CN110845807A

CN110845807A - Rubber modified resin composition and molded article produced from the same

Info

Publication number: CN110845807A
Application number: CN201910404048.1A
Authority: CN
Inventors: 薛展立; 林耕竹
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2018-08-20
Filing date: 2019-05-15
Publication date: 2020-02-28
Also published as: KR20200021430A; TW202009268A; TWI675875B

Abstract

A rubber-modified resin composition comprising: 27 to 43% by weight of an acrylate-based rubber graft copolymer (a), 54 to 70% by weight of a styrene-acrylonitrile copolymer (B), and 1 to 15% by weight of a styrene-unsaturated dicarboxylic anhydride copolymer (C); wherein the styrene-acrylonitrile copolymer (B) comprises 27 to 35% by weight of an acrylonitrile monomer unit. The invention also provides a molded product prepared from the rubber modified resin composition, which has the physical characteristics of high heat resistance, good fluidity, impact resistance and the like in balance.

Description

Rubber modified resin composition and molded article produced from the same

Technical Field

The present invention relates to a resin composition, and more particularly to a rubber modified resin composition and a molded article prepared therefrom.

Background

In general, most of components contained in plastic molded articles used for electric appliances, household goods, and the like are rubber-modified styrene resins, polycarbonate resins (polycarbonate resins), rubber-modified methacrylate resins, and the like. The rubber modified methacrylate resin is a ternary graft copolymer consisting of acrylonitrile, styrene and acrylate rubber, and compared with the rubber modified styrene resin, the acrylate rubber with low double bond content replaces butadiene rubber, so the weather resistance is essentially improved, is about 10 times higher than that of the rubber modified styrene resin, can be directly used outdoors, and is typically applied to outdoor parts in the automobile field, such as exterior mirrors, radiator grilles, tail baffles, lampshades and the like; or in the field of electronics, for example: all-weather shells such as sewing machines, telephones, kitchen equipment, satellite antennas and the like; or applied to the building field and the like. However, the impact strength of the rubber-modified methacrylic ester-based resin is inferior to that of the rubber-modified styrene-based resin, and if the amount of the rubber used is increased in order to improve the impact resistance, the fluidity thereof is deteriorated. Further, the heat resistance of the rubber-modified methacrylate resin has not yet reached the industrial demand.

Therefore, it has become an urgent subject to be studied in the industry how to prepare a thermoplastic resin composition having the advantages of good impact resistance, fluidity and heat resistance.

Disclosure of Invention

The present invention relates to a rubber-modified resin composition and a molded article obtained therefrom, which have physical properties in a balance of high heat resistance, good fluidity, impact resistance and the like.

According to an embodiment, a rubber modified resin composition is provided, comprising: 27 to 43% by weight of an acrylate-based rubber graft copolymer (a), 54 to 70% by weight of a styrene-acrylonitrile copolymer (B), and 1 to 15% by weight of a styrene-unsaturated dicarboxylic anhydride copolymer (C); wherein the styrene-acrylonitrile copolymer (B) comprises 27 to 35% by weight of an acrylonitrile monomer unit.

According to one embodiment, the rubber modified resin composition comprises 29 to 38 wt% of an acrylate rubber graft copolymer (a), 58 to 67 wt% of a styrene-acrylonitrile copolymer (B), and 1.5 to 10 wt% of a styrene-unsaturated dicarboxylic anhydride copolymer (C).

According to one embodiment, the acrylate-based rubber graft copolymer (a) includes rubber particles and a graft copolymer, and the weight average particle size of the rubber particles is bimodal distribution of 0.10 μm to 0.20 μm and 0.30 μm to 0.50 μm.

According to one embodiment, the styrene-acrylonitrile copolymer (B) includes 65 to 73 wt% of a styrenic monomer unit, 27 to 35 wt% of an acrylonitrile monomer unit, and 0 to 8 wt% of other copolymerizable monomer unit.

According to one embodiment, the styrene-acrylonitrile copolymer (B) includes 70 to 72 wt% of a styrenic monomer unit, 28 to 30 wt% of an acrylonitrile monomer unit, and 0 to 2 wt% of other copolymerizable monomer unit.

According to one embodiment, the styrene-acrylonitrile copolymer (B) has a weight average molecular weight of 10 to 20 ten thousand.

According to one embodiment, the styrene-acrylonitrile copolymer (B) has a weight average molecular weight of 11 to 15 ten thousand.

According to an embodiment, the styrene-unsaturated dicarboxylic anhydride-based copolymer (C) comprises 45 to 95 mol% of styrene-based monomer units, 1 to 55 mol% of unsaturated dicarboxylic anhydride-based monomer units, and 0 to 54 mol% of unsaturated dicarboxylic imide-based monomer units. Wherein, the mol% refers to mole percentage.

According to one embodiment, the styrene-unsaturated dicarboxylic anhydride-based copolymer (C) has a weight average molecular weight of 6 to 25 ten thousand.

According to an embodiment, the acrylate-based rubber graft copolymer (a) includes rubber particles and a graft copolymer, the graft copolymer of the acrylate-based rubber graft copolymer (a), the styrene-acrylonitrile-based copolymer (B) and the styrene-unsaturated dicarboxylic anhydride-based copolymer (C) form a continuous phase, and the rubber particles of the acrylate-based rubber graft copolymer (a) form a dispersed phase, wherein the rubber-modified resin composition includes 70 wt% to 90 wt% of the continuous phase and 10 wt% to 30 wt% of the dispersed phase, based on 100 wt% of the total content of the rubber-modified resin composition.

According to one embodiment, a molded article is provided, which is formed from the rubber modified resin composition.

The invention has the beneficial effects that:

the rubber modified resin composition of the present invention has high heat resistance, good fluidity, impact resistance and other physical properties, and can obtain a composition with good balance of physical properties. And according to the physical property requirements required by the application products, the rubber modified resin composition meeting the physical property requirements of the products is prepared.

Detailed Description

In the embodiment of the invention, a rubber modified resin composition and a molded product prepared by using the same are provided. The rubber-modified resin composition of the example comprises: an acrylic rubber graft copolymer (A), a styrene-acrylonitrile copolymer (B), and a styrene-unsaturated dicarboxylic anhydride copolymer (C). In one embodiment (but not limited thereto), the rubber modified resin composition of the present invention is, for example, an acrylate rubber modified resin composition, a rubber modified styrene-acrylonitrile resin composition, or an acrylate rubber modified styrene-acrylonitrile resin composition.

In one embodiment, the rubber modified resin composition comprises: 27 to 43% by weight of an acrylate-based rubber graft copolymer (a), 54 to 70% by weight of a styrene-acrylonitrile copolymer (B), and 1 to 15% by weight of a styrene-unsaturated dicarboxylic anhydride copolymer (C); wherein the styrene-acrylonitrile copolymer (B) comprises 27 to 35% by weight of an acrylonitrile monomer unit. In one embodiment, the styrene-acrylonitrile copolymer (B) comprises 65 wt% to 73 wt% of styrene monomer units, 27 wt% to 35 wt% of acrylonitrile monomer units, and 0 wt% to 8 wt% of other copolymerizable monomer units.

In another embodiment, a rubber modified resin composition comprises: 29 to 38% by weight of an acrylate-based rubber graft copolymer (A), 58 to 67% by weight of a styrene-acrylonitrile copolymer (B), and 1.5 to 10% by weight of a styrene-unsaturated dicarboxylic anhydride copolymer (C). In another embodiment, the styrene-acrylonitrile copolymer (B) comprises 68 to 72.5 wt% of styrenic monomer units, 27.5 to 32 wt% of acrylonitrile monomer units, and 0 to 4.5 wt% of other copolymerizable monomer units. In another embodiment, the styrene-acrylonitrile copolymer (B) includes 70 to 72 wt% of styrene monomer units, 28 to 30 wt% of acrylonitrile monomer units, and 0 to 2 wt% of other copolymerizable monomer units.

In one embodiment, the acrylate-based rubber graft copolymer (A) includes rubber particles and a graft copolymer, wherein the weight average particle size of the rubber particles is bimodal distribution of 0.10 μm to 0.20 μm and 0.30 μm to 0.50 μm. In another embodiment, the rubber particles have a bimodal distribution of weight average particle sizes of 0.10 μm to 0.18 μm and 0.35 μm to 0.50 μm. In another embodiment, the rubber particles have a bimodal distribution of weight average particle sizes of 0.10 μm to 0.15 μm and 0.40 μm to 0.50 μm.

In one embodiment, the rubber particles comprise 90 wt% to 100 wt% of acrylate-based rubber particles, based on 100 wt% of the total content of the rubber particles.

Further, in one embodiment, the styrene-acrylonitrile copolymer (B) of the rubber-modified resin composition has a weight average molecular weight of 10 to 20 ten thousand. In another embodiment, the styrene-acrylonitrile copolymer (B) has a weight average molecular weight of 10.5 to 17 ten thousand. In another embodiment, the styrene-acrylonitrile copolymer (B) has a weight average molecular weight of 11 to 15 ten thousand.

In one embodiment, the styrene-unsaturated dicarboxylic anhydride copolymer (C) comprises 45 mol% to 95 mol% of styrene monomer units, 1 mol% to 55 mol% of unsaturated dicarboxylic anhydride monomer units, and 0 mol% to 54 mol% of unsaturated dicarboxylic imide monomer units. In another embodiment, the styrene-unsaturated dicarboxylic anhydride-based copolymer (C) comprises 50 to 90 mol% of styrene-based monomer units, 2 to 45 mol% of unsaturated dicarboxylic anhydride-based monomer units, and 5 to 46 mol% of unsaturated dicarboxylic imide-based monomer units. In another embodiment, the styrene-unsaturated dicarboxylic anhydride-based copolymer (C) comprises 55 to 85 mol% of styrene-based monomer units, 3 to 35 mol% of unsaturated dicarboxylic anhydride-based monomer units, and 10 to 35 mol% of unsaturated dicarboxylic imide-based monomer units.

In one embodiment, the weight average molecular weight of the styrene-unsaturated dicarboxylic anhydride copolymer (C) is from 6 to 25 ten thousand. In another embodiment, the weight average molecular weight of the styrenic-unsaturated dicarboxylic anhydride-based copolymer (C) is from 8 to 22 ten thousand. In another embodiment, the weight average molecular weight of the styrenic-unsaturated dicarboxylic anhydride-based copolymer (C) is from 10 to 19 ten thousand.

In one embodiment, the acrylate-based rubber graft copolymer (a) includes rubber particles and a graft copolymer; the graft copolymer of the acrylic rubber graft copolymer (A), the styrene-acrylonitrile copolymer (B) and the styrene-unsaturated dicarboxylic anhydride copolymer (C) form a continuous phase, and the rubber particles of the acrylic rubber graft copolymer (A) form a dispersed phase. In one embodiment, the rubber modified resin composition comprises 70 wt% to 90 wt% of a continuous phase and 10 wt% to 30 wt% of a dispersed phase, based on 100 wt% of the total content of the rubber modified resin composition. In another embodiment, it comprises 72 wt% to 88 wt% of a continuous phase and 12 wt% to 28 wt% of a dispersed phase, based on 100 wt% of the total content of the rubber-modified resin composition. In another embodiment, it comprises 74 to 86 wt% of continuous phase and 14 to 26 wt% of dispersed phase based on the total content of the rubber modified resin composition being 100 wt%.

In one application example, a molded article is prepared from the rubber modified resin composition of the above example.

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

[ acrylate-based rubber graft copolymer (A) ]

The acrylic ester-based rubber graft copolymer (A) includes rubber particles and a graft copolymer. The rubber particles include acrylate rubber particles obtained by polymerizing an acrylate monomer as a main component. In one embodiment, the acrylate-based rubber particles include 90 wt% to 100 wt% of acrylate-based monomer units and 0 wt% to 10 wt% of other copolymerizable monomer units.

In one embodiment of the present invention, a method for preparing the acrylate-based rubber graft copolymer (a) includes: graft polymerization of the acrylate-based rubber emulsion was carried out. In detail, the preparation method of the acrylate rubber emulsion comprises the following steps: an acrylate monomer is subjected to emulsion polymerization in the presence of an initiator. The acrylate-based rubber emulsion is preferably prepared by an emulsion polymerization method. The acrylate rubber latex is prepared by polymerizing acrylate monomers as a main component. In one embodiment, the acrylate-based rubber emulsion comprises 90 wt% to 100 wt% of acrylate-based monomer units, 0 wt% to 10 wt% of other copolymerizable monomer units, and 0 wt% to 10 wt% of other mixtures.

The above acrylate monomers may be used alone or in combination, and the acrylate monomers are, for example, but not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, etc., with n-butyl acrylate being preferred. The above-mentioned other copolymerizable monomers may be used alone or in combination, and the other copolymerizable monomers are, for example, but not limited to, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, benzyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, ethylene glycol dimethacrylate, or neopentyl dimethacrylate, etc. The above-mentioned other mixtures may be used alone or in admixture, and the other mixtures are exemplified by, but not limited to, initiators, graft-linking agents, emulsifiers, activators, chain transfer agents, and the like.

As the above-mentioned initiator, various conventional radical polymerization initiators can be used, and the addition thereof may be carried out by one-time addition, continuous or incremental addition, etc.; specific examples of the above-mentioned initiator: dibenzoyl peroxide (benzoyl peroxide), lauroyl peroxide (lauroyl peroxide), octadecanoyl peroxide (oleyl peroxide), toluoyl peroxide (toluyl peroxide), cumyl peroxide (dicumyl peroxide), t-butyl peroxide (tert-butyl peroxide), t-butyl hydroperoxide (tert-butyl hydroperoxide), di-t-butyl-dipentyl-phthalate, t-butyl-peracetate, isopropylperoxy dicarbonate, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane [2,5-dimethyl-2,5-di (tert-butyl peroxide) ], 5-di (t-butyl peroxide) -hexyl-3-t-butylhydroperoxide [2,5-dimethyl-2,5-di (t-butyl peroxide) hexane-3-t-butyl hydroperoxide ], cumene hydroperoxide (cumene hydroperoxide), p-menthane hydroperoxide, cyclopentylated hydroperoxide, diisopropylated hydroperoxide, p-t-butylisopropylbenzene hydroperoxide, pinane hydroperoxide, 2,5-dimethyl-2, 5-dihydroxide, and the like, or mixtures thereof. The initiator is used in an amount ranging from 0.01 parts by weight to 5 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture.

The acrylic rubber emulsion may be prepared by polymerizing with the addition of a graft-linking agent such as, but not limited to, ethylene diacrylate, butylene diacrylate, divinylbenzene, butylene glycol dimethacrylate, trimethylolpropane tri (meth) acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl methacrylate, triallyl cyanurate, triallyl isocyanurate, the acrylate of tricyclodecenylalcohol, the diacrylate of polyalkylene glycol, and the like, and these graft-linking agents may be used alone or in combination of 2 or more. Preferably, the total amount of the acrylate monomers and the graft-linking agent is 100 wt%, and the usage amount of the graft-linking agent is 0.1 wt% to 10 wt%.

In one embodiment, but not limited thereto, the graft polymerization of the acrylate-based rubber graft copolymer (a) comprises graft polymerizing 100 parts by weight (dry weight) of the acrylate-based rubber emulsion with 50 to 100 parts by weight of a monomer mixture comprising 64 to 78% by weight of a styrenic monomer and 22 to 36% by weight of an acrylonitrile-based monomer, which may be used alone or in combination, and styrenic monomers such as, but not limited to, styrene, α -methylstyrene, p-t-butylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2, 4-dimethylstyrene, ethylstyrene, α -methyl-p-methylstyrene, bromostyrene, etc., wherein styrene or α -methylstyrene or a combination thereof is preferred.

The graft polymerization reaction of the acrylate-based rubber graft copolymer (a) comprises graft polymerizing a monomer mixture onto the acrylate-based rubber; in an embodiment (but not limited thereto), the graft copolymer in the acrylate-based rubber graft copolymer (a) may include a monomer unit copolymer in which a monomer mixture is grafted on the acrylate-based rubber and a monomer unit copolymer in which a monomer mixture is not grafted on the acrylate-based rubber, depending on the ratio of the monomers added and the polymerization conditions. In one example, the acrylate-based rubber graft copolymer (a) is formed by an acrylate-based rubber and a graft copolymer grafted to the acrylate-based rubber, wherein the graft copolymer is a monomer unit copolymer formed by polymerization of a styrene-based monomer and an acrylonitrile-based monomer.

The weight-average particle diameter of the rubber particles in the acrylic rubber emulsion and the graft ratio of the acrylic rubber graft copolymer (a) can be controlled by polymerization conditions such as: the polymerization temperature, the amount and kind of initiator, emulsifier, activator, chain transfer agent, the amount of monomer and the method of addition. The molecular weight of the acrylate-based rubber graft copolymer (A) can also be adjusted by changing the polymerization conditions such as the polymerization temperature, the type and amount of the initiator, and the method of adding the monomer, and the reaction temperature of the graft polymerization is preferably 90 ℃ or lower, particularly preferably 25 to 40 ℃. The monomer for grafting can be added at one time, or added in batches, or continuously added or various monomers are grafted and polymerized in stages.

Specific examples of the chain transfer agent include n-butyl mercaptan (n-butyl mercaptan), n-octyl mercaptan (n-octyl mercaptan), n-dodecyl mercaptan (n-dodecyl mercaptan), and tert-dodecyl mercaptan (tert-dodecyl mercaptan). In one embodiment, the chain transfer agent is used in an amount ranging from 0.01 to 0.1 parts by weight, based on 100 parts by weight of the total monomer mixture. The emulsifier is not particularly limited, and is selected from various carboxylic acid salts such as sodium succinate, potassium fatty acid, sodium fatty acid, dipotassium alkenyl succinate, and soap rose acid, in order to improve the stability of the emulsion during emulsion polymerization and to increase the polymerization rate; various sulfonates such as dioctyl Sodium sulfosuccinate (Sodium dihexyl sulfosuccinate), alkyl sulfates, Sodium alkylbenzenesulfonate, etc.; anionic emulsifiers such as sodium polyoxyethylene nonylphenyl ether sulfate are preferred. In one embodiment, the emulsifier is used in an amount ranging from 1 part by weight to 10 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture. Examples of the activator include ferrous sulfate, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, and tetrasodium pyrophosphate. In one embodiment, the activator is used in an amount ranging from 1 part by weight to 10 parts by weight, based on 100 parts by weight of the total monomer mixture.

In one embodiment, the weight average particle diameter of the rubber particles in the acrylate rubber graft copolymer (A) may be a monomodal distribution or a bimodal distribution. In another embodiment, the acrylate-based rubber graft copolymer (a) may include two or more rubber particles having different weight average particle diameters, and the two or more rubber particles having different weight average particle diameters may be prepared by separately performing graft polymerization on two acrylate-based rubber emulsions and then mixing them, or by performing graft polymerization on two acrylate-based rubber emulsions in a mixed state.

In one embodiment, the weight average particle size of the acrylate rubber particles is bimodal distribution of 0.10 μm to 0.20 μm and 0.30 μm to 0.50 μm, preferably 0.10 μm to 0.18 μm and 0.35 μm to 0.50 μm, more preferably 0.10 μm to 0.15 μm and 0.40 μm to 0.50 μm.

[ styrene-acrylonitrile copolymer (B) ]

In one embodiment of the present invention, the styrene-acrylonitrile copolymer (B) is prepared by polymerizing a monomer mixture comprising a styrene monomer, an acrylonitrile monomer and optionally other copolymerizable monomers. In one embodiment, the styrene-acrylonitrile copolymer (B) comprises 65 wt% to 73 wt% of styrene monomer units, 27 wt% to 35 wt% of acrylonitrile monomer units, and 0 wt% to 8 wt% of other copolymerizable monomer units. In another embodiment, the styrene-acrylonitrile copolymer (B) comprises 68 to 72.5 wt% of styrenic monomer units, 27.5 to 32 wt% of acrylonitrile monomer units, and 0 to 4.5 wt% of other copolymerizable monomer units. In another embodiment, the styrene-acrylonitrile copolymer (B) comprises 70 to 72 wt% of styrenic monomer units, 28 to 30 wt% of acrylonitrile monomer units, and 0 to 2 wt% of other copolymerizable monomer units.

The above styrene monomers may be used alone or in combination, and the kind of the styrene monomers is the same as that of the above acrylic ester-based rubber graft copolymer (a), and thus, a detailed description thereof will not be repeated.

The other copolymerizable monomers mentioned above may be used alone or in combination, and include, but are not limited to, acrylic monomers, methacrylic monomers, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, ethylene chloride, vinylidene chloride, ethylene tetrafluoride, vinylidene chloride, ethylene trifluoride monochloride, propylene hexafluoride, butadiene, propenyl (propenylamine), isobutyleneamine (isobutenylamine), vinyl acetate, ethyl vinyl ether (ethyl vinyl ether), methyl vinyl ketone (methyl vinyl ketone), anhydrous maleic acid (maleic acid), anhydrous methyl maleic acid (cis-methylisobutylene dioic acid), anhydrous methyl fumaric acid (trans-methylidenedioic acid), and the like. Acrylic monomers include, but are not limited to, acrylic acid and the like. The methacrylic monomer includes, but is not limited to, methacrylic acid and the like.

The styrene-acrylonitrile copolymer (B) is obtained by polymerizing the above styrene monomer, acrylonitrile monomer and optionally other copolymerizable monomer, and the polymerization reaction can be carried out by a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method, and among them, the bulk polymerization method or the solution polymerization method is preferable. Taking the solution polymerization as an example, the preparation method of the styrene-acrylonitrile copolymer (B) comprises the step of performing the solution polymerization of the styrene monomer, the acrylonitrile monomer, the other copolymerizable monomer and the polymerization initiator in the presence of the solvent, wherein the operation temperature is preferably in the range of 70 ℃ to 140 ℃, more preferably 90 ℃ to 130 ℃. Examples of the solvent used include toluene, ethylbenzene, methyl ethyl ketone, and the like.

Optionally, a polymerization initiator may be added in the solution polymerization. The polymerization initiator is selected from the group consisting of monofunctional polymerization initiators, multifunctional polymerization initiators, and combinations thereof. The monofunctional polymerization initiator may be used alone or in combination, and includes, but is not limited to, dibenzoyl peroxide (benzoyl peroxide), dicumyl peroxide (dicumyl peroxide), t-butyl peroxide (t-butyl peroxide), t-butyl hydroperoxide (t-butyl hydroperoxide), cumene hydroperoxide (cumene hydroperoxide), t-butyl peroxybenzoate (t-butyl-peroxide), bis-2-ethylhexyl peroxydicarbonate (bis-2-ethylhexyl peroxydicarbonate), t-butyl peroxyisopropylcarbonate (t-butyl-peroxyisocyanate carbonate, abbreviated as BPIC), cyclohexanone peroxide (cyclohexanone peroxide), 2' -azo-bis-isobutyronitrile (2, 2' -azo-bionitrile, abbreviated as AIBN 1,1 ' -azobis-1-cyclohexane (AIBN 1-azocarbonyl-1), 1 ' -azo-biscyclohexane-1-carbonitrile), or 2,2' -azo-bis-2-methylbutyronitrile (2, 2' -azo-bis-2-methyl butyronitrile), and the like. Among them, dibenzoyl peroxide and 2,2' -azo-bis-isobutyronitrile are preferable.

The polyfunctional polymerization initiator may be used alone or in combination, and includes, but is not limited to, 1-bis-t-butylperoxycyclohexane (1, 1-bis-t-butylperoxycyclohexane, abbreviated as TX-22), 1-bis-t-butylperoxy-3, 3,5-trimethylcyclohexane (1, 1-bis-t-butylperoxy-3, 3,5-trimethylcyclohexane, abbreviated as TX-29A), 2,5-dimethyl-2,5-bis- (2-ethylperoxyhexanoyl) hexane [2,5-dimethyl-2,5-bis- (2-ethylperoxyhexanoyl) hexane ], 4- (t-butylperoxycarbonyl) -3-hexyl-6- [7- (t-butylperoxycarbonyl) heptyl ] cyclohexane {4- (t-butylperoxycarbonyl) heptyl ] cyclohexane -butyl peroxide-3-hexyl-6- [7- (t-butyl peroxide) hexyl ] cyclohexoxane }, di-t-butyl diperoxynonanoate (di-t-butyl-diperoxyzelate), 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane [2,5-dimethyl-2,5-bis- (benzoyl peroxide) hexane ], di-t-butyl peroxy-hexahydro-terephthalate (di-t-butyl peroxide-hexahydro-terephthalate, BPHTH for short), or 2,2-bis (4, 4-di-t-butylperoxy) cyclohexylpropane [2,2-bis- (4,4-di-t-butyl peroxide) cyclohexyl propane, abbreviated as PX-12], and the like. The addition amount of the polymerization initiator is in the range of 0.01 to 2.0 parts by weight, preferably 0.01 to 1.0 part by weight, based on 100 parts by weight of the total amount of the styrenic monomer, the acrylonitrile monomer and the other copolymerizable monomer.

Further, a chain transfer agent may be optionally added in the above solution polymerization reaction, and the chain transfer agent may be used alone or in combination, and includes, but is not limited to, a mercaptan (melamine) based compound, such as methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, n-dodecyl mercaptan (n-dodecyl mercaptan, NDM), stearyl mercaptan (stearyl mercaptan), t-dodecyl mercaptan (TDM), n-propyl mercaptan, n-octyl mercaptan, t-nonyl mercaptan, pentaerythritol tetra (3-mercapto) tetra (3-mercaptopropionic acid), pentaerythritol tetra (2-mercaptoacetate), pentaerythritol tetra (4-mercaptobutyrate) (4-mercaptopropionate), pentaerythritol tetra (2-mercaptoacetate), pentaerythritol tetra (2-mercaptopropionate), a trimethylolpropane tetra (3-mercaptopropionate), a trimethylolpropane tetra (4-mercaptopropionate), a trimethylolpropane tetra (3-mercaptoethane), a trimethylolpropane tetra (2-mercaptopropionate), a trimethylolpropane tetra (3-mercaptoethane (2-mercaptopropionate), a trimethylolpropane (5 parts by weight, a pentaerythritol mono-, di-dodecylmercaptan-pentaerythritol (isopropyl mercaptan), pentaerythritol (2-pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (2-pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol (pentaerythritol), pentaerythritol.

In addition, in the preparation of the styrene-acrylonitrile copolymer (B), a thermal polymerization method may be employed in addition to the addition of the polymerization initiator to the reaction as described above.

Additionally, the reactors used to carry out the foregoing reactions may include (but are not limited to): a complete mixing continuous reactor (CSTR), a Plug Flow Reactor (PFR), or a tube reactor containing static mixing elements, etc., wherein a complete mixing continuous reactor is preferred. The number of the reactors to be used may be one, or two or more of them may be used in combination.

In one embodiment, the weight average molecular weight of the styrene-acrylonitrile copolymer (B) is 10 to 20 ten thousand. In another embodiment, the styrene-acrylonitrile copolymer (B) has a weight average molecular weight of 10.5 to 17 ten thousand. In another embodiment, the styrene-acrylonitrile copolymer (B) has a weight average molecular weight of 11 to 15 ten thousand.

[ styrene-unsaturated dicarboxylic anhydride copolymer (C) ]

In one embodiment of the present invention, the styrene-unsaturated dicarboxylic anhydride copolymer (C) is prepared by polymerizing reaction components including a styrene monomer, an unsaturated dicarboxylic anhydride monomer, and optionally an unsaturated dicarboxylic imide monomer. Furthermore, a solvent and/or a functional agent may be added to the polymerization reaction. The kind of the solvent is the same as that of the styrene-acrylonitrile copolymer (B), and thus, the description thereof is omitted. The functional agents such as the initiator, the emulsifier, the activator, and the chain transfer agent are the same as those of the styrene-acrylonitrile copolymer (B), and thus the details thereof are omitted.

The above styrene monomers can be used alone or in combination, and the kind of the styrene monomers is the same as that of the above acrylic ester-based rubber graft copolymer (A), and a description thereof will not be repeated.

The unsaturated dicarboxylic anhydride-based monomer may be used alone or in combination, and the unsaturated dicarboxylic anhydride-based monomer may be, for example, but not limited to, maleic anhydride, citraconic anhydride, itaconic anhydride, aconitic anhydride, or the like. Preferably, the unsaturated dicarboxylic anhydride monomer is maleic anhydride.

The unsaturated dicarboxylic acid imide-based monomers mentioned above may be used alone or in combination, and include, but are not limited to, maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-2, 3-tolylmaleimide, N-2, 4-tolylmaleimide, N-2, 3-ethylphenylmaleimide, N-2, 4-ethylphenylmaleimide, N-2, 3-butylbenylmaleimide, N-2, 4-butylbenylmaleimide, N-butylmaleimide, N-2, 4-butylmaleimide, N-, N-2, 6-tolylmaleimide, N-2, 3-chlorophenylmaleimide, N-2, 4-chlorophenylmaleimide, N-2, 3-bromophenylmaleimide, or N-2, 4-bromophenylmaleimide. Preferably, the unsaturated dicarboxylic acid imide-based monomer is N-phenyl maleimide.

In one embodiment, the polymerization reaction for preparing the styrene-unsaturated dicarboxylic anhydride copolymer (C) may be, for example, but not limited to, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc., and the polymerization reaction may be batch or continuous polymerization. Preferably, the styrenic-unsaturated dicarboxylic anhydride-based copolymer (C) is prepared by continuous solution polymerization.

The weight average molecular weight of the styrene-unsaturated dicarboxylic anhydride-based copolymer (C) is, but not limited to, 6 to 25 ten thousand, preferably 8 to 22 ten thousand; more preferably 10 to 19 ten thousand.

In another embodiment, the styrene-unsaturated dicarboxylic anhydride copolymer (C) can be prepared by copolymerizing monomer components comprising styrene monomers and unsaturated dicarboxylic anhydride monomers to form an intermediate product, and reacting the intermediate product with ammonia or a primary amine to perform imidization, wherein a portion of the unsaturated dicarboxylic anhydride monomer units on the intermediate product and the ammonia or the primary amine form unsaturated dicarboxylic imide monomer units. The primary amines may be used alone or in combination, and include, but are not limited to, alkylamines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, cyclohexylamine, decylamine, and chlorine-or bromine-substituted alkylamines, aniline, toluidine, naphthylamine, and other aromatic amines. Preferably, the primary amine is aniline or cyclohexylamine.

In another embodiment, a catalyst may be added to enhance the dehydration ring-closure reaction during the reaction of a portion of the unsaturated dicarboxylic anhydride monomer units with ammonia or a primary amine. The catalyst includes, but is not limited to, tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, N-dimethylaniline and N, N-diethylaniline.

[ rubber-modified resin composition ]

The method for preparing the rubber modified resin composition of the present invention is not particularly limited, and a general mixing method may be employed, for example, a method comprising uniformly mixing the acrylic ester-based rubber graft copolymer (a), the styrene-acrylonitrile copolymer (B), and the styrene-unsaturated dicarboxylic anhydride copolymer (C), and further optionally adding additives; in order to obtain the rubber modified resin composition of the present invention, the mixing method is typically: the resulting mixture is dry-blended in a general Henschel mixer and then melt-blended in a mixer such as an extruder, kneader or Banbury mixer.

The rubber modified resin composition of the present invention may optionally further comprise additives such as, but not limited to: antioxidants, plasticizers, lubricants, processing aids, ultraviolet absorbers, ultraviolet stabilizers, antistatic agents, fillers, reinforcing agents, colorants, heat stabilizers, flame retardants, flame retardant aids, coupling agents, or other additives, or a combination thereof. The timing of adding the additive is not particularly limited, and the additive may be added during, after or before the polymerization reaction for preparing the acrylate-based rubber graft copolymer (a), the styrene-acrylonitrile-based copolymer (B) or the styrene-unsaturated dicarboxylic anhydride-based copolymer (C), or during the preparation of the rubber-modified resin composition, depending on the actual process requirements. In one embodiment, the content of the additive is in a range of 0.01 to 20 parts by weight based on 100 parts by weight of the total amount of the acrylate-based rubber graft copolymer (a) and the styrene-acrylonitrile copolymer (B).

In one embodiment, the antioxidants may be used alone or in combination, and the antioxidants include, but are not limited to, phenolic antioxidants, thioether antioxidants, or phosphorus antioxidants. In one embodiment, the antioxidant is contained in an amount ranging from 0.005 to 3 parts by weight, based on 100 parts by weight of the total weight of the acrylate-based rubber graft copolymer (a) and the styrene-acrylonitrile copolymer (B).

In one embodiment, phenolic antioxidants such as, but not limited to, octadecyl 3,5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionate [3,5-bis (1, 1-dimethylthio) -4-hydroxybenzenepropanoic acid octadececyl ester, type: 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-tert-butyl-2-hydroxy-6-methylbenzyl) -4-methylphenyl acrylate, 2 '-methylene-bis (4-methyl-6-tert-butylphenol) [2,2' -methylene (4-methyl-6-tert-butylphenol), type: antioxidant 2246], 2' -thiobis (4-methyl-6-tert-butylphenol), 2' -thio-diethenyl-bis [3- (3, 5-bis-tert-butyl-4-hydroxyphenyl) propionate ], 2' -ethanediamide-bis [ ethyl-3- (3, 5-bis-tert-butyl-4-hydroxyphenyl) propionate ], or the like.

In one embodiment, the thioether-based antioxidants can be used alone or in combination, and the thioether-based antioxidants can be, for example, but not limited to, distearylthiodipropionate, dipalmitoylthiodipropionate, pentaerythritol-tetrakis- (β -dodecylmethyl-thiopropionate), or dioctadecylthioether.

In one embodiment, the phosphorus-based antioxidants can be used alone or in combination, and the phosphorus-based antioxidants can be, for example, but not limited to, compounds of phosphorous acids, phosphoric acids, phosphinic acids, phosphonic acids, phosphites, phosphates, phosphonites, phosphonates, tertiary phosphines, triorganophosphates, or acidic phosphates. Among the above phosphorus antioxidants, phosphorous acids, phosphonic acids, triorganophosphoric esters or acidic phosphoric esters are particularly preferable. Furthermore, in the acidic phosphate ester compound, the organic group may also include mono-substituted, di-substituted, or poly-substituted. The following exemplified compounds may be used alone or in admixture thereof.

Examples of the phosphate ester compounds include, but are not limited to, tetrakis (2, 4-t-butylphenyl) -4,4' -biphenylene phosphate, phenanthrene-10-oxolene 9, 10-dihydro-9-oxo-10-phosphate, and the like.

Examples of the above-mentioned triorganophosphate-based compound include, but are not limited to, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, dotriacontayl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenylcresyl phosphate, diphenyl mono-o-biphenyl phosphate, tris (butoxyethyl) phosphate, and the like. Preferably, the triorganophosphate compound is a trialkyl phosphate compound; more preferably, the carbon number of the three alkyl phosphate ester compounds is 1 to 22; still more preferably, the carbon number is 1 to 4. Most preferably, the trialkyl phosphate compound is trimethyl phosphate.

Examples of the acidic phosphate ester-based compound include, but are not limited to, methyl acidic phosphate, ethyl acidic phosphate, butyl acidic phosphate, butoxyethyl acidic phosphate, octyl acidic phosphate, decyl acidic phosphate, lauryl acidic phosphate, stearyl acidic phosphate, oleyl acidic phosphate, behenyl acidic phosphate, phenyl acidic phosphate, nonylphenyl acidic phosphate, cyclohexyl acidic phosphate, phenoxyethyl acidic phosphate, alkoxypolyethylene glycol acidic phosphate, and bisphenol a acidic phosphate.

The above phosphite compounds include, but are not limited to, triphenyl phosphite, tris (nonylphenyl) phosphite, dodecyl phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecylphenyl phosphite, dioctylphenyl phosphite, diisopropylphenyl phosphite, butyldiphenyl phosphite, decyldiphenyl phosphite, octyldiphenyl phosphite, tris (diethylphenyl) phosphite, tris (diisopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2, 4-ditertiarybutylphenyl) phosphite, tris (2, 6-ditertiarybutylphenyl) phosphite, distearylneopentylglycol diphosphite, bis (2, 4-ditertiarybutylphenyl) neopentylglycol diphosphite, and the like, Bis (2, 6-ditertiary butyl-4-methylphenyl) neopentyltetraol diphosphite, bis (2, 6-ditertiary butyl-4-ethylphenyl) neopentyltetraol diphosphite, bis {2, 4-bis (1-methyl-1-phenylethyl) phenyl } neopentyltetraol diphosphite, 4' -butylidenebis (3-methyl-6-tert-butylphenyl-ditridecyl phosphite), phenyl bisphenol A neopentyltetraol diphosphite, bis (nonylphenyl) neopentyltetraol diphosphite, dicyclohexylneopentyltetraol diphosphite and the like.

The above slip agents can be used alone or in combination, and the slip agents are, for example (but not limited to): (1) metal soap: calcium stearate, magnesium stearate, lithium stearate, or the like; (2) a compound: ethylene bis (stearamide), abbreviated as EBS, methylene bis (stearamide), palmitamide, butyl stearate, palmityl stearate, polyallyl tristearate, pentaerythritol stearate, behenic acid, stearic acid or stearyl alcohol; (3) waxes: polyethylene wax, octacosanoic acid wax, carnauba wax (Carnuba wax), petroleum wax, or the like; (4) higher alcohols: stearyl alcohol (stearyl alcohol), and the like. In one embodiment, the content of the lubricant is 0.01 to 5 parts by weight based on 100 parts by weight of the total weight of the acrylate-based rubber graft copolymer (a) and the styrene-acrylonitrile copolymer (B).

The above processing aids can be used alone or in admixture, and the processing aids are exemplified by (but not limited to): silicone oil or a styrene processing aid with a weight average molecular weight of more than 100 ten thousand. In one embodiment, the content of the processing aid is 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the acrylate-based rubber graft copolymer (a) and the styrene-acrylonitrile copolymer (B).

The above ultraviolet absorbers can be used alone or in combination, and the ultraviolet absorbers are exemplified by (but not limited to): benzotriazole (benzotriazole) compounds, benzophenone (benzophenone) compounds, cyanoacrylic acid (cyanoacrylic acid) compounds, and the like.

The UV stabilizers can be used alone or in combination, and include, but are not limited to: hindered amine compounds, and the like. In one embodiment, the content of the uv absorber and the uv stabilizer is 0.01 to 3 parts by weight, respectively, based on 100 parts by weight of the total amount of the acrylate rubber graft copolymer (a) and the styrene-acrylonitrile copolymer (B).

The above-mentioned electrification preventing agents can be used alone or in combination, and the electrification preventing agents are exemplified by (but not limited to): low molecular weight compounds such as tertiary amine compounds and quaternary ammonium salt compounds, and polymers having permanent charge preventing properties such as polyamide polyether.

The above fillers can be used alone or in admixture, and the fillers include, but are not limited to: calcium carbonate, silica, mica, and the like.

The above-mentioned reinforcing agents can be used alone or in admixture, and are exemplified by (but not limited to): glass fibers, carbon fibers, various crystal filaments (whisker), and the like.

The above colorants can be used alone or in admixture, and the colorants are exemplified by (but not limited to): titanium oxide, iron oxide, graphite, phthalocyanine dye, and the like.

The foregoing thermal stabilizers can be used alone or in combination, and the thermal stabilizers are exemplified by (but not limited to): dibutyltin maleate, basic magnesium aluminum hydroxycarbonate, and the like.

The invention will be 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 the practice of the invention.

[ preparation example 1] acrylic ester-based rubber graft copolymer (A)

Preparation of acrylate-based rubber graft copolymer (A-1)

First, 99.0 parts by weight of n-butyl acrylate, 1.0 part by weight of allyl methacrylate, 5.0 parts by weight of dioctyl sodium sulfosuccinate, 2.0 parts by weight of a tributyl hydroperoxide solution (concentration 70 wt%), 3.0 parts by weight of a ferrous sulfate solution (concentration 0.2 wt%), 3.0 parts by weight of a sodium formaldehydesulfoxylate solution (concentration 10 wt%) and 4000.0 parts by weight of distilled water were reacted at a reaction temperature of 60 ℃ for 7 hours to obtain an acrylate rubber emulsion containing acrylate rubber particles having a weight average particle diameter of 0.10 μm (conversion rate of about 99%, solid content of about 38%).

100.0 parts by weight of the above-mentioned acrylate-based rubber emulsion having a weight average particle diameter of 0.10 μm (dry weight), 70.0 parts by weight of styrene, 30.0 parts by weight of acrylonitrile, 6.0 parts by weight of dioctyl sodium sulfosuccinate, 1.0 part by weight of cumene hydroperoxide, 3.0 parts by weight of a ferrous sulfate solution (concentration of 0.2% by weight), 3.0 parts by weight of a sodium formaldehydesulfoxylate solution (concentration of 10% by weight), and 3000.0 parts by weight of distilled water were mixed and subjected to graft polymerization, wherein styrene and acrylonitrile were continuously added to the reaction system over 5 hours. After the graft polymerization reaction was completed, an acrylate-based rubber graft emulsion containing acrylate-based rubber particles having a weight average particle diameter of 0.12 μm was obtained.

Next, 99.0 parts by weight of n-butyl acrylate, 1.0 part by weight of allyl methacrylate, 3.0 parts by weight of dioctyl sodium sulfosuccinate, 1.0 part by weight of a tributyl hydroperoxide solution (concentration 70 wt%), 3.0 parts by weight of a ferrous sulfate solution (concentration 0.2 wt%), 3.0 parts by weight of a sodium formaldehydesulfoxylate solution (concentration 10 wt%), and 4000.0 parts by weight of distilled water were reacted at a reaction temperature of 65 ℃ for 7 hours to obtain an acrylate rubber emulsion containing acrylate rubber particles having a weight average particle diameter of 0.40 μm (conversion rate of about 99%, solid content of about 38%).

100.0 parts by weight of the above-mentioned acrylate-based rubber emulsion having a weight average particle diameter of 0.40 μm (dry weight), 37.6 parts by weight of styrene, 16.1 parts by weight of acrylonitrile, 4.0 parts by weight of dioctyl sodium sulfosuccinate, 1.0 part by weight of cumene hydroperoxide, 3.0 parts by weight of a ferrous sulfate solution (concentration of 0.2% by weight), 3.0 parts by weight of a sodium formaldehydesulfoxylate solution (concentration of 10% by weight), and 2000.0 parts by weight of distilled water were mixed and subjected to graft polymerization, wherein styrene and acrylonitrile were continuously added to the reaction system over 5 hours. After the graft polymerization reaction was completed, an acrylate-based rubber graft emulsion containing acrylate-based rubber particles having a weight average particle diameter of 0.46 μm was obtained.

Finally, the acrylic ester rubber graft emulsion with the weight average particle size of 0.12 μm and the acrylic ester rubber graft emulsion with the weight average particle size of 0.46 μm are mixed, coagulated by calcium chloride, dehydrated and dried until the moisture content is below 2 percent, thus obtaining the required acrylic ester rubber graft copolymer (A-1). Wherein the content of the acrylate rubber was 54.5% by weight, and the weight-average particle diameters of the acrylate rubber particles were 0.12 μm and 0.46 μm.

Preparation of acrylate-based rubber graft copolymer (A-2)

99.0 parts by weight of n-butyl acrylate, 1.0 part by weight of allyl methacrylate, 5.0 parts by weight of dioctyl sodium sulfosuccinate, 2.0 parts by weight of a tertiary butyl hydroperoxide solution (concentration 70 wt%), 3.0 parts by weight of a ferrous sulfate solution (concentration 0.2 wt%), 3.0 parts by weight of a sodium formaldehydesulfoxylate solution (concentration 10 wt%) and 4000.0 parts by weight of distilled water were reacted at a reaction temperature of 60 ℃ for 7 hours to obtain an acrylate rubber emulsion containing acrylate rubber particles having a weight average particle diameter of 0.10 μm (conversion rate about 99%, solid content about 38%).

100.0 parts by weight of the above-mentioned acrylate-based rubber emulsion having a weight average particle diameter of 0.10 μm (dry weight), 70.0 parts by weight of styrene, 30.0 parts by weight of acrylonitrile, 6.0 parts by weight of dioctyl sodium sulfosuccinate, 1.0 part by weight of cumene hydroperoxide, 3.0 parts by weight of a ferrous sulfate solution (concentration of 0.2% by weight), 3.0 parts by weight of a sodium formaldehydesulfoxylate solution (concentration of 10% by weight), and 3000.0 parts by weight of distilled water were mixed and subjected to graft polymerization, wherein styrene and acrylonitrile were continuously added to the reaction system over 5 hours. After the graft polymerization reaction was completed, an acrylate-based rubber graft emulsion containing acrylate-based rubber particles having a weight average particle diameter of 0.10 μm was obtained.

Finally, after coagulation and dehydration with calcium chloride, the resulting product was dried to a moisture content of 2% or less to obtain the desired acrylate-based rubber graft copolymer (A-2) having an acrylate-based rubber content of 50% by weight and an acrylate-based rubber particle weight-average particle diameter of 0.10. mu.m.

[ preparation example 2] styrene-acrylonitrile copolymer (B)

Preparation of styrene-acrylonitrile copolymer (B-1)

64 parts by weight of styrene, 36 parts by weight of acrylonitrile and 8 parts by weight of ethylbenzene were mixed, and then 0.015 part by weight of t-dodecyl mercaptan and 0.12 part by weight of 1, 1-bis-t-butylperoxy-3, 3,5-trimethylcyclohexane were mixed, and 35kg/hr of styrene was addedThe flow rate was continuously supplied into a completely mixed continuous reactor having a volume of 40 liters, internal temperatures of 145 ℃ and pressures of 4kg/cm²The overall conversion is about 55%.

After the completion of the polymerization, the obtained copolymer solution was heated by a preheater, and unreacted monomers and volatile substances such as solvents were removed by a vacuum degassing vessel. Subsequently, the obtained polymer melt was extruded and pelletized to obtain a styrene-acrylonitrile copolymer (B-1) having a weight average molecular weight of 12 ten thousand, and having a styrene monomer unit content of 72% by weight and an acrylonitrile monomer unit content of 28% by weight.

Preparation of styrene-acrylonitrile copolymer (B-2)

72 parts by weight of styrene, 28 parts by weight of acrylonitrile and 8 parts by weight of ethylbenzene were mixed, and then 0.4 part by weight of t-dodecylmercaptan and 0.035 part by weight of 1, 1-bis-t-butylperoxy-3, 3,5-trimethylcyclohexane were mixed and continuously fed into a complete mixing continuous reactor at a flow rate of 35kg/hr, wherein the volume of the reactor was 40 liters, the internal temperature was maintained at 145 ℃ and the pressure was maintained at 4kg/cm²The overall conversion is about 55%.

After the completion of the polymerization, the obtained copolymer solution was heated by a preheater, and unreacted monomers and volatile substances such as solvents were removed by a vacuum degassing vessel. Then, the obtained polymer melt was extruded and pelletized to obtain a styrene-acrylonitrile copolymer (B-2) having a weight average molecular weight of 10 ten thousand, and having a styrene monomer unit content of 72% by weight and an acrylonitrile monomer unit content of 28% by weight.

Preparation of styrene-acrylonitrile copolymer (B-3)

72 parts by weight of styrene, 28 parts by weight of acrylonitrile and 8 parts by weight of ethylbenzene were mixed, and then 0.48 part by weight of t-dodecyl mercaptan and 0.04 part by weight of 1, 1-bis-t-butylperoxy-3, 3,5-trimethylcyclohexane were mixed and continuously fed into a complete mixing continuous reactor at a flow rate of 35kg/hr, wherein the volume of the reactor was 40 liters and the internal temperature was maintained at each of the same levelsAt 145 deg.C, the pressure was maintained at 4kg/cm²The overall conversion is about 55%.

After the completion of the polymerization, the obtained copolymer solution was heated by a preheater, and unreacted monomers and volatile substances such as solvents were removed by a vacuum degassing vessel. Subsequently, the obtained polymer melt was extruded and pelletized to obtain a styrene-acrylonitrile copolymer (B-3) having a weight average molecular weight of 8.5 ten thousand and a styrene monomer unit content of 73.5% by weight and an acrylonitrile monomer unit content of 26.5% by weight.

Preparation of styrene-acrylonitrile copolymer (B-4)

72 parts by weight of styrene, 28 parts by weight of acrylonitrile and 8 parts by weight of ethylbenzene were mixed, and then 0.02 part by weight of t-dodecyl mercaptan and 0.03 part by weight of 1, 1-bis-t-butylperoxy-3, 3,5-trimethylcyclohexane were mixed and continuously fed into a complete mixing continuous reactor at a flow rate of 35kg/hr, wherein the volume of the reactor was 40 liters, the internal temperature was maintained at 145 ℃ and the pressure was maintained at 4kg/cm²The overall conversion is about 55%.

After the completion of the polymerization, the obtained copolymer solution was heated by a preheater, and unreacted monomers and volatile substances such as solvents were removed by a vacuum degassing vessel. Subsequently, the obtained polymer melt was extruded and pelletized to obtain a styrene-acrylonitrile copolymer (B-4) having a weight average molecular weight of 21 ten thousand, and having a styrene monomer unit content of 72% by weight and an acrylonitrile monomer unit content of 28% by weight.

[ preparation example 3] styrene-based unsaturated dicarboxylic anhydride-based copolymer (C)

The styrene-unsaturated dicarboxylic anhydride copolymer (C) had a styrene monomer unit content of 72 mol%, a N-phenylmaleimide monomer unit content of 18 mol%, a maleic anhydride monomer unit content of 10 mol%, and a weight average molecular weight of 14.5 ten thousand.

[ example 1]

In a dry state, 35 wt% of the acrylate-based rubber graft copolymer (A), 62 wt% of the styrene-acrylonitrile copolymer (B) and 3 wt% of the styrene-unsaturated dicarboxylic anhydride copolymer (C) were kneaded and extruded at a kneading temperature of 220 ℃ by means of a biaxial extruder (model: ZPT-25, manufactured by Zezer industries, Ltd.) to obtain the rubber-modified resin composition of example 1 of the present invention. The measurement results of the physical properties of the composition of example 1 are shown in Table 1.

Examples 2 and 3 and comparative examples 1 to 5

Examples 2 and 3 and comparative examples 1 to 5 were prepared by the same kneading extrusion method as in example 1, except that: the kinds and amounts of the raw materials were changed, as shown in Table 1. The results of analysis and evaluation of physical properties are also shown in Table 1.

The related detection items in the present invention are briefly described below.

1. Measurement of monomer units:

nuclear Magnetic Resonance (NMR) analysis was used to determine the NMR spectrum. The content of each monomer unit was calculated from the area ratio of a specific peak in the hydrogen spectrum of nuclear magnetic resonance.

2. Melt flow index (indicating flowability, melt flow rate, abbreviated MVR):

the compositions of examples 1 to 3 and comparative examples 1 to 5 were tested according to ISO 1133 at a temperature of 220 ℃ under a load of 10kg, in units: cm³And/10 min. Generally, a higher melt flow index indicates better fluidity, i.e., better moldability of the composition.

3. Vicat softening point temperature (SP):

the compositions of examples 1 to 3 and comparative examples 1 to 5 were measured for softening point temperature under a load of 10 newtons (N) and at a temperature rise rate of 50 ℃ per hour in accordance with ISO306, in the following units: DEG C. Generally, a higher softening point temperature indicates a better heat resistance of the composition.

4. Impact strength test (Charpy impact strength strip):

the compositions of examples 1 to 3 and comparative examples 1 to 5 were measured according to ISO 180 method using 80mm with notch (opening depth of 2mm) at 23 ℃The measurement was carried out on a 10mm × 4mm test piece. Unit: kJ/m². Generally, a higher impact resistance value indicates a better impact resistance of the composition.

5. Determination of weight average molecular weight:

the analyte was dissolved in a solvent of tetrahydrofuran, and then analyzed and measured by a Gel permeation chromatograph (manufactured by Waters corporation), in which polystyrene was used as an analysis standard. The analysis conditions of the gel dialysis chromatograph are as follows: KD-806M; a detector: WaterrI-2410; mobile phase: THF (flow rate 1.0/min).

6. Weight average particle diameter measurement of rubber particles:

the compositions of examples 1 to 3 and comparative examples 1 to 5 were each treated with ruthenium tetroxide (RuO)₄) Dyeing, and after dyeing, photographing rubber particles (number 200 to 1,000) obtained in the photo-piece by a transmission electron microscope of 10,000 magnification, measuring the particle diameter (D, unit μm) of each of the rubber particles, and finding the average particle diameter (Davg) according to the following formula:

wherein Ni is the number of rubber particles; di is the particle diameter of the ith rubber particle.

TABLE 1

According to a preferred embodiment of the present invention, the weight average particle diameter of the rubber particles of the acrylate-based rubber graft copolymer (A) is bimodal distribution of 0.10 μm to 0.20 μm and 0.30 μm to 0.50 μm. When the rubber particles of the acrylic rubber graft copolymer (a) are changed from a monomodal distribution to a bimodal distribution, the impact resistance is improved. For example, examples 1 to 3 in Table 1 have an impact resistance value of from 4.3kJ/m as compared with comparative example 4²The concentration of the carbon dioxide is greatly increased to about 11.2 to 13.1kJ/m². For example, comparative example 2 in table 1 is compared to comparative example 4.

According to a preferred embodiment of the present invention, the styrene-acrylonitrile copolymer (B) has an acrylonitrile monomer unit content of 27 to 35% by weight. When the content of the acrylonitrile monomer unit in the styrene-acrylonitrile copolymer (B) is increased, the impact resistance is increased, but the fluidity is decreased. For example, examples 1 to 3 in table 1 are compared to comparative examples 2 and 3.

According to a preferred embodiment of the present invention, the weight average molecular weight of the styrene-acrylonitrile copolymer (B) is 10 to 20 ten thousand. When the weight average molecular weight of the styrene-acrylonitrile copolymer (B) is increased, the impact resistance is increased, but the fluidity is decreased. For example, comparative example 1 in Table 1 has an impact resistance value of from 12.3kJ/m as compared with comparative example 5²Is increased significantly to about 20.3kJ/m²But having a melt flow index of from 19.84cm³The/10 min is greatly reduced to 4.20cm³And/10 min. For example, examples 1 to 3 in Table 1 have impact resistance values of from 8.1 to 9.5kJ/m as compared with comparative examples 2 and 3²The concentration is increased to about 11.2-13.1 kJ/m²But has a melt flow index of from 14.10 to 18.20cm³The temperature drops to 7.24-9.30 cm in 10min³/10min。

According to a preferred embodiment of the present invention, the styrene-acrylonitrile copolymer (B) is used in an amount of 54 to 70% by weight. When the amount of the styrene-acrylonitrile copolymer (B) used is increased, the fluidity is increased, but the impact resistance is decreased. For example, comparative example 2 in Table 1 has a melt flow index of from 14.10cm compared to comparative example 3³The/10 min is greatly increased to 18.20cm³10min, but with an impact resistance value of from 9.5kJ/m²Down to 8.1kJ/m²。

According to a preferred embodiment of the present invention, the styrene-unsaturated dicarboxylic anhydride copolymer (C) is used in an amount of 1 to 15 wt%. If the styrene-unsaturated dicarboxylic anhydride copolymer (C) is not used, the heat resistance is poor. For example, examples 1 to 3 in Table 1 have Vicat softening point temperatures that increase significantly from 94.0 to 94.6 ℃ to about 104.2 to 105.8 ℃ as compared to comparative examples 1 and 5. When the amount of the styrene-unsaturated dicarboxylic anhydride copolymer (C) used is increased, the fluidity is improved, but the impact resistance is lowered. Referring to table 1, the styrene-unsaturated dicarboxylic anhydride-based copolymer (C) of example 3 was used in an amount of 6 wt%, and the melt flow index of example 3 was greater than that of examples 1 and 2, compared to 3 wt% of the styrene-unsaturated dicarboxylic anhydride-based copolymer (C) of examples 1 and 2, thereby improving fluidity; however, the impact resistance value of example 3 is smaller than those of examples 1 and 2, and therefore the impact resistance is lowered.

As described above, the rubber-modified resin composition of the present invention has high heat resistance, good fluidity, impact resistance and other physical properties, and can provide a composition having well-balanced physical properties. And according to the physical property requirements required by the application products, the rubber modified resin composition meeting the physical property requirements of the products is prepared.

The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims

1. A rubber-modified resin composition, comprising: 27 to 43% by weight of an acrylate-based rubber graft copolymer (a), 54 to 70% by weight of a styrene-acrylonitrile copolymer (B), and 1 to 15% by weight of a styrene-unsaturated dicarboxylic anhydride copolymer (C); wherein the styrene-acrylonitrile copolymer (B) comprises 27 to 35% by weight of an acrylonitrile monomer unit.

2. The rubber-modified resin composition according to claim 1, wherein the rubber-modified resin composition comprises 29 to 38 wt% of the acrylate-based rubber graft copolymer (a), 58 to 67 wt% of the styrene-acrylonitrile copolymer (B), and 1.5 to 10 wt% of the styrene-unsaturated dicarboxylic anhydride copolymer (C).

3. The rubber-modified resin composition according to claim 1, wherein the acrylate-based rubber graft copolymer (A) comprises rubber particles and a graft copolymer, and the weight average particle size of the rubber particles is bimodal distribution of 0.10 to 0.20 μm and 0.30 to 0.50 μm.

4. The rubber-modified resin composition according to claim 1, wherein the styrene-acrylonitrile copolymer (B) comprises 65 to 73 wt% of styrene monomer units, 27 to 35 wt% of acrylonitrile monomer units, and 0 to 8 wt% of other copolymerizable monomer units.

5. The rubber-modified resin composition according to claim 1, wherein the styrene-acrylonitrile copolymer (B) comprises 70 to 72 wt% of styrene monomer units, 28 to 30 wt% of acrylonitrile monomer units, and 0 to 2 wt% of other copolymerizable monomer units.

6. The rubber-modified resin composition according to claim 1, wherein the styrene-acrylonitrile copolymer (B) has a weight-average molecular weight of 10 to 20 ten thousand.

7. The rubber-modified resin composition according to claim 1, wherein the styrene-acrylonitrile copolymer (B) has a weight-average molecular weight of 11 to 15 ten thousand.

8. The rubber-modified resin composition according to claim 1, wherein the styrene-unsaturated dicarboxylic anhydride copolymer (C) comprises 45 to 95 mol% of styrene monomer units, 1 to 55 mol% of unsaturated dicarboxylic anhydride monomer units, and 0 to 54 mol% of unsaturated dicarboxylic imide monomer units.

9. The rubber-modified resin composition according to claim 1, wherein the styrene-unsaturated dicarboxylic anhydride copolymer (C) has a weight-average molecular weight of 6 to 25 ten thousand.

10. The rubber-modified resin composition of claim 1, wherein the acrylate-based rubber graft copolymer (a) comprises rubber particles and a graft copolymer, the graft copolymer of the acrylate-based rubber graft copolymer (a), the styrene-acrylonitrile copolymer (B), and the styrene-unsaturated dicarboxylic anhydride copolymer (C) form a continuous phase, and the rubber particles of the acrylate-based rubber graft copolymer (a) form a dispersed phase, wherein the rubber-modified resin composition comprises 70 to 90 wt% of the continuous phase and 10 to 30 wt% of the dispersed phase, based on 100 wt% of the total content of the rubber-modified resin composition.

11. A molded article formed from the rubber-modified resin composition as defined in any one of claims 1 to 10.