TW201811902A - Rubber-modified resin composition and preparation method thereof - Google Patents

Abstract

A rubber-modified resin composition is provided. The rubber-modified resin composition includes a continuous phase formed by a styrene-acrylonitrile-based copolymer, a dispersed phase formed by an acrylate rubber graft copolymer, and p-menthane, wherein the content of p-menthane is larger than 5 ppm and less than 180 ppm, and the rubber-modified resin composition does not contain acetophenone.

Description

Rubber modified resin composition and preparation method thereof

The present invention relates to a resin composition, and more particularly, to a rubber modified resin composition and a preparation method thereof.

Generally speaking, the components contained in plastic molded products used in electrical appliances, household goods, etc. are mostly rubber-modified styrene resins, polycarbonate resins, or rubber-modified methacrylate resins. Among them, the rubber-modified styrene resin is divided into a butadiene rubber-modified styrene resin and an acrylate rubber-modified styrene resin. The acrylate rubber modified styrene resin is a ternary graft copolymer composed of acrylonitrile, styrene, and acrylate rubber. Compared with butadiene rubber modified styrenic resin, rubber modified methacrylate resin has greatly improved weather resistance because it replaces butadiene rubber with acrylate rubber with less double bond content, which is not easy. Light or heat to crack. Furthermore, since the weather resistance of the acrylate rubber modified styrene resin is greatly improved than that of the butadiene rubber modified styrene resin, it can be used directly outdoors. Acrylic rubber modified styrene resin is usually used in automotive fields (such as exterior mirrors, radiator grilles, tailgates, lamp covers and other outdoor components); or in electrical and electronic fields (such as sewing machines, telephones, kitchen equipment , Satellite antennas, etc.); or used in the construction field.

However, as far as the conventional preparation method is concerned, acrylate rubber modified styrenic resin is susceptible to acetophenone, which causes odor, which not only causes discomfort to the human body, but also limits the applicability of the resin. Therefore, how to prepare an acrylate rubber modified styrenic resin that is completely free of acetophenone residues and maintains physical properties required for processing in the industry has become an urgent research subject in the industry.

The invention provides a rubber modified resin composition and a preparation method thereof, which are completely free of acetophenone residues, and have good impact resistance, heat resistance and surface gloss.

The rubber modified resin composition of the present invention includes a continuous phase formed by a styrene-acrylonitrile copolymer (A), a dispersed phase formed by an acrylate rubber graft copolymer (B), and The content of pentane is more than 5 ppm and less than 180 ppm, and the rubber modified resin composition does not contain acetophenone.

In one embodiment of the present invention, the content of para-pentane is greater than 8 ppm and less than 150 ppm.

In one embodiment of the present invention, the styrene-acrylonitrile-based copolymer (A) is based on the total weight of the styrene-acrylonitrile-based copolymer (A) and the acrylate-based rubber graft copolymer (B). ) Is 40 to 90% by weight, and acrylate rubber graft copolymer (B) is 10 to 60% by weight.

In one embodiment of the present invention, the above-mentioned rubber modified resin composition includes: 15 weights based on the total weight of the styrene-acrylonitrile copolymer (A) and the acrylate rubber graft copolymer (B). % To 25% by weight of an acrylonitrile-based monomer unit, 55% to 65% by weight of a styrene-based monomer unit, and 15% to 25% by weight of an acrylate-based monomer unit.

In one embodiment of the present invention, the weight average particle diameter of the acrylic rubber graft copolymer (B) is in a unimodal distribution form between 0.05 μm and 0.22 μm, and is between 0.26 μm. A unimodal distribution pattern between 0.55 μm or a bimodal distribution pattern between 0.05 μm and 0.22 μm and between 0.26 μm and 0.55 μm.

The method for preparing a rubber modified resin composition of the present invention includes the following steps. Provides a styrene-acrylonitrile copolymer (A) and an acrylic rubber graft copolymer (B). The styrene-acrylonitrile copolymer (A) and the acrylic rubber graft copolymer (B) are kneaded, wherein the rubber modified resin composition contains para-pentane, and the content of para-pentane is more than 5 ppm and less than 180 ppm, and the rubber modified resin composition does not contain acetophenone.

In one embodiment of the present invention, a method for providing the above-mentioned acrylic rubber graft copolymer (B) includes the following steps. An acrylate monomer is subjected to an emulsion polymerization reaction to form an acrylate rubber emulsion. The acrylate rubber emulsion is subjected to a graft polymerization reaction, wherein the graft polymerization reaction includes the use of hydrogen peroxide / pentane as a starter.

In one embodiment of the present invention, the total amount of hydrogen peroxide to pentane is less than 1.3 parts by weight and greater than 0.35 parts by weight based on 100 parts by weight of the acrylate rubber emulsion.

In one embodiment of the present invention, the above-mentioned emulsification polymerization reaction includes using hydrogen peroxide to pentane as a starter. In the emulsion polymerization reaction, based on 100 parts by weight of an acrylate monomer, the hydrogen peroxide The total amount of pentane used is less than 1 part by weight and greater than 0.05 parts by weight.

Based on the above, the rubber modified resin composition of the present invention includes a styrene-acrylonitrile copolymer (A), an acrylate rubber graft copolymer (B), and para-pentane having a specific content range, but does not contain Acetophenone not only solves the problem of odor caused by the residue of acetophenone, but also further improves the odor through the para-pentane containing one of the perfume raw materials. In this way, the rubber modified resin composition of the present invention has good applicability. In addition, the rubber-modified resin composition of the present invention has both a styrene-acrylonitrile-based copolymer (A), an acrylate-based rubber graft copolymer (B), and p-pentane having a specific content range. Good impact resistance, heat resistance and surface gloss.

In order to make the above features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail below.

In this article, a range represented by "one value to another value" is a summary representation that avoids enumerating all the values in the range one by one in the specification. Therefore, the record of a specific numerical range covers any numerical value within the numerical range and a smaller numerical range defined by any numerical value within the numerical range, as if the arbitrary numerical value and the smaller numerical value were explicitly written in the description. Same scope.

Herein, the monomer unit means a structural unit formed by a polymerization reaction of a monomer.

A rubber modified resin composition provided by an embodiment of the present invention includes a continuous phase formed by a styrene-acrylonitrile copolymer (A), a dispersed phase formed by an acrylate rubber graft copolymer (B), and Menthane, but not containing acetophenone, contains more than 5 ppm and less than 180 ppm of pentane based on the total weight of the rubber-modified resin composition. In this way, the rubber modified resin composition of the present embodiment not only solves the problem of acetophenone residues, but also further improves the odor through p-pentane, thereby improving its applicability. On the other hand, the rubber according to the present embodiment includes a styrene-acrylonitrile-based copolymer (A), an acrylate rubber graft copolymer (B), and a specific content range for pentane. The modified resin composition also has good impact resistance, heat resistance and surface gloss.

If the content of pentane is greater than or equal to 180 ppm, the fluidity of the rubber modified resin composition is poor, which will affect subsequent processing molding; if the content of pentane is less than or equal to 5 ppm, the Physical properties such as impact resistance, heat resistance, and surface gloss will be affected, failing to meet industry standards. In one embodiment, the content of pentane is preferably more than 8 ppm and less than 150 ppm, more preferably more than 10 ppm and less than 100 ppm, and even more preferably more than 10 ppm and less than 80 ppm.

In this embodiment, the content of the styrene-acrylonitrile-based copolymer (A) is 40 based on the total weight of the styrene-acrylonitrile-based copolymer (A) and the acrylate-based rubber graft copolymer (B). The content is from 10% by weight to 90% by weight, and the content of the acrylic rubber graft copolymer (B) is from 10% by weight to 60% by weight. From another viewpoint, the rubber modified resin composition includes 15% to 25% by weight based on the total weight of the styrene-acrylonitrile-based copolymer (A) and the acrylate-based rubber graft copolymer (B). Acrylonitrile-based monomer units, 55% to 65% by weight of styrene-based monomer units, and 15% to 25% by weight of acrylate-based monomer units. Here, the acrylate-based monomer unit, the styrene-based monomer unit, and the acrylonitrile-based monomer unit respectively refer to an acrylate-based monomer, a styrene-based monomer, and an acrylonitrile-based monomer formed by polymerization reaction. Building blocks.

Specifically, in this embodiment, the styrene-acrylonitrile-based copolymer (A) is obtained by polymerizing a styrene-based monomer and an acrylonitrile-based monomer. The composition of the styrene-acrylonitrile copolymer (A) includes 60 to 85% by weight of a styrene-based monomer unit and 15 to 40% by weight of an acrylonitrile-based monomer unit, and is preferably 64% by weight. To 78% by weight of a styrene-based monomer unit and 22 to 36% by weight of an acrylonitrile-based monomer unit. The aforementioned monomer unit refers to a residue (ie, a residual structure) in a polymer molecule obtained by polymerizing a monomer. Specific examples of the styrene-based monomer include, but are not limited to: styrene, α-methylstyrene, p-third butylstyrene, p-methylstyrene, o-methylstyrene, M-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, α-methyl-p-methylstyrene or bromostyrene, etc., among which styrene or α-methylstyrene Is better. Specific examples of the acrylonitrile-based monomer include, but are not limited to, acrylonitrile or α-methacrylonitrile, among which acrylonitrile is preferred.

The polymerization reaction can be performed by using a block polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method, and among them, a block polymerization method or a solution polymerization method is preferred. Taking solution polymerization as an example, the method for preparing a styrene-acrylonitrile copolymer (A) includes a solution polymerization reaction of a styrene-based monomer, an acrylonitrile-based monomer, and a polymerization initiator in the presence of a solvent. The operating temperature range is preferably 70 ° C to 140 ° C, and more preferably 90 ° C to 130 ° C. The solvent used is, for example, toluene, ethylbenzene, or methylhexanone.

The polymerization initiator includes (but is not limited to): hydrogen peroxide compounds, such as tert-butyl hydroperoxide, paramenthane hydroperoxide, etc. ; Peroxyketal compounds, such as: 1,1-bis-tertiary butyl peroxy-3,3,5-trimethylcyclohexane (1,1-di- (tert-butylperoxy ) -3,3,5-trimethylcyclohexane), 2,2-di (4,4-di (t-butylperoxy) cyclohexyl) propane (2,2-di (4,4-di (tert-butylperoxy) cyclohexyl) propane), etc .; peroxyesters, such as: t-butyl peroxypivalate, 2,5-dimethyl-2,5-bis (2-ethyl Hexyl alcohol peroxy) hexane (2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane), etc .; ketal peroxide compounds, for example: 4,4-diperoxy third butyl- Valeric acid-n-butyl ester (4,4-di-t-butyl peroxy valeric acid-n-butyl ester, TX-17 for short), etc .; peroxycarbonate compounds, for example: 2-ethylhexyl tertiary Amyl peroxide carbonate mylperoxy 2-ethylhexyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, etc .; or azo compounds with nitro and cyclohexane. Based on the total weight of the styrene-based monomer and the acrylonitrile-based monomer being 100 parts by weight, the addition amount of the polymerization initiator ranges from 0.01 to 2.0 parts by weight, and preferably from 0.01 to 1.0 part by weight.

In addition, when preparing the styrene-acrylonitrile copolymer (A), a polymerization initiator may be added to the reaction as described above, and a thermal polymerization method may also be used.

In addition, the reactor used for carrying out the foregoing reaction may include (but is not limited to): a fully mixed continuous reactor (CSTR), a column flow reactor (PFR), or a tube containing a static mixing element As the reactor, a fully-mixed continuous reactor is preferred. The number of the reactors may be one, or two or more of them may be used in combination.

In one embodiment, the molecular weight of the styrene-acrylonitrile-based copolymer (A) is 60,000 to 400,000.

In addition, in this embodiment, the method for producing an acrylic rubber graft copolymer (B) includes performing a graft polymerization reaction on an acrylic rubber emulsion. Specifically, a method for preparing an acrylate rubber emulsion includes: subjecting an acrylate monomer to an emulsion polymerization reaction in the presence of an initiator. Specific examples of the acrylate monomer include (but are not limited to): methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, methacrylic acid Hexyl, heptyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, acrylic acid 2-Ethylhexyl, dodecyl acrylate, etc., of which n-butyl acrylate is preferred.

The initiator may be various conventional free radical polymerization initiators other than cumene hydroperoxide (CHP), and the method for adding the initiator may be one-time addition. , Or add continuously or incrementally. In detail, specific examples of the initiator include (but are not limited to): p-menthane hydroperoxide (PMHP), tert-butyl peroxide, dodecane Layroyl peroxide, oleyl peroxide, tert-butyl peracetate, isoperopyl peroxy dicarbonate ), 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane, tert-butyl Tert-butyl hydroperoxide, 2,5-dimethyl-2,5-bis (third perbutyl peroxide) -hexyl-3-tert-butyl hydroperoxide (2,5-dimethyl- 2,5-di (tert-butylperoxy) hexane-3-tert-butyl hydroperoxide), cyclopentane hydroperoxide, pinane hydroperoxide, 2,5-dimethyl -Hexyl-2,5-dihydroperoxide (2,5-dimethyl-hexane-2,5-dihydroperoxide) or a mixture thereof. In one embodiment, the total amount of the initiator is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the total weight of the acrylate-based monomer.

In addition, the method for preparing the acrylic rubber emulsion may further include adding a bridging agent during the polymerization reaction. The bridging agent includes (but is not limited to): ethylene diacrylate, butadiene diacrylate, divinylbenzene, butenediol dimethacrylate, dimethacrylate, and tri (meth) acrylic acid Trimethylolpropane, allyl methacrylate (AMA), diallyl methacrylate, diallyl maleate, diallyl fumarate, diallyl phthalate , Triallyl methacrylate, triallyl tricyanate, triallyl isocyanurate, acrylate of tricyclodecenol, diacrylate of polyalkylene glycol, etc., among which The bridging agent can be used alone or in combination of two or more. In one embodiment, based on the total weight of the acrylate monomer and the bridging agent being 100% by weight, the amount of the bridging agent used is preferably 0.1% to 10% by weight.

In addition, the average particle size of the acrylate rubber emulsion can be controlled by the polymerization reaction conditions, such as: polymerization temperature; the amount and type of the initiator, emulsifier, and activator; and the method of adding monomers. The emulsifier is not particularly limited, and is selected from sodium succinate, potassium fatty acid, sodium fatty acid, dipotassium alkenyl succinate, and rose acid soap in order to improve the stability of the emulsion during the emulsion polymerization reaction and improve the polymerization rate. Carboxylic acid salts such as sulfonic acid salts, sulfonic acid salts such as alkyl sulfates, sodium alkylbenzenesulfonates, and anionic emulsifiers such as polyethylene oxide nonylphenyl ether sodium sulfate are preferred. Specific examples of the activator include, but are not limited to, ferrous sulfate, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, tetrasodium pyrophosphate, and the like.

In addition, the weight average particle diameter of the acrylate rubber emulsion may be in a unimodal distribution form or a bimodal distribution form. In one embodiment, the weight average particle diameter of the acrylic rubber emulsion has a unimodal distribution pattern between 0.05 μm and 1 μm. In another embodiment, the weight average particle diameter of the acrylic rubber emulsion has a unimodal distribution pattern between 0.05 μm and 0.2 μm. In another embodiment, the weight average particle diameter of the acrylate rubber emulsion has a unimodal distribution pattern between 0.26 μm and 0.5 μm. In yet another embodiment, the weight average particle diameter of the acrylate rubber emulsion has a bimodal distribution pattern between 0.05 μm and 0.2 μm and between 0.26 μm and 0.5 μm.

The graft polymerization reaction of the acrylate rubber emulsion includes: grafting 100 parts by weight (dry weight) of the acrylate rubber emulsion with 50 to 100 parts by weight of a monomer mixture in the presence of an initiator. In the polymerization reaction, the monomer mixture includes 64 to 78% by weight of a styrene-based monomer and 22 to 36% by weight of an acrylonitrile-based monomer. The aforementioned monomer mixture can be added in one time, in batches, continuously, or in various monomers in the monomer mixture. In addition, as described above, when the weight average particle size of the acrylate rubber emulsion is a bimodal distribution, the two acrylate rubber emulsions can be separately and separately subjected to graft polymerization and then mixed, or two This acrylate-based rubber emulsion can undergo graft polymerization in a mixed state.

Specific examples of the styrene-based monomer include, but are not limited to: styrene, α-methylstyrene, p-third butylstyrene, p-methylstyrene, o-methylstyrene, M-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, α-methyl-p-methylstyrene or bromostyrene, etc., among which styrene or α-methylstyrene Is better. Specific examples of the acrylonitrile-based monomer include, but are not limited to, acrylonitrile or α-methacrylonitrile, among which acrylonitrile is preferred.

The initiator may be various conventional free radical polymerization initiators other than cumene hydroperoxide, and the method for adding the initiator may be one-time addition, or Join continuously or incrementally, etc. In detail, specific examples of the initiator include (but are not limited to): hydrogen peroxide to p-menthane hydroperoxide, tert-butyl peroxide, dodecylfluorene Layroyl peroxide, oleyl peroxide, tert-butyl peracetate, isoperopyl peroxy dicarbonate, 2 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane, tert-butyl hydrogen peroxide (Tert-butyl hydroperoxide), 2,5-dimethyl-2,5-bis (third perbutyl peroxide) -hexyl-3-third butyl hydroperoxide (2,5-dimethyl-2,5 -di (tert-butylperoxy) hexane-3-tert-butyl hydroperoxide), cyclopentane hydroperoxide, pinane hydroperoxide, 2,5-dimethyl-hexyl- 2,5-dihydroperoxide (2,5-dimethyl-hexane-2,5-dihydroperoxide) or a mixture thereof. In one embodiment, based on the total weight of the monomer mixture being 100 parts by weight, the total amount of the initiator used is preferably from 0.01 to 2 parts by weight.

It is worth noting that if hydrogen peroxide / pentane is used as the initiator in the aforementioned emulsion polymerization reaction, hydrogen peroxide / pentane may be used as the initiator in the graft polymerization reaction or hydrogen peroxide is not used. P-pentane is used as a starter; and if hydrogen peroxide-p-pentane is not used as the starter in the aforementioned emulsion polymerization reaction, then hydrogen peroxide-p-pentane must be used as a starter in the graft polymerization reaction. That is, in the present embodiment, in the process of preparing the acrylate rubber graft copolymer (B), at least one of the emulsification polymerization reaction and the graft polymerization reaction uses hydrogen peroxide to menthane as a starting point. Agent. Furthermore, it is preferred that in the process of preparing the acrylate-based rubber graft copolymer (B), the graft polymerization reaction uses hydrogen peroxide / pentane as an initiator.

Specifically, in the present embodiment, in the emulsion polymerization reaction, based on 100 parts by weight of the acrylate-based monomer, the total amount of hydrogen peroxide to be used as a starter is less than 1 part by weight and greater than 0.05. Parts by weight. In the emulsification polymerization reaction, if the amount of hydrogen peroxide used for pentane is 1 part by weight or more, the gloss and heat resistance of the rubber modified resin composition are poor; if the amount of hydrogen peroxide used for pentane is less than or equal to 0.05 parts by weight, the impact resistance of the rubber modified resin composition will be significantly insufficient. In addition, in the present embodiment, in the graft polymerization reaction, based on 100 parts by weight of the acrylate-based rubber emulsion, the total amount of hydrogen peroxide to be used as a starter is less than 1.3 parts by weight and greater than 0.35 weight Serving. In the graft polymerization reaction, if hydrogen peroxide is used in an amount of 1.3 parts by weight or more, the fluidity of the rubber-modified resin composition will be too high; if hydrogen peroxide is used in an amount of less than or If it is equal to 0.35 parts by weight, the fluidity of the rubber-modified resin composition will be too low.

Furthermore, the para-pentane contained in the rubber modified resin composition is a product produced by the reaction of the hydrogen peroxide initiator, that is, the preparation of acrylate-based rubber graft copolymer (B) for para-pentane By-products of the process. In addition, as described above, since the initiator is not a hydrogen peroxide initiator that generates acetophenone after the reaction, whether in the emulsion polymerization reaction or the graft polymerization reaction, the composition of the rubber modified resin The substance does not contain acetophenone.

In addition, the graft ratio of the acrylic rubber graft copolymer (B) can be controlled by the polymerization reaction conditions, such as: polymerization temperature; the amount and type of the initiator, emulsifier, activator, and chain transfer agent; The amount of monomer and the method of addition are controlled. In one embodiment, the reaction temperature of the graft polymerization reaction is below 90 ° C, preferably between 25 ° C and 40 ° C.

The emulsifier is not particularly limited, and is selected from sodium succinate, potassium fatty acid, sodium fatty acid, dipotassium alkenyl succinate, and rose acid soap in order to improve the stability of the emulsion during the emulsion polymerization reaction and improve the polymerization rate. Carboxylic acid salts such as sulfonic acid salts, sulfonic acid salts such as alkyl sulfates, sodium alkylbenzenesulfonates, and anionic emulsifiers such as polyethylene oxide nonylphenyl ether sodium sulfate are preferred. Specific examples of the activator include, but are not limited to, ferrous sulfate, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, tetrasodium pyrophosphate, and the like. Specific examples of the chain transfer agent include (but are not limited to): n-butyl mercaptan, n-octyl mercaptan, and n-dodecyl sulfur Alcohol (n-dodecyl mercaptan), tert-dodecyl mercaptan. In one embodiment, based on the total weight of the monomer mixture being 100 parts by weight, the use amount of the chain transfer agent is preferably from 0.01 to 5 parts by weight.

The weight average particle diameter of the acrylic rubber graft copolymer (B) may be in a unimodal distribution type or a bimodal distribution type. In one embodiment, the weight average particle diameter of the acrylic rubber graft copolymer (B) has a unimodal distribution pattern between 0.05 μm and 0.22 μm. In another embodiment, the weight average particle diameter of the acrylic rubber emulsion has a unimodal distribution pattern between 0.26 μm and 0.55 μm. In yet another embodiment, the weight average particle diameter of the acrylate rubber emulsion has a bimodal distribution pattern between 0.05 μm and 0.22 μm and between 0.26 μm and 0.55 μm.

The rubber-modified resin composition of the present embodiment may further contain additives. The additive is selected from the group consisting of antioxidants, lubricants, plasticizers, processing aids, UV stabilizers, UV absorbers, fillers, reinforcing agents, colorants, antistatic agents, flame retardants, flame retardant additives, heat Stabilizers, coupling agents, or combinations thereof.

The antioxidants can be used alone or in combination, and the antioxidants include (but are not limited to): phenol-based antioxidants, thioether-based antioxidants, or phosphorus-based antioxidants. The phenolic antioxidants can be used alone or in combination, and specific examples of the phenolic antioxidants include (but are not limited to): 3,5-bis (1,1-dimethylethyl) -4-hydroxyphenylpropyl Octadecyl ester (3,5-bis (1,1-dimethylethyl) -4-hydroxybenzenepropanoic acid octadecyl ester, model: antioxidant IX-1076), triethylene glycol bis [3- (3-tert-butyl Methyl-5-methyl-4-hydroxyphenyl) propionate], tetrakis [methylidene-3- (3,5-bis-third-butyl-4-hydroxyphenyl) propionate] methane, 2 -Third-butyl-6- (3-third-butyl-2-hydroxy-6-methylbenzyl) -4-methylphenylacrylate, 2,2'-methylidene-bis (4 -Methyl-6-tert-butylphenol) (2,2'-methylenebis (4-methyl-6-tert-butylphenol), model: antioxidant 2246), 2,2'-thiobis (4-methyl -6-Third-butylphenol), 2,2'-thio-diethylidene-bis [3- (3,5-bis-third-butyl-4-hydroxyphenyl) propionate], or 2,2'-ethylenediamine-bis [ethyl-3- (3,5-bis-third-butyl-4-hydroxyphenyl) propionate] and the like. The thioether-based antioxidants may be used singly or in combination, and specific examples of the thioether-based antioxidants include (but are not limited to): distearyl thiodipropionate, dipalmitine thiodipropionate, pentaerythr Erythritol-tetra- (β-dodecyl-thiopropionate), or dioctadecyl sulfide and the like. The phosphorus-based antioxidants can be used alone or in combination, and the phosphorus-based antioxidants include (but are not limited to): phosphorus-based antioxidants containing phosphorous acid esters or phosphorus-based antioxidants containing phosphoric acid esters. Specific examples of the phosphite-containing phosphorus-based antioxidant include (but are not limited to): tris (nonylphenyl) phosphite, dodecylphosphite, 4,4'-butylenebis (3 -Methyl-6-tert-butylphenyl-bistridecylphosphite) or tris (2,4-tert-butylphenyl) phosphite and the like. Specific examples of the phosphate-containing phosphorus-based antioxidant include (but are not limited to): tetra (2,4-third butylphenyl) -4,4'-biphenylphenyl phosphate, or 9,10 -Dihydro-9-oxy-10-phenanthrene-10-oxophosphate and the like.

The lubricants may be used alone or in combination, and specific examples of the lubricants include (but are not limited to): metal soaps such as calcium stearate, magnesium stearate, lithium stearate, and ethylene distearylamine ( ethylene bis-stearamide (EBA for short), pentaerythritol stearate (PETS), methylene distearylamine, ammonium palmitate, butyl stearate, palmityl stearate, pentaerythritol Tetrafatty acid esters, polyalcohol tristearate, n-docosaic acid, stearic acid compounds, polyethylene wax, octacosanoic acid wax, carnuba wax, petroleum wax, etc. .

In one embodiment, based on the total weight of the rubber-modified resin composition being 100 parts by weight, the content of the additive ranges from 0.01 to 20 parts by weight.

A method for preparing a rubber modified resin composition according to another embodiment of the present invention includes: providing any one of the styrene-acrylonitrile copolymers (A) and acrylate rubber graft copolymers (B) in the foregoing embodiments. ), The styrene-acrylonitrile copolymer (A) and the acrylate rubber graft copolymer (B) are kneaded to form a rubber modified resin composition. Relevant descriptions of the rubber modified resin composition, the styrene-acrylonitrile copolymer (A), and the acrylate rubber graft copolymer (B) have been described in detail in the above embodiment, and will not be repeated here. .

In this embodiment, the method of kneading a styrene-acrylonitrile-based copolymer (A) and an acrylate-based rubber graft copolymer (B) is not particularly limited, and a method known to those skilled in the art can be used. Any of the mixing methods. In one embodiment, a method of kneading the styrene-acrylonitrile copolymer (A) and the acrylate rubber graft copolymer (B) includes: dry-mixing with a commonly used Hanschel mixer, and then It is melt-mixed in a mixer such as an extruder mixer, a kneader, or a Banbury mixer.

In addition, the rubber-modified resin composition may further contain additives that can be used in the polymerization reaction for preparing the styrene-acrylonitrile copolymer (A) and the acrylic rubber graft copolymer (B), after the polymerization reaction, and before the coagulation. Or it is added in the process of kneading a styrene-acrylonitrile copolymer (A) and an acrylate rubber graft copolymer (B).

It is worth noting that, as described above, in the process of preparing the acrylate rubber graft copolymer (B), at least one of the emulsification polymerization reaction and the graft polymerization reaction uses hydrogen peroxide as a starting agent for pentane. As a starting agent, the final product will contain a by-product of parapentane, thereby kneading the styrene-acrylonitrile copolymer (A) and the acrylic rubber graft copolymer (B) to form a pair containing a specific content. A rubber modified resin composition of pentane. On the other hand, in the process of preparing the acrylic rubber graft copolymer (B), since the initiator does not generate acetophenone after the reaction, whether in the emulsion polymerization reaction or the graft polymerization reaction, Isopropyl benzene hydrogen peroxide, so the styrene-acrylonitrile copolymer (A) and acrylate rubber graft copolymer (B) were kneaded to form a rubber modified resin completely free of acetophenone组合 物。 Composition.

In this way, the rubber modified resin composition prepared by the method for preparing a rubber modified resin composition of the present embodiment not only solves the problem of acetophenone residues, but also further improves odor by containing para-pentane. On the other hand, the rubber according to the present embodiment includes a styrene-acrylonitrile-based copolymer (A), an acrylate rubber graft copolymer (B), and a specific content range for pentane. The rubber modified resin composition obtained by the preparation method of the modified resin composition has good impact resistance, heat resistance and surface glossiness at the same time.

Hereinafter, features of the present invention will be described more specifically with reference to Examples 1 to 8 and Comparative Examples 1 to 4. Although the following examples 1 to 8 are described, the materials used, their amounts and ratios, processing details, processing flow, and the like can be appropriately changed without going beyond the scope of the present invention. Therefore, the present invention should not be interpreted restrictively by the examples described below. Synthesis Example 1 Styrene - acrylonitrile copolymer prepared in (A),

76 parts by weight of styrene, 24 parts by weight of acrylonitrile, 8 parts by weight of ethylbenzene, and 0.01 part by weight of 1,1-bis-third butylperoxy-3,3,5-trimethylcyclohexyl The raw materials of alkane and 0.15 parts by weight of tertiary dodecyl mercaptan were mixed and continuously fed into two series-type complete mixing continuous reactors at a rate of 35 kg / hr, wherein the volume of the reactors was At 40 liters, the internal temperatures of the two reactors were maintained at 110 ° C and 115 ° C, respectively. The pressures of the reactors were maintained at 4 kg / cm ² , and the overall conversion rate was about 50%.

After the polymerization was completed, the obtained copolymer solution was heated by a preheater. Next, after removing the unreacted monomer and other volatile components in a reduced-pressure degassing tank, the resin was extruded and granulated to obtain a styrene-acrylonitrile copolymer (A) of Synthesis Example 1. Synthesis Example 2 Preparation of acrylate-based rubber graft copolymer (B) is

First, 99.0 parts by weight of n-butyl acrylate, 1.0 parts by weight of allyl methacrylate, 0.1 parts by weight of hydrogen peroxide versus pentane, 3.0 parts by weight of ferrous sulfate solution (concentration 0.2 wt%), 3.0 Part by weight of a formaldehyde sodium sulfoxylate solution (concentration: 10 wt%) and 4000.0 parts by weight of distilled water were subjected to an emulsion polymerization reaction at a reaction temperature of 60 ° C. for 7 hours to obtain an acrylic rubber having a weight average particle size of 0.1 μm. Emulsion (about 38% solids).

Next, 99.0 parts by weight of n-butyl acrylate, 1.0 parts by weight of allyl methacrylate, 0.1 parts by weight of hydrogen peroxide-to-pentane, 3.0 parts by weight of ferrous sulfate solution (concentration 0.2 wt%), 3.0 Part by weight of a formaldehyde sodium sulfoxylate solution (concentration: 10 wt%) and 4000.0 parts by weight of distilled water were subjected to an emulsion polymerization reaction at a reaction temperature of 65 ° C for 7 hours to obtain an acrylic rubber having a weight average particle diameter of 0.4 μm Emulsion (about 38% solids).

Next, 30.0 parts by weight of the acrylate rubber emulsion (dry weight) with a weight average particle diameter of 0.4 μm and 70.0 parts by weight of the acrylate rubber emulsion (dry weight) with a weight average particle diameter of 0.1 μm, 70.0 Parts by weight of styrene, 30.0 parts by weight of acrylonitrile, 0.86 parts by weight of hydrogen peroxide / pentane, 3.0 parts by weight of ferrous sulfate solution (concentration 0.2 wt%), 3.0 parts by weight of formaldehyde sodium hyposulfite solution ( The concentration is 10 wt%) and 3000.0 parts by weight of distilled water are mixed and subjected to a graft polymerization reaction. After the completion of the graft polymerization reaction, an acrylic rubber graft emulsion can be obtained.

Finally, the obtained acrylate rubber graft emulsion was coagulated with calcium chloride (CaCl ₂ ), dehydrated, and then dried to a moisture content of 2% or less, and the acrylate rubber graft copolymerization of Synthesis Example 2 was obtained. With a bimodal distribution of 0.12 µm and 0.45 µm in weight average particle size. Synthesis Example 3-12 Preparation of acrylate-based rubber graft copolymer (B) is

The acrylate rubber graft copolymers of Synthesis Examples 3-12 were prepared according to a preparation procedure similar to Synthesis Example 1, and according to the types and amounts of the initiators shown in Table 1.

The abbreviations in Table 1 are explained below: Table 1 a: The amount is calculated based on the total weight of the acrylate-based monomer as 100 parts by weight b: The amount is calculated based on the total weight of the acrylate-based rubber emulsion as 100 parts by weight Example 1 Preparation of the rubber modified resin composition

In a dry state, 54.1% by weight of the styrene-acrylonitrile copolymer (A) and 45.9% by weight of Synthesis Example 1 were produced using a biaxial extruder (model: ZPT-25, manufacturer: Zeki Industry Co., Ltd.) The acrylic rubber graft copolymer (B) of Synthesis Example 2 and 2.0% by weight of the lubricant were kneaded at a kneading temperature of 220 ° C. Next, after extruding with a biaxial extruder, the rubber modified resin composition of Example 1 was obtained. Preparation of rubber modified resin compositions of Examples 2-8 and Comparative Examples 1-4

The rubber-modified resin compositions of Examples 2-8 and Comparative Examples 1-4 were prepared according to a preparation procedure similar to Example 1, and according to the types and amounts of raw materials shown in Table 2. In addition, (weight%) in Table 2 is based on the total weight of a styrene-acrylonitrile-type copolymer (A) and the said acrylate-type rubber graft copolymer (B). Table 2 Table 2 (continued)

Thereafter, the rubber modified resin compositions of Examples 1-8 and Comparative Examples 1-4 were respectively measured: the content of acetophenone, the content of pentane, the measurement of the melt index (MI), Measurement of vicat softening temperature, measurement of Izod, and measurement of surface gloss. The foregoing items are explained below, and the measurement results are shown in Table 3. In addition, nd in Table 3 indicates that it was not measured. <Determination of Acetophenone>

Instrument: gas chromatography (GC) (model: Agilent 6890 GC / FID)

Column model: HP-5 30M * 0.32mm * 0.25um.

Pretreatment: 1 g of the sample (ie, the rubber modified resin composition of Examples 1-8 and Comparative Examples 1-4) was dissolved in 5 ml of dichloromethane, and then extracted with 10 ml of methanol. After that, the clear solution was taken and injected into the GC for quantification.

Temperature rising conditions: from 60 ° C to 10 ° C per minute and 300 ° C for 11 minutes. <Determination of Pentane Content>

Same as the above acetophenone content determination. <Measurement of melting coefficient>

Measured in accordance with ASTM D-1238. The measurement conditions are 220 ° C, the load is 10 Kg, and the unit is g / 10 min. In the field of general rubber modified resin composition, the MI standard must be at least greater than 5 g / 10 min and less than 12 g / 10 min, and the higher the value, the better the fluidity, that is, the rubber modified resin composition. The better the moldability. <Measurement of softening point temperature>

Measure the softening point temperature according to ASTM D-1525. The unit is ° C. Generally, the higher the softening point temperature, the better the heat resistance. <Measurement of Ai impact strength>

The injection molding machine (model: SM-150, manufacturer: Chen Hsong Machinery Works Co., Ltd.) was used to injection-mold the rubber-modified resin composition of Examples 1-8 and Comparative Examples 1-4 with a thickness of 1 / An 8-inch test piece was measured in accordance with ASTM D-256. The unit is: Kg cm / cm. In the field of general rubber modified resin compositions, the Izod standard must be at least 10 Kg cm / cm, and a higher value indicates better impact resistance. <Measurement of surface gloss>

The injection molding machine (model: SM-150, manufacturer: Chen Hsong Machinery Works Co., Ltd.) was used to test the rubber modified resin composition of Example 1-8 and Comparative Example 1-4 into a disc having a diameter of 5.5 cm. And measured in accordance with ASTM D-523, the unit is:%. <Measurement of odor>

Take fifty grams of the made resin and seal it in a glass sample bottle for one day, then open it and smell it directly by the human body. No odor and aromatic: ◎ No odor: ○ Slightly odor: △ Strong odor: X Table 3 Table 3 (continued)

As can be seen from the above Table 3, none of the rubber modified resin compositions of Examples 1 to 8 contained acetophenone and all contained p-pentane, and the content range was from 19 ppm to 68 ppm. In contrast, Comparative Example 1 -4 rubber modified resin composition all contain acetophenone, which easily causes unpleasant odor. Therefore, compared with the rubber-modified resin composition of Comparative Example 1-4, the rubber-modified resin composition of Example 1-8 not only does not have the problem of odor caused by the residue of acetophenone, Alkanes further improve the odor, thereby avoiding discomfort to the human body during application and having good applicability.

In addition, it can be seen from the above Table 3 that the rubber modified resin composition of Example 1-8 has excellent performance in terms of softening point temperature, Ai impact strength, and surface gloss. This result confirms that the rubber modified resin composition of Example 1-8 not only has no acetophenone residue, but also maintains the physical properties required for processing in the industry.

In addition, it can be seen from the above Table 3 that the rubber modified resin composition of Examples 1-6 has excellent performance in terms of a melting coefficient. This result indicates that, in the process of preparing the acrylate rubber graft copolymer (B), the graft polymerization reaction was performed by using less than 1.3 parts by weight and more than 0.35 parts by weight of hydrogen peroxide on pentane as an initiator, The rubber-modified resin composition can achieve good fluidity.

Although the present invention has been disclosed as above in the embodiments, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouches without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

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Claims (10)

A rubber modified resin composition comprising: a continuous phase formed by a styrene-acrylonitrile copolymer (A); a dispersed phase formed by an acrylate rubber graft copolymer (B); and p-pentane, wherein The content of the para-pentane is more than 5 ppm and less than 180 ppm, and the rubber modified resin composition does not contain acetophenone. The rubber modified resin composition according to item 1 of the scope of the patent application, wherein the content of the para-pentane is more than 8 ppm and less than 150 ppm. The rubber modified resin composition according to item 1 of the scope of patent application, wherein the total weight of the styrene-acrylonitrile copolymer (A) and the acrylate rubber graft copolymer (B) is based on the total weight The content of the styrene-acrylonitrile copolymer (A) is 40% to 90% by weight, and the content of the acrylic rubber graft copolymer (B) is 10% to 60% by weight. The rubber modified resin composition according to item 1 of the scope of patent application, wherein the rubber modified resin composition includes: the styrene-acrylonitrile copolymer (A) and the acrylate rubber 15 to 25% by weight of acrylonitrile-based monomer units, 55% to 65% by weight of styrene-based monomer units, and 15% to 25% by weight of acrylic acid based on the total weight of the branch copolymer (B) Ester-based monomer unit. The rubber modified resin composition according to item 1 of the patent application range, wherein the weight average particle diameter of the acrylic rubber graft copolymer (B) is a unimodal formula between 0.05 μm and 0.22 μm Distribution pattern, unimodal distribution pattern between 0.26 μm and 0.55 μm, or bimodal distribution pattern between 0.05 μm and 0.22 μm and between 0.26 μm and 0.55 μm . A method for preparing a rubber modified resin composition includes: providing a styrene-acrylonitrile copolymer (A) and an acrylate rubber graft copolymer (B); and the styrene-acrylonitrile copolymer (A) kneading with the acrylic rubber graft copolymer (B), wherein the rubber modified resin composition contains para-pentane, and the content of the para-pentane is more than 5 ppm and less than 180 ppm, And the rubber modified resin composition does not contain acetophenone. The method for preparing a rubber modified resin composition according to item 6 of the scope of patent application, wherein the method for providing the acrylic rubber graft copolymer (B) comprises: subjecting an acrylic monomer to an emulsion polymerization reaction, To form an acrylate-based rubber emulsion; and subjecting the acrylate-based rubber emulsion to a graft polymerization reaction, wherein the graft polymerization reaction includes the use of hydrogen peroxide to pentane as an initiator. The method for preparing a rubber modified resin composition according to item 7 of the scope of the patent application, wherein the total amount of hydrogen peroxide to pentane is less than 1.3 weight based on 100 parts by weight of the acrylate rubber emulsion. Parts and more than 0.35 parts by weight. The method for preparing a rubber modified resin composition according to item 7 of the scope of the patent application, wherein the emulsification polymerization reaction includes using the hydrogen peroxide-pentane as a starter. The method for preparing a rubber-modified resin composition according to item 9 of the scope of the patent application, wherein in the emulsification polymerization reaction, the hydrogen peroxide is used for the polymerization of 100 parts by weight of the acrylate monomer. The total amount of alkane used is less than 1 part by weight and greater than 0.05 part by weight, and in the graft polymerization reaction, based on 100 parts by weight of the acrylate-based rubber emulsion, the total use of hydrogen peroxide to pentane The amount is less than 1.3 parts by weight and greater than 0.35 parts by weight.