubber modified styrene of the present invention. Resin.

In the process of preparing the rubber-modified styrene-based resin of the present invention, various additives may be added as necessary, and the additive is selected from the group consisting of an antioxidant, a plasticizer, a processing aid, an ultraviolet stabilizer, an ultraviolet absorber, a filler, A reinforcing agent, a coloring agent, a slip agent, a charging inhibitor, a flame retardant, a flame retardant, a heat stabilizer, a coupling agent, or a combination thereof. The above additives may be respectively the above-mentioned emulsion polymerized rubber graft copolymer (I), bulk polymer rubber graft copolymer (II), styrene-maleic anhydride copolymer (A ₁ ) or solution polymerized ethylene copolymer ( In the polymerization reaction of III), after the polymerization reaction, before the coagulation, or the above additives may be added during the process of preparing the rubber-modified styrene resin by performing the extrusion kneading treatment.

The antioxidant may be used singly or in combination, and the antioxidant includes, but is not limited to, a phenol-based antioxidant, a thioether-based antioxidant, or a phosphorus-based antioxidant. Preferably, the antioxidant is contained in an amount of 2 parts by weight or less based on 100 parts by weight of the total of the rubber-modified styrene resin.

The phenolic antioxidant may be used singly or in combination, and the phenolic antioxidant includes, but is not limited to, octadecyl 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate. [3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester, model: antioxidant IX-1076], triethylene glycol bis[3-(3-tert-butyl-5-methyl) 4-hydroxyphenyl)propionate], tetrakis[methylene-3-(3,5-bis-tert-butyl-4-hydroxyphenyl)propionate]methane, 2-tert-butyl- 6-(3-Tertibutyl-2-hydroxy-6-methylbenzyl)-4-methylphenyl acrylate, 2,2'-methylene-bis(4-methyl-6- Third butyl phenol) [2,2'-methylenebis (4-methyl-6-tert-butylphenol), model: antioxidant 2246], 2,2'-thiobis(4-methyl-6-third butyl Phenol), 2,2'-thio-diethylene-bis[3-(3,5-bis-tert-butyl-4-hydroxyphenyl)propionate], or 2,2'-B Diamine-bis[ethyl-3-(3,5-bis-tert-butyl-4-hydroxyphenyl)propionate] and the like.

The thioether-based antioxidant may be used singly or in combination, and the thioether-based antioxidant includes, but is not limited to, distearyl thiodipropionate, dipalmitole thiodipropionate, pentaerythritol-tetra-( --dodecyl-thiopropionate, or dioctadecyl sulfide, and the like.

The phosphorus-based antioxidant may be used singly or in combination, and the phosphorus-based antioxidant is selected from a phosphite-containing phosphorus-based antioxidant or a phosphate-containing phosphorus-based antioxidant. The phosphite-containing phosphorus-based antioxidant includes, but is not limited to, tris(nonylphenyl) phosphite, dodecyl phosphite, 4,4'-butylene bis(3-methyl-6- Tributylphenyl-bistridecylphosphite), tris(2,4-t-butylphenyl)phosphite, and the like. The phosphate-containing phosphorus-based antioxidant includes, but is not limited to, tetrakis(2,4-t-butylphenyl)-4,4'-extended biphenyl phosphate, or 9,10-dihydro-9-oxygen -10-phosphate phenoxy-10-oxygen and the like.

The slip agent may be used singly or in combination, and the slip agent includes, but is not limited to, metal soap such as calcium stearate, magnesium stearate, lithium stearate, and ethylene bis-stearamide. EBA), methylene distearylamine, decyl palmitate, butyl stearate, palmitate stearate, pentaerythritol tetra-fatty acid ester, polypropionic acid tristearate, n-docosanoic acid, A compound such as stearic acid, a polyethylene wax, a octadecanoic acid wax, a carnuba wax, a petroleum wax or the like. Preferably, the content of the slip agent is in the range of 2 parts by weight or less based on 100 parts by weight of the total of the rubber-modified styrene-based resin.

In the process of preparing the rubber-modified styrene-based resin of the present invention, various polymers may be added as necessary, and the polymer includes, but is not limited to, polycarbonate, polyamine, polyethylene terephthalate, and poly-pair. Butylene phthalate, polyphenylene ether, polyvinyl chloride, polymethyl methacrylate, ethylene-methyl methacrylate copolymer, polypropylene, styrene-butadiene block copolymer, hydrogenated propylene Nitrile-butadiene copolymer, hydrogenated styrene-butadiene block copolymer, and the like. Preferably, the content of the polymer is from 5 parts by weight to 200 parts by weight based on 100 parts by weight of the total of the rubber-modified styrene-based resin.

The molded article of the rubber-modified styrene-based resin of the present invention is obtained by subjecting a rubber-modified styrene-based resin as described above to a kneading process. The kneading processing and molding process can be carried out in a conventional manner, and therefore will not be described again.

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

<Example> [Synthesis Example 1] Emulsion Polymerized Rubber Graft Copolymer (I)

95.0 parts by weight of 1,3-butadiene, 5.0 parts by weight of acrylonitrile, 15.0 parts by weight of potassium persulfate solution, 3.0 parts by weight of sodium pyrophosphate, 1.5 parts by weight of potassium oleate, and 140.0 parts by weight of distilled water And 0.2 part by weight of the third-dodecyl mercaptan was reacted at a reaction temperature of 65 ° C for 12 hours to obtain a rubber emulsion having a conversion of 94%, a solid content of about 40% and a weight average particle diameter of 0.1 μm.

85.0 parts by weight of ethyl acrylate, 15.0 parts by weight of acrylic acid, 0.3 parts by weight of thirteen-dodecyl mercaptan, 2.0 parts by weight of potassium oleate, 1.0 part by weight of sodium dioctylsulfosuccinate, 0.4 The parts by weight of cumene hydroperoxide, 0.3 parts by weight of sodium formaldehyde sulfoxylate and 200.0 parts by weight of distilled water are reacted at a reaction temperature of 75 ° C for 5 hours to obtain a conversion of 95% and a pH of 6.0. A carboxylic acid based polymer aggregating agent.

Next, 3 parts by weight of the above-mentioned carboxylic acid group-containing polymer flocculant (dry weight) is used to ferment 100 parts by weight of the above rubber emulsion (dry weight), and the obtained enlarged rubber emulsion has a pH of 8.5 and an average weight of particles. The diameter is 0.30 μm.

Thereafter, 100.0 parts by weight of the above-mentioned enlarged rubber emulsion (dry weight), 25.0 parts by weight of styrene, 8.3 parts by weight of acrylonitrile, 1.2 parts by weight of potassium oleate, and 0.2 parts by weight of a third-dodecyl group Mercaptan, 0.5 parts by weight of cumene hydroperoxide, 3.0 parts by weight of ferrous sulfate solution (concentration: 0.2 wt%), 3.0 parts by weight of sodium formaldehyde sulfoxylate solution (concentration: 10 wt%), 20.0 parts by weight Ethylenediamine tetraacetic acid solution (concentration: 0.25 wt%) and 200.0 parts by weight of distilled water are mixed and reacted, wherein the styrene and acrylonitrile are added to the reaction system for polymerization within 5 hours by continuous addition, followed by chlorine After the calcium (CaCl ₂ ) is coagulated, dehydrated, and then dried to a moisture content of 2% or less, the emulsion polymerized rubber graft copolymer (I) required by the present invention can be obtained, and the rubber component content is 75% by weight. Dissolving the emulsion-polymerized rubber graft copolymer (I) with tetrahydrofuran and filtering, and then adding methanol to the filtrate to precipitate and filter the rubber particles (B ₂ ) having a non-occluded structure, thereby calculating the obtained Emulsified polymeric rubber graft copolymer (I) contains 7 weights % styrene-acrylonitrile-based copolymer (A ₂ ), and 93% by weight of rubber particles (B ₂ ) having a non-occlusive structure, and the weight average of the rubber particles (B ₂ ) having a non-occlusive structure The particle size was 0.31 μm.

[Synthesis Example 2] Bulk polymeric rubber graft copolymer (II)

103.2 parts by weight of styrene, 15 parts by weight of styrene/butadiene rubber (styrene/butadiene content = 25% by weight / 75% by weight, Mw = 130,000), 45.4 parts by weight of ethylbenzene, 31.4 Parts by weight of acrylonitrile, 3.9 parts by weight of butyl acrylate, 0.08 parts by weight of n-dodecyl mercaptan, 0.063 parts by weight of 3,5-bis(1,1-dimethylethyl)-4- Octadecyl hydroxyphenylpropionate and 0.063 parts by weight of ethylenedistearylamine were mixed to form a mixture.

100 parts by weight of styrene, 3.0 parts by weight of 1,1-bis-tert-butylperoxycyclohexane, and 1.8 parts by weight of diphenylguanidinium peroxide were used to form a polymerization initiator solution.

The above mixture was pumped at a flow rate of 61 kg/hour, and the above polymerization initiator solution was continuously supplied to the first reactor at a flow rate of 1.3 kg/hour to carry out a reaction, and the polymer solution after the reaction was further reacted. The reaction proceeds to the second reactor, the third reactor, and the fourth reactor. The first, second, third, and fourth reactors are sequentially connected in series, and the reactors are all columnar flow reactors having a capacity of 100 liters. The first reactor reaction temperature is 75 ° C ~ 90 ° C, stirring at 110 rpm, the second reactor reaction temperature is 95 ~ 105 ° C, stirring at 80 rpm, the third reactor reaction temperature 110 ~ 125 ° C, at 60 rpm Stirring, the fourth reactor reaction temperature was 135-150 ° C, and the mixture was stirred at a rotation speed of 5 rpm, and finally the polymer solid content was 62.5%. After the reaction is completed, the unreacted monomer and solvent are removed by devolatilization equipment for recycling, and then the strip is extruded through a die, and then cooled and pelletized to obtain a bulk polymer rubber graft copolymer (II). ). Adding acetone to the bulk polymeric rubber graft copolymer (II), allowing the rubber particles (B ₁ ) having a occluding structure to precipitate and filtering, and calculating the obtained emulsion polymerized rubber graft copolymer (I) It contains 75% by weight of a styrene-acrylonitrile-based copolymer (A ₂ ), and 25% by weight of rubber particles (B ₂ ) having a occluding structure.

[Synthesis Example 3] Solution polymerization of ethylene-based copolymer (III)

76 wt% of styrene and 24 wt% of acrylonitrile were placed at a rate of 12 kg/hr in a continuous kettle type reactor equipped with a stirrer at an internal temperature of 108 ° C and a capacity of 45 liters. Mixing and reacting, adding ethylene distearylamine, benzoyl peroxide and tert-dodecyl mercaptan to the reaction at a rate of 3.0 g/hr, and maintaining the proportion of toluene in the reaction solution at After 15%, and the polymerization rate was maintained at 55%, the reaction liquid was passed through a devolatilizer to remove volatile components, and then a pellet of a styrene-acrylonitrile copolymer having a melt flow index of 3.0 was obtained.

While obtaining the particles of the styrene-acrylonitrile copolymer, the removed volatile components can be condensed by a condenser as a recovery liquid, and continuously added to the reaction for reuse.

[Example 1] Rubber-modified styrene-based resin and molded article thereof

The emulsion-polymerized rubber graft copolymer (I) of Synthesis Example 1, the bulk or solution rubber graft copolymer (II) of Synthesis Example 2, and the styrene-maleic anhydride copolymer (A ₁ ) were mixed according to Table 1. And adding 0.7 parts by weight of a slip agent, and 0.5 parts by weight of a mixture containing a phenolic antioxidant and a phosphorus-based antioxidant, and mixing and granulating at 235 ° C with a Werner & Pfleidrer ZSK 35 extruder to obtain a rubber modification After the styrene resin is injected into the test piece at 230 ° C in the injection molding machine of the company's factory number SM-90, the molded article of the rubber-modified styrene resin can be obtained. The analysis and physical property evaluation results are shown in the table. 2.

[Examples 2 to 7]

In Examples 2 to 7, the rubber-modified styrene-based resin and the molded article thereof were prepared in the same manner as in Example 1, except that the emulsion polymerized rubber graft copolymer (I) and the block rubber were changed. The amounts of the branched copolymer (II), the styrene-maleic anhydride copolymer (A ₁ ) and the solution polymerized ethylene copolymer (III) are shown in Table 1. The analysis and physical property evaluation results are shown in Table 2.

[Comparative Example 1] Rubber-modified styrene-based resin and molded article thereof

Comparative Example 1 The rubber-modified styrene-based resin and its molded article were prepared in the same manner as in Example 1, except that the emulsion-polymerized rubber graft copolymer (I) of Synthesis Example 1 and styrene were changed. The amount of the solution of the maleic anhydride-based copolymer (A ₁ ) and the solution-polymerized ethylene-based copolymer (III) of Synthesis Example 3 is shown in Table 1. The analysis and physical property evaluation results are shown in Table 2.

[Comparative Example 2]

In Comparative Example 2, the rubber-modified styrene-based resin and its molded article were prepared in the same manner as in Comparative Example 1, except that the emulsion polymerized rubber graft copolymer (I) and the block rubber graft copolymerization were changed. The amounts of the materials (II), the styrene-maleic anhydride copolymer (A ₁ ) and the solution-polymerized ethylene copolymer (III) are shown in Table 1. The analysis and physical property evaluation results are shown in Table 2.

【Test items】 1. Melting coefficient (indicating fluidity, melt index, referred to as MI) evaluation and determination:

The rubber-modified styrene-based resins of Examples 1 to 7 and Comparative Examples 1 and 2 were tested at 220 ° C × 10 kg in accordance with JIS K-7210, and the unit was g/10 min.

2. Determination of softening point temperature:

The rubber-modified styrene-based resins of Examples 1 to 7 and Comparative Examples 1 and 2 were measured for softening point temperature (Vicat softening temp.) in accordance with ASTM D-1525, and the unit was °C.

3. Impact strength (Izod) evaluation:

The rubber-modified styrene-based resins of Examples 1 to 7 and Comparative Examples 1 and 2 were injected, and were prepared according to the standard method of ASTM D-256 (23 ° C, a 1/4 thickness test piece with a notch). The test piece was then tested in accordance with ASTM D-256 (unit: Kg-cm/cm).

4. Drop-ball evaluation:

The rubber-modified styrene-based resins of Examples 1 to 7 and Comparative Examples 1 and 2 were each prepared into a test piece of 107 mm × 107 mm × 1/8"; the impact strength of the low-temperature falling ball was measured in a freezer at -20 ° C. After freezing for 24 hours, the normal temperature falling ball impact strength should be placed at room temperature for 24 hours, using the instrument Dynatup 8250, according to ASTM-3763, the weight drop weight is 23.64 kg, the drop weight is 0.56 m, and the impact speed is 3.34 m/sec. A test is performed to measure the energy required to rupture the test pieces, the unit being expressed in J.

5. Weight average particle size measurement method:

The rubber-modified styrene-based resins of Examples 1 to 7 and Comparative Examples 1 and 2 were each stained with osmium tetroxide (OsO ₄ ), and after dyeing, the photos were photographed by a transmission electron microscope at 10,000 magnification. The rubber particles (200 to 1,000 in number) were measured, and the particle diameter (D, unit μm) was measured, and the average particle diameter (D _avg ) was determined according to the following formula.

Wherein, N _i is the number of rubber particles having a particle diameter D _i ; and D _i is a particle diameter of the i-th rubber particle.

6. Measurement of the average thickness of the graft copolymer:

The rubber-modified styrene-based resins of Examples 1 to 7 and Comparative Examples 1 and 2 were each dissolved in acetone, and the insoluble rubber particles were taken out by centrifugation. Next, the rubber particles were dispersed in acetone to form a dispersion, and a few drops were dropped into a main component of a two-liquid epoxy resin-based adhesive (trade name: Araldite Rapid, manufactured by Ciba-Geigy Co., Ltd.) to make a main component. The agent is mixed with the rubber particles in a sufficient amount, and then acetone is removed by vacuum drying. Then, a hardener of the two-component epoxy resin-based adhesive is added, and the mixture is mixed and mixed, and then heated and hardened to obtain 9 to be tested. sheet.

The waiting test piece was stained with ruthenium tetroxide, sliced with a microtome, and photographed by a 60,000-fold transmission electron microscope. After dyeing with ruthenium tetroxide, the rubber body and epoxy resin are dyed black, and the graft copolymer is white, and the rubber particles (25 or more) photographed in the photograph are depicted as "drawing paper" The shape of the rubber body and the graft layer copolymer, and the weight is cut, the area of the graft copolymer can be converted according to the unit area of the unit weight (A), and the area of the graft copolymer is divided by the rubber body The circumference (L) gives the thickness of the graft copolymer (T, unit ), and determine the average thickness (T _avg ) according to the following formula,

Wherein, T _i is the thickness of the i-th graft copolymer; D _i is the diameter of the i-th rubber particle; n is the total number of samples of the rubber particles during the analysis, n≧25.

From the results of Examples 1 to 5 and 7 in Table 1, it can be seen that when the weight ratio of A ₁ to A _{2 and} the weight ratio of B ₁ to B _{2 are} in the range of 0.463 to 0.510 and 0.251 to 2.103, respectively, the rubber can be modified. The styrene-based resin has a preferred softening point (122.1 ° C to 125.4 ° C) and a melting coefficient (4.88 g/10 min to 6.26 g/10 min), which is shown in the subsequent processing, except that the resin has better fluidity. Moreover, because of the high softening point, the resin does not crack and thermally decompose in the process, and at the same time, it has a good ball drop impact strength (5.33-7) at low temperature, indicating that the resin can also be used in subsequent processing. Operating at a low temperature; compared with Comparative Example 1, the weight ratio of A ₁ to A ₂ , and the weight ratio of B ₁ to B ₂ are respectively 0.453 and 0, the low temperature ball drop of the rubber modified styrene resin The impact strength (3.89) and the melting coefficient (4.24 g/10 min) were not good; compared with Comparative Example 2, the weight ratio of A ₁ to A _{2 and} the weight ratio of B ₁ to B ₂ were 0 and 2.16, respectively. The rubber modified styrene resin has a poor softening point temperature (105.8 ° C).

From the results of Examples 6 and 7, it can be seen that when the weight ratio of A ₁ to A _{2 and} the weight ratio of B ₁ and B ₂ are controlled within the range of 0.2 to 0.510 and 2.060 to 2.450, respectively, the rubber can be modified to be benzene. The vinyl resin has a preferred softening point (113.8 to 125.4 ° C) and a melting coefficient (4.88 g/10 min to 11.4 g/10 min). The content of the styrene-maleic anhydride copolymer (A ₁ ) affects the softening point and impact strength. When the amount increases, the softening point temperature increases, but the low temperature ball drop impact strength decreases; In Examples 1 to 5, when the content of the rubber particles (B ₁ ) having the absorbing structure is increased, the low-temperature ball impact strength can be improved. Therefore, the rubber is modified into a styrene resin by a synergistic effect generated between the styrene-maleic anhydride-based copolymer (A ₁ ) and the rubber particles (B ₁ ) having a occluding structure. A balance is struck between properties and low temperature mechanical properties.

In summary, the present invention allows the rubber modified styrene resin to have a better softening point and fluidity by adjusting the weight ratio of A ₁ to A _{2 and} the weight ratio of B ₁ to B ₂ . It has good impact strength at low temperature operation, and has good operation convenience for subsequent processing processes, whether at high temperature or low temperature, and transmits styrene-maleic anhydride copolymer (A ₁ ) with suction. The synergistic effect between the rubber particles (B ₁ ) of the Tibetan structure can further balance the thermal properties and the low-temperature mechanical properties of the rubber-modified styrene resin of the present invention, so that the present invention can be achieved. The purpose.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

Claims (15)

A rubber-modified styrene-based resin comprising: 70% by weight to 85% by weight of a continuous phase formed by the copolymer (A); and 15% by weight to 30% by weight of a dispersed phase of the rubber particles (B). Wherein the copolymer (A) comprises a styrene-maleic anhydride-based copolymer (A ₁ ) and a styrene-acrylonitrile-based copolymer (A ₂ ); the rubber particles (B) comprise rubber particles having a occluding structure (B ₁ ) and rubber particles (B ₂ ) having a non-occluded structure, and the weight ratio of A ₁ to A ₂ is in the range of 0.15 to 0.55, and the weight ratio of B ₁ to B ₂ is in the range of 0.1 to 2.5. The rubber-modified styrene-based resin according to claim 1, wherein the copolymer (A) comprises 12% by weight to 47% by weight based on 100% by weight of the total of the copolymer (A). A styrene-maleic anhydride copolymer (A ₁ ), and 53% by weight to 88% by weight of a styrene-acrylonitrile copolymer (A ₂ ). The rubber-modified styrene-based resin according to claim 1, wherein the rubber particles (B) comprise 15% by weight to 75% by weight based on 100% by weight of the total of the rubber particles (B). Rubber particles (B ₁ ) having a occlusion structure, and 25% by weight to 85% by weight of rubber particles (B ₂ ) having a non-occlusive structure. The rubber-modified styrene-based resin according to the above aspect of the invention, wherein the styrene-maleic anhydride-based copolymer (A ₁ ) comprises 45% by weight to 54.5 % by weight of a styrene-based monomer unit, 45 wt% to 54.5 wt% of an unsaturated dicarboxylic acid quinone imine monomer unit, and 0.5 wt% to 10 wt% of an unsaturated dicarboxylic anhydride monomer unit. The rubber-modified styrene-based resin according to claim 1, wherein the styrene-acrylonitrile-based copolymer (A ₂ ) comprises 65% by weight to 76% by weight of a styrene-based monomer unit, and 24% by weight to 35% by weight of an acrylic monomer unit. The rubber-modified styrene-based resin according to the above aspect of the invention, wherein the first graft copolymer of the rubber particles (B ₁ ) having the occluding structure has an average thickness ranging from 90 ~300 And the second graft copolymer in the rubber particles (B ₂ ) having the non-occluded structure has an average thickness ranging from 30 ~160 . The rubber-modified styrene-based resin according to the first aspect of the invention, wherein the rubber particles (B ₁ ) having the occluding structure have a weight average particle diameter ranging from 0.1 μm to 10 μm, and the non-absorbent layer The rubber particles (B ₂ ) of the structure have a weight average particle diameter ranging from 0.05 μm to 0.8 μm. A rubber-modified styrene-based resin comprising: 70% by weight to 85% by weight of a continuous phase formed by the copolymer (A); and 15% by weight to 30% by weight of a dispersed phase of the rubber particles (B). Wherein the copolymer (A) comprises 12% by weight to 47% by weight of the styrene-maleic anhydride-based copolymer (A ₁ ), and 53% by weight to 88% by weight of the styrene-acrylonitrile-based copolymer (A). ₂ ); the rubber particles (B) include 15% by weight to 75% by weight of rubber particles (B ₁ ) having a occluding structure, and 25% by weight to 85% by weight of rubber particles having a non-occlusive structure (B _{2 )} The styrene-maleic anhydride copolymer (A ₁ ) is composed of 45% by weight to 54.5 % by weight of a styrene monomer unit, and 45% by weight to 54.5 % by weight of an unsaturated dicarboxylic acid sulfonium imide system. a monomer unit, and 0.5% by weight to 10% by weight of an unsaturated dicarboxylic anhydride monomer unit; the styrene-acrylonitrile copolymer (A ₂ ) is composed of 65% by weight to 76% by weight of a styrene series The bulk unit is composed of 24% by weight to 35% by weight of the acrylic monomer unit; and the weight ratio of A ₁ to A ₂ is in the range of 0.2 to 0.51. A molded article of a rubber-modified styrene-based resin obtained by subjecting a rubber-modified styrene-based resin according to any one of claims 1 to 8 to a kneading process. A method for preparing a rubber-modified styrene-based resin by graft copolymerization of a bulk polymer rubber comprising 5% by weight to 20% by weight of an emulsion polymerized rubber graft copolymer (I) and 15% by weight to 85% by weight Mixture of the product (II), 10% by weight to 35% by weight of the styrene-maleic anhydride copolymer (A ₁ ) and 0% by weight to 45% by weight of the solution polymerized ethylene copolymer (III) Got it. The method for preparing a rubber-modified styrene-based resin according to claim 10 of the patent application, further comprising a processing and molding process after the kneading. A method for producing a rubber-modified styrene-based resin according to claim 10, wherein the emulsion-polymerized rubber graft copolymer (I), the bulk polymer rubber graft copolymer (II), and solution-polymerized ethylene are used. The copolymer (III) is prepared by polymerization of a monomer component comprising a styrene monomer comprising 50% by weight to 90% by weight, and an Acrylonitrile monomer in an amount of 10% by weight to 50% by weight. Got it. The method for preparing a rubber-modified styrene-based resin according to claim 12, wherein the emulsion-polymerized rubber graft copolymer (I), the bulk polymer rubber graft copolymer (II), and the solution polymerization ethylene The copolymer (III) is prepared by a polymerization reaction comprising a monomer component comprising 58% by weight to 80% by weight of a styrene monomer, and 20% by weight to 42% by weight of an acrylic monomer. Got it. The method for producing a rubber-modified styrene-based resin according to claim 13, wherein the monomer used in the bulk polymer rubber graft copolymer (II) or the solution-polymerized ethylene copolymer (III) The weight percentage of the acrylonitrile-based monomer in the component is slightly smaller than the weight percentage of the acrylonitrile-based monomer in the monomer component used in the emulsion-polymerized rubber graft copolymer (I). The method for producing a rubber-modified styrene-based resin according to claim 10, wherein the styrene-maleic anhydride-based copolymer (A ₁ ) comprises 45% by weight to 54.5 % by weight of a styrene-based single sheet. The bulk unit, 45% by weight to 54.5% by weight of the unsaturated bismuth quinone iodide monomer unit, and 0.5% by weight to 10% by weight of the unsaturated dicarboxylic anhydride monomer unit.