TW201425435A - Rubber-modified methacrylate-based resin composition - Google Patents

Abstract

This present invention provides a rubber-modified methacrylate-based resin composition comprising a continuous phase, formed with a copolymer(A) and, a dispersive phase, formed with an acrylate-based rubber grafted copolymer(B) as rubber particles. Said copolymer(A) contains 2 to 27 weight percentage of first styrene-acrylonitrile-based copolymer (A1), 30 to 75 weight percentage of methacrylate-based polymer (A2), and 10 to 50 weight percentage of second styrene-acrylonitrile-based copolymer (A3), based on 100 weight percentage of said copolymer(A). Said first styrene-acrylonitrile-based copolymer (A1) contains a styrene-based monomer unit, and 26 to 29 weight percentage of acrylonitrile-based monomer unit. Said second styrene-acrylonitrile-based copolymer (A3) contains a styrene-based monomer unit, and 31 to 40 weight percentage of acrylonitrile-based monomer unit.

Description

Rubber modified methacrylate resin composition

The present invention relates to a rubber modified methacrylate resin composition, and more particularly to a styrene-acrylonitrile copolymer containing a methacrylate polymer and a content of a high acrylonitrile monomer unit. A rubber modified methacrylate resin composition.

Most of the components contained in plastic molded articles for electrical equipment, household goods, and the like are rubber-modified styrene resins, polycarbonate resins, rubber-modified methacrylate resins, and the like. Wherein, the rubber modified methacrylate resin is a ternary graft copolymer comprising acrylonitrile, styrene and acrylate rubber, and has a lower double bond content than a rubber modified styrene resin. The acrylate rubber replaces the butadiene rubber, so the weather resistance is improved substantially. It is about 10 times higher than the rubber modified styrene resin. It can be directly used outdoors, and is typically used in automotive fields such as exterior mirrors. Outdoor components such as radiator grille, tail baffle, lampshade, etc.; or used in electrical and electronic fields, such as sewing machines, telephones, kitchen equipment, satellite antennas, etc.; or in the construction field. However, other properties such as tensile fracture strength, elongation, and heat resistance of the rubber-modified methacrylate-based resin have not yet reached the industry requirements.

In view of the above, there is still a need to develop a rubber-modified acrylate-based resin composition having a good balance of physical properties such as tensile strength, elongation, and heat resistance to meet the needs of the industry.

Accordingly, an object of the present invention is to provide a rubber-modified methacrylate-based resin composition having a good balance of physical properties such as tensile strength, elongation, and heat resistance.

Thus, the rubber modified methacrylate resin composition of the present invention comprises:

70% by weight to 90% by weight of the continuous phase formed by the copolymer (A), and 10% by weight to 30% by weight of the dispersed phase of the rubber particles of the acrylate rubber graft copolymer (B) to copolymerize The copolymer (A) contains 2% by weight to 27% by weight of the first styrene-acrylonitrile-based copolymer (A ₁ ), 30% by weight to 75% by weight based on 100% by weight of the total amount of the substance (A). a methacrylate polymer (A ₂ ) and 10% by weight to 50% by weight of a second styrene-acrylonitrile copolymer (A ₃ ); wherein the first styrene-acrylonitrile copolymer (A) ₁ ) comprising 71% by weight to 74% by weight of a styrene monomer unit and 26% by weight to 29% by weight of an acrylic monomer unit, and the second styrene-acrylonitrile type copolymer (A ₃ ) comprises 60 parts by weight % to 69% by weight of the styrene monomer unit and 31% to 40% by weight of the acrylic monomer unit.

Preferably, the first styrene-acrylonitrile-based copolymer (A ₁ ), from 35% by weight to 70% by weight, based on 100% by weight of the total copolymer (A), comprises from 5% by weight to 20% by weight. The methacrylate polymer (A ₂ ) and 12% by weight to 45% by weight of the second styrene-acrylonitrile copolymer (A ₃ ).

More preferably, the first styrene-acrylonitrile-based copolymer (A ₁ ), 50% by weight to 70% by weight, based on 100% by weight based on the total amount of the copolymer (A), comprises from 7% by weight to 18% by weight. The methacrylate polymer (A ₂ ) and 20% by weight to 32% by weight of the second styrene-acrylonitrile copolymer (A ₃ ).

Preferably, the first styrene-acrylonitrile-based copolymer (A ₁ ) comprises 72% by weight to 74% by weight of styrene-based monomer units and 26% by weight to 28% by weight of acrylonitrile-based monomer units.

Preferably, the second styrene-acrylonitrile-based copolymer (A ₃ ) comprises 62% by weight to 68% by weight of styrene-based monomer units, and 32% by weight to 38% by weight of acrylonitrile-based monomer units. .

Preferably, the rubber particles have a weight average particle diameter of from 0.05 μm to 1 μm.

More preferably, the rubber particles have a weight average particle diameter of from 0.05 μm to 0.22 μm, a weight average particle diameter of from 0.26 μm to 0.55 μm, or a mixture of the two.

Preferably, the copolymer (A) is contained in an amount ranging from 72% by weight to 86% by weight based on 100% by weight of the total of the rubber modified methacrylate resin composition, and the acrylate rubber is bonded. The content of the branched copolymer (B) ranges from 14% by weight to 28% by weight.

More preferably, the copolymer (A) is contained in an amount ranging from 73% by weight to 80% by weight based on 100% by weight of the total of the rubber-modified methacrylate-based resin composition, and an acrylate-based rubber joint The content of the branch copolymer (B) ranges from 20% by weight to 27% by weight.

The effect of the present invention is that the rubber modified methacrylate resin composition of the present invention is permeable to the methacrylate polymer (A ₂ ) and the second benzene having a high acrylonitrile monomer unit content. The ethylene-acrylonitrile-based copolymer (A ₃ ), and adjusting the content of the components, allows the rubber-modified methacrylate resin composition to have a good balance of physical properties such as tensile strength, elongation and heat resistance. Equal physical balance.

The rubber modified methacrylate resin composition of the present invention comprises: 70% by weight to 90% by weight of the continuous phase formed by the copolymer (A), and 10% by weight to 30% by weight of the acrylate rubber graft The dispersed phase of the rubber particles of the copolymer (B) is from 100% by weight based on the total amount of the copolymer (A), and the copolymer (A) comprises from 2% by weight to 27% by weight of the first styrene-propylene Nitrile copolymer (A ₁ ), 30% by weight to 75% by weight of methacrylate polymer (A ₂ ), and 10% by weight to 50% by weight of second styrene-acrylonitrile copolymer (A _{3 )} Wherein the first styrene-acrylonitrile-based copolymer (A ₁ ) comprises 71% by weight to 74% by weight of the styrene monomer unit and 26% by weight to 29% by weight of the acrylic monomer unit, The stilbene-acrylonitrile-based copolymer (A ₃ ) includes 60% by weight to 69% by weight of the styrene-based monomer unit and 31% by weight to 40% by weight of the acrylonitrile-based monomer unit.

Preferably, the first styrene-acrylonitrile-based copolymer (A ₁ ), from 35% by weight to 70% by weight, based on 100% by weight of the total copolymer (A), comprises from 5% by weight to 20% by weight. The methacrylate polymer (A ₂ ) and the second styrene-acrylonitrile copolymer (A ₃ ) in an amount of 12% by weight to 45% by weight.

More preferably, the first styrene-acrylonitrile-based copolymer (A ₁ ), 50% by weight to 70% by weight, based on 100% by weight based on the total amount of the copolymer (A), comprises from 7% by weight to 18% by weight. The methacrylate polymer (A ₂ ) and 20% by weight to 32% by weight of the second styrene-acrylonitrile copolymer (A ₃ ).

Preferably, the rubber particles have a weight average particle diameter of from 0.05 μm to 1 μm. . More preferably, the rubber particles have a weight average particle diameter of from 0.05 μm to 0.22 μm, a weight average particle diameter of from 0.26 μm to 0.55 μm, or a mixture of the two.

Preferably, the copolymer (A) is contained in an amount ranging from 72% by weight to 86% by weight based on 100% by weight of the total of the rubber modified methacrylate resin composition, and the acrylate rubber is bonded. The content of the branched copolymer (B) ranges from 14% by weight to 28% by weight.

Preferably, the copolymer (A) is contained in an amount ranging from 73% by weight to 80% by weight based on 100% by weight of the total of the rubber modified methacrylate resin composition, and the acrylate rubber is bonded. The content of the branch copolymer (B) ranges from 20% by weight to 27% by weight.

The first styrene-acrylonitrile copolymer (A ₁ ) and the acrylate rubber graft copolymer (B) form a graft copolymer mixture, which is described in detail as follows: the graft copolymer mixture is 100 weights Parts (dry weight) of the acrylate-based rubber emulsion and 20 parts by weight to 120 parts by weight of a single styrene-based monomer containing 60% by weight to 74% by weight and 26% by weight to 40% by weight of the acrylonitrile-based monomer The bulk mixture is obtained by graft polymerization.

The acrylate rubber emulsion is preferably produced by an emulsion polymerization method. The acrylate rubber emulsion is composed of an acrylate monomer as a main component, and specific examples of the acrylate monomer are, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and acrylic acid-2- Ethylhexyl ester, dodecyl acrylate, etc., of which n-butyl acrylate is preferred. The above acrylate rubber emulsion may be prepared by adding a graft bridging agent, for example, but not limited to, butylene diacrylate, two Vinyl benzene, butylene glycol dimethacrylate, dimethacrylate, trimethylolpropane tris(meth)acrylate, allyl methacrylate, diallyl methacrylate, Malay Diallyl acrylate, diallyl fumarate, diallyl phthalate, triallyl methacrylate, triallyl cyanurate, triallyl cyanurate, tricyclic An acrylate of a terpene alcohol, a diacrylate of a polyalkylene glycol, etc. These graft-grafting agents can be used individually or in combination of 2 or more types. Preferably, the graft bridging agent is used in an amount ranging from 0.1% by weight to 10% by weight based on 100% by weight of the total of the acrylate monomer and the grafting agent.

The acrylate rubber emulsion has a weight average particle diameter of from 0.05 μm to 1 μm, preferably an acrylate rubber emulsion having a weight average particle diameter of from 0.05 μm to 0.2 μm, and an acrylate having a weight average particle diameter of from 0.26 μm to 0.5 μm. A rubber emulsion, or a mixture of the two.

The graft polymerization of the graft copolymer mixture comprises graft polymerization of a monomer mixture comprising a styrene monomer and an acrylonitrile monomer in the presence of the above acrylate rubber emulsion, and the obtained graft copolymer mixture The weight average particle diameter of the rubber particles in the medium may be a unimodal distribution type or a bimodal distribution type. Preferably, the rubber particles have a weight average particle diameter of from 0.05 μm to 1 μm. More preferably, the weight average particle diameter is from 0.05 μm to 0.22 μm, the weight average particle diameter is from 0.26 μm to 0.55 μm, or a mixture of the two.

The graft polymerization of the above graft copolymer mixture comprises graft-polymerizing a monomer mixture onto the acrylate rubber; and grafting on the acrylate rubber can be simultaneously obtained according to the ratio of monomer addition and polymerization. Monomer unit copolymer and monomer unit copolymer not grafted onto the acrylate rubber. The first styrene-acrylonitrile copolymer (A ₁ ) of the present invention is a styrene-acrylonitrile monomer unit copolymer which is not grafted on the rubber; the acrylate rubber graft copolymer (B) It is formed of the acrylate rubber and a styrene-acrylonitrile monomer unit grafted on the acrylate rubber.

The graft ratio of the above acrylate rubber graft copolymer (B) can be controlled by polymerization conditions, for example, polymerization temperature, initiator, emulsifier, activator, chain transfer agent amount and type, single The amount of the body and the method of addition are controlled. The above chain transfer agent is specifically, for example, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and third. - Tert-dodecyl mercaptan. The emulsifier is not particularly limited, and is selected from various materials selected from the group consisting of sodium succinate, potassium fatty acid, sodium fatty acid, potassium dibasic succinate, and rosmarin soap in order to improve the stability of the emulsion during emulsion polymerization and to increase the polymerization rate. An anionic emulsifier such as a carboxylate, an alkyl sulfate, a sodium alkylbenzenesulfonate or the like, or an anionic emulsifier such as sodium polysulfonate. The above activator is specifically, for example, ferrous sulfate, sodium formaldehyde sulfoxylate, sodium ethylenediaminetetraacetate, tetrasodium pyrophosphate or the like.

The molecular weight of the above-mentioned graft copolymer mixture can also be adjusted by the polymerization temperature, the kind and amount of the initiator, the addition method of the monomer, and the like, and the reaction temperature of the graft polymerization is below 90 ° C, especially in It is preferably between 25 ° C and 40 ° C. The grafting monomer may be added at once, or may be added in portions, or may be continuously added or graft-polymerized into various monomers. Various conventional radical polymerization initiators can be used as the aforementioned initiator, and the manner of addition thereof can be used. It may be added in one time or continuously or incrementally; the specific examples of the above initiators are: benzoyl peroxide, layroyl peroxide, eighteen Oleyl peroxide, toluyl peroxide, dicumyl peroxide, tert-butyl-peroxide, Di-tert-butyl-diperphthalate, tert-butyl-peracetate, tert-butyl-perbenzoate, heavy Isoperopyl peroxy dicarbonate, 2,5-dimethyl-2,5-di(third butylperoxy)hexane [2,5-dimethyl-2,5-di ( Tert-butyl peroxy)hexane], 2,5-dimethyl-2,5-di(third butyl peroxide)-hexyl-3-tert-butyl hydroperoxide [2,5-dimethyl-2, 5-di(tert-butylperoxy)hexane-3-tert-butyl hydroperoxide], cumene hydroperoxide, p-methane hydroperoxide, cyclopentylation Hydrogen peroxide (cyclopentane hydroperoxide) , diisopropylbenzene hydroperoxide, p-tert-butylcumene hydroperoxide, pinane hydroperoxide, 2 , 5,5-dimethyl-hexane-2, 5-dihydroperoxide, or the like, or a mixture thereof. The initiator is used 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 monomer mixture.

Specific examples of the styrene monomer used in the graft polymerization of the aforementioned graft copolymer mixture: styrene, α-methylstyrene, p-tert-butyl Styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, α-methyl-p-methylstyrene And bromostyrene, etc., of which styrene or α-methylstyrene is preferred. Specific examples of the above-mentioned acrylonitrile-based monomer include acrylonitrile and α-methacrylonitrile, and among them, acrylonitrile is preferred.

[methacrylate polymer (A ₂ )]

The methacrylate polymer (A ₂ ) of the present invention is selected from a methacrylate homopolymer, a methacrylate-acrylate copolymer, or a combination thereof. The methacrylate polymer (A ₂ ) has a weight average molecular weight of 50,000 to 450,000, preferably 70,000 to 200,000, and most preferably 70,000 to 150,000.

Preferably, the methacrylate-acrylate copolymer comprises 80% by weight to 99.8% by weight of methacrylate monomer units and 0.2% by weight to 20% by weight of acrylate monomer units. More preferably, the methacrylate-acrylate copolymer comprises from 85% by weight to 98% by weight of the methacrylate monomer unit and from 2% by weight to 15% by weight of the acrylate monomer unit.

The above methacrylate-acrylate copolymer is obtained by polymerization of a component including a monomethacrylate monomer and an acrylate monomer. The polymerization can be carried out by bulk, solution, suspension or emulsion polymerization. Preferably, the polymerization is carried out at a temperature ranging from 50 ° C to 160 ° C.

The above methacrylate monomers may be used singly or in combination, and the methacrylate monomers are, for example but not limited to, methyl methacrylate, methyl propyl acrylate. Ethyl acrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, methacrylate 2- Hydroxyethyl ester, glycidyl methacrylate, dimethylaminoethyl methacrylate, ethylene dimethacrylate, or neopentyl dimethacrylate. Preferably, the methacrylate monomer is selected from methyl methacrylate, butyl methacrylate, or a combination thereof.

The acrylate monomer may be used singly or in combination, and the acrylate monomer is, for example but not limited to, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, or polyethylene glycol diacrylate. Preferably, the acrylate monomer is butyl acrylate.

[Second styrene-acrylonitrile copolymer (A ₃ )]

The second styrene-acrylonitrile-based copolymer (A ₃ ) of the present invention is composed of a group comprising 55% by weight to 68% by weight of a styrene-based monomer and 32% by weight to 45% by weight of an acrylic monomer. The fraction is obtained by polymerization. The polymerization reaction may be a bulk, solution, suspension or emulsion polymerization method, wherein a bulk or solution polymerization method is preferred, and specific examples of the above styrene monomer and acrylonitrile monomer are described above. The monomers used for the graft polymerization of the copolymer mixture are the same and will not be described again.

The preferred preparation method of the second styrene-acrylonitrile copolymer (A ₃ ) of the present invention can be carried out by a continuous block or solution polymerization reactor comprising: a columnar flow reaction , a fully mixed (CSTR) reactor, or a tube reactor containing a static mixing element, etc., wherein a fully mixed reactor is preferred, and the number of the above reactors may be one, or two or more may be used in combination. In the production of the second styrene-acrylonitrile-based copolymer (A ₃ ) of the present invention, the polymerization initiator may be added to the reaction by thermal polymerization or, for example, but not limited to, ruthenium peroxide. Oxide esters, peroxy ketals, peroxycarbonates, azo compounds having a nitro group and cyclohexanes, and the like. The polymerization initiator is added in an amount ranging from 0 part by weight to 1.0 part by weight, preferably from 0.01 part by weight to 0.5 part by weight, based on 100 parts by total of the total amount of the monomers.

The second styrene-acrylonitrile-based copolymer (A ₃ ) of the present invention comprises 60% by weight to 69% by weight of styrene-based monomer units, and 31% by weight to 40% by weight of acrylonitrile-based monomer units. Preferably, the second styrene-acrylonitrile-based copolymer (A3) comprises 62% by weight to 68% by weight of styrene-based monomer units, and 32% by weight to 38% by weight of acrylonitrile-based monomer units. The second styrene-acrylonitrile-based copolymer (A ₃ ) has a weight average molecular weight of from 60,000 to 400,000, preferably from 80,000 to 300,000.

The method for preparing the rubber-modified methacrylate resin composition of the present invention is not particularly limited, and a general mixing method such as a first styrene-acrylonitrile-based copolymer (A ₁ ) and the like may be employed. The graft copolymer mixture formed by the acrylate rubber graft copolymer (B) and the methacrylate polymer (A ₂ ) are uniformly mixed with the second styrene-acrylonitrile copolymer (A ₃ ). Further, an additive may be further selectively added; in order to obtain the rubber-modified methacrylate-based resin composition of the present invention, the mixing method is representative: after dry mixing by a generally used Hanschel mixer The mixture is melt-mixed by a mixer such as an extrusion mixer, a kneader or a Banbury mixer.

The rubber modified methacrylate resin composition of the present invention further contains an additive selected from the group consisting of an antioxidant, a plasticizer, a processing aid, an ultraviolet stabilizer, a UV absorber, a filler, a reinforcing agent, and a coloring agent. Agent, slip agent, antistatic agent, flame retardant, flame retardant, thermal stabilizer, coupling agent, or a combination thereof. The additive may be respectively in the polymerization reaction of the above graft copolymer mixture with the methacrylate polymer (A ₂ ), the second styrene-acrylonitrile copolymer (A ₃ ), after the polymerization reaction, and before the condensation. Or added during the preparation of the rubber-modified methacrylate resin composition. The content of the additive is in the range of 100 parts by weight based on 100 parts by weight of the total of the graft copolymer mixture and the methacrylate polymer (A ₂ ) and the second styrene-acrylonitrile copolymer (A ₃ ). From 0.01 parts by weight to 20 parts by weight.

The antioxidant may be used singly or in combination, and the antioxidant is, for example but not limited to, a phenol-based antioxidant, a thioether-based antioxidant, or a phosphorus-based antioxidant.

The phenolic antioxidant may be used singly or in combination, and the phenolic antioxidant is, for example but 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'-ethylenediamine-bis[ethyl-3-( 3,5-Bis-tert-butyl-4-hydroxyphenyl)propionate].

The thioether-based antioxidant may be used singly or in combination, and the thioether-based antioxidant is, for example but not limited to, distearyl thiodipropionate, dipalmitoside dipropionate, 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 a phosphorus-based antioxidant selected from a phosphite or a phosphate-based phosphorus-based antioxidant. The phosphite-containing phosphorus-based antioxidants such as, but not limited to, tris(nonylphenyl) phosphite, dodecyl phosphite, 4,4'-butylene bis(3-methyl-6- Tributylphenyl-bistridecylphosphite) or tris(2,4-tert-butylphenyl)phosphite. The phosphate-containing phosphorus-based antioxidant such as, but 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 is, for example but not limited to, metal soap such as calcium stearate, magnesium stearate, lithium stearate, or 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 or a petroleum wax.

The invention will be further illustrated by the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as The restrictions imposed by the implementation.

[Preparation Example 1] Graft Copolymer Mixture

The first styrene-acrylonitrile-based copolymer (A ₁ ) and the acrylate rubber graft copolymer (B) form a graft copolymer mixture, and the graft copolymer mixture is produced as follows:

(1) First, an acrylate-based rubber emulsion having a weight average particle diameter of 0.1 μm is obtained by polymerizing 99.0% by weight of n-butyl acrylate and 1.0% by weight of allyl methacrylate, and has a solid content of about 38% by weight. The average particle diameter was 0.1 μm.

(2) Next, an acrylate-based rubber emulsion having a weight average particle diameter of 0.4 μm is used.

The solid content was about 38% and the weight average particle diameter was 0.4 μm.

(3) Finally, 70% by weight of the above acrylate rubber emulsion having a weight average particle diameter of 0.1 μm and 30% by weight of the above acrylate rubber emulsion having a weight average particle diameter of 0.4 μm were grafted according to the following formula. Polymerization.

Distilled water 3000

After polymerization for 5 hours, the calcium chloride (CaCl ₂ ) is coagulated, dehydrated, and then dried to a moisture content of 2% or less to obtain a graft copolymer mixture, and the rubber particles have a weight average particle diameter of 0.12 μm. , 0.45 μm bimodal distribution pattern. The content of the acrylonitrile monomer unit of the first styrene-acrylonitrile-based copolymer (A ₁ ) in the above graft copolymer mixture was 28% by weight.

[Preparation Example 2]

The methacrylate polymer (A ₂ ) was manufactured by Chi Mei Co., product model Acryrex CM-205.

[Preparation Example 3] Second styrene-acrylonitrile copolymer (A ₃ )

The raw materials of 60% by weight of styrene and 40% by weight of acrylonitrile were mixed at a rate of 12 kg/hr, and then 3.0 g/hr of ethylenedistearylamine, benzammonium peroxide, and thirteen-dodecylsulfide. The alcohol and the recovered liquid formed by the condensation of the volatile matter removed by the reaction described later were combined as a feed liquid to supply a continuous kettle type reactor equipped with a stirrer at a temperature of 108 ° C and a volume of 45 liters.

When the reaction liquid was removed by a devolatilization apparatus to obtain a volatile component, a second styrene-acrylonitrile-based copolymer having an acrylonitrile unit content of 32% by weight was obtained.

[Preparation Example 4]

The raw materials of 68% by weight of styrene and 32% by weight of acrylonitrile were mixed at a rate of 12 kg/hr, and then 3.0 g/hr of ethylenedistearylamine, benzammonium peroxide, and thirteen-dodecylsulfide. The alcohol, and the recovered liquid formed by the condensation of the volatiles removed by the reaction described later, are combined as a feed liquid, and supplied to the continuous kettle type with a stirrer maintained at a temperature of 108 ° C and a volume of 45 liters. The device.

When the reaction liquid was removed by a devolatilization apparatus to obtain a volatile component, a styrene-acrylonitrile-based copolymer (C) having an acrylonitrile unit content of 28% by weight was obtained.

[Example 1]

In a dry state, 34.9% by weight [Example 1] Preparation of graft copolymer mixture (B + A _1), 45% by weight [Example 2] Preparation of methacrylate - methacrylate copolymer ( A ₂ ), 20.1% by weight of the second styrene-acrylonitrile-based copolymer (A ₃ ) of [Preparation Example 3] was kneaded at a kneading temperature of 220 ° C by a biaxial extruder, and then mixed by an extruder, and then The rubber modified methacrylate resin composition of the present invention was obtained, and the physical properties thereof were as shown in Table 2. in

[Example 1 and Comparative Examples 1 to 2]

In Example 1 and Comparative Examples 1 and 2, the rubber modified methacrylate resin composition was prepared by the same kneading extrusion method as in Example 1, except that the type and amount of each raw material were changed. Table 1, the analysis and physical property evaluation results are shown in Table 2.

【Test items】

1. Melting coefficient (indicating liquidity, melt index, referred to as MI) measurement:

The rubber-modified methacrylate-based resin compositions of Example 1 and Comparative Examples 1 and 2 were tested in accordance with D-1238 at 220 ° C × 10 kg, and the unit was g/10 min.

2. Measurement of softening point temperature (Vicat softening temp.):

The rubber modified methacrylate resin composition of Example 1 and Comparative Examples 1 to 2 was measured for softening point temperature in accordance with ASTM D-1525, and the unit was °C.

3. Elongation (EL) measurement:

The rubber modified methacrylate resin composition of Example 1 and Comparative Examples 1 to 2 was measured for elongation (unit: %) according to the ASTM D-638 method.

4. Tensile strength (TSb) measurement:

The rubber-modified methacrylate-based resin compositions of Example 1 and Comparative Examples 1 and 2 were defined in accordance with ASTM D-638 test method, and the unit was kg/cm ² .

5. Determination of the weight average particle diameter of the rubber particles of the rubber modified methacrylate resin composition:

The rubber-modified methacrylate-based resin compositions of Example 1 and Comparative Examples 1 and 2 were each photographed by an ultra-thin sectioning method of an electron microscope and calculated by the following formula, and the photograph contained at least 300 particles or more:

Wherein ni represents the particle diameter of the rubber particles; Di represents the number of rubber particles.

In summary, the rubber modified methacrylate resin composition of the present invention is permeable to the methacrylate polymer (A ₂ ) and the second styrene-acrylonitrile copolymer (A ₃ ), and the The content of the component may be such that the rubber modified methacrylate resin composition has good physical properties such as good tensile strength, elongation and heat resistance, and the physical properties such as the resin composition are balanced, so The object of the invention is achieved.

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 (9)

A rubber modified methacrylate resin composition comprising: 70% by weight to 90% by weight of a continuous phase formed by the copolymer (A), and 10% by weight to 30% by weight of an acrylate-based rubber graft copolymerization The dispersed phase of the rubber particles of the substance (B) is from 100% by weight based on the total amount of the copolymer (A), and the copolymer (A) comprises from 2% by weight to 27% by weight of the first styrene-acrylonitrile Copolymer (A ₁ ), 30% by weight to 75% by weight of methacrylate polymer (A ₂ ) and 10% by weight to 50% by weight of second styrene-acrylonitrile copolymer (A ₃ ) Wherein the first styrene-acrylonitrile-based copolymer (A ₁ ) comprises 71% by weight to 74% by weight of styrene-based monomer units and 26% by weight to 29% by weight of acrylonitrile-based monomer units, and second The styrene-acrylonitrile-based copolymer (A ₃ ) includes 60% by weight to 69% by weight of the styrene monomer unit and 31% by weight to 40% by weight of the acrylic monomer unit. The rubber-modified methacrylate-based resin composition according to claim 1, wherein the total amount of the copolymer (A) is 100% by weight, and the styrene is included in an amount of 5% by weight to 20% by weight. Acrylonitrile-based copolymer (A ₁ ), 35% by weight to 70% by weight of methacrylate-based polymer (A ₂ ), and 12% by weight to 45% by weight of second styrene-acrylonitrile-based copolymer (A ₃ ). The rubber-modified methacrylate-based resin composition according to claim 2, wherein the total amount of the copolymer (A) is 100% by weight, including 7 to 18% by weight of the first styrene- Acrylonitrile copolymer (A ₁ ), 50% by weight to 70% by weight of methacrylate polymer (A ₂ ), and 20% by weight to 32% by weight of second styrene-acrylonitrile copolymer (A ₃ ). The rubber-modified methacrylate-based resin composition according to claim 1, wherein the first styrene-acrylonitrile-based copolymer (A ₁ ) comprises 72% by weight to 74% by weight of a styrene-based monomer. The unit and 26% by weight to 28% by weight of the acrylic monomer unit. The rubber-modified methacrylate-based resin composition according to claim 1, wherein the second styrene-acrylonitrile-based copolymer (A ₃ ) comprises 62% by weight to 68% by weight of a styrene-based monomer. a unit, and 32% by weight to 38% by weight of an acrylic monomer unit. The rubber-modified methacrylate-based resin composition according to claim 1, wherein the rubber particles have a weight average particle diameter of from 0.05 μm to 1 μm. The rubber-modified methacrylate-based resin composition according to claim 6, wherein the rubber particles have a weight average particle diameter of from 0.05 μm to 0.22 μm, a weight average particle diameter of from 0.26 μm to 0.55 μm, or the foregoing two Mixed. The rubber-modified methacrylate-based resin composition according to claim 1, wherein the copolymer (A) is 100% by weight based on the total amount of the rubber-modified methacrylate resin composition. The content ranges from 72% by weight to 86% by weight, and the content of the acrylate-based rubber graft copolymer (B) ranges from 14% by weight to 28% by weight. The rubber-modified methacrylate resin composition according to claim 8, wherein the rubber-modified methacrylate resin composition is a total of The content of the copolymer (A) is in the range of 73% by weight to 80% by weight based on 100% by weight, and the content of the acrylate-based rubber graft copolymer (B) is in the range of 20% by weight to 27% by weight.