TWI242577B - Rubber modified styrene system resin composition - Google Patents

Abstract

Provided is one kind of rubber modified styrene system resin composition simultaneously having good impact resistance and fluidity, as well as superior stress cracking resistance and few stains which is composed of styrenic copolymer (A) used as a continuous phase and rubber particles (B) used as a dispersed phase. The styrenic copolymer (A) is copolymerized by (i-1) 50 to 90 weight % of styrene system monomer, (i-2) 10 to 50 weight % of vinyl nitrile monomer, (i-3) 0 to 40 weight % of other polymerizable vinyl system monomer in which (i-1), (i-2), (i-3) mentioned above amount to 100 weight %, and 0.0005 to 1.0 weight % of maleimide system monomer with polyfunctionality. Among which are mentioned above, the rubber modified styrene system resin composition contains 1 to 40 weight % of rubber. The measured MFR of styrene copolymer (A) at temperature 200 DEG C with load weight of 1 kg is MI (g/10 minutes), the measured MFR at temperature 200 DEG C with load weight of 10 kg is HMI (g/10 minutes), its MIR (=HMI/MI) is between 21.5 to 30.0, and its weight average molecular weight is between 60000 to 145000.

Description

1242577 V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a kind of rubber-modified styrene vinyl grease group which provides a kind of special impact cracking and fluidity with good impact resistance #, The styrenic resin with low stains and falsified ^ should be [prior art]. General styrene resins have good evaluations of their processability and mechanical properties, especially the good appearance and gloss of the molded products = their large color, so they are widely used in electronics and electrical appliances. . A car is zero, but for styrene resins, the preferred physical property balance is not achieved. For example, when the impact resistance is improved by adding the molecular weight of the polymer, the fluidity is lowered. In the method for improving fluidity, if To improve the day guard with ^ easy-type temperature, it is easy to cause yellowing and thermal decomposition of the molded product, and the physical properties of the final molded product are still adversely affected; if it is not changed by high-temperature molding, the fluidity is changed, and the added amount is increased. When it is improved by agents, etc., it is easy to cause low mechanical properties. If you do not add a large amount of lubricant to improve fluidity, and change to molding conditions (such as injection molding, increase injection pressure) to improve, it is likely to cause molding. The residual stress of the product is too large, which causes shortcomings such as poor chemical resistance and cracking. In order to solve the problems mentioned above, Japanese Unexamined Patent Publication No. 2- 1 82 7 1 1 proposes to improve the polymerization of aromatic monovinyl compounds by adding a polyfunctional vinyl compound, such as diethylbenzylbenzyl, to improve Moldability and impact resistance; however, when divinylbenzene is used alone, it is not easy to obtain a styrene resin with high flow and impact resistance, and the use of diethylbenzene is easy.

Page 5 1242577 The final JP-A polymer compound 50 A in the reaction is used together with the flow for a long time, and the benzene can be obtained for a long time. 5. Description of the invention (2) Causes a copolymerized bridge foreign body, and is like a alkenyl compound Organic peroxic impact, but at the same time has a high amount of chemical compounds, therefore, those with good properties and stains have long [SUMMARY OF THE INVENTION The composition of the present invention has characteristics and resistance to stress. In the reaction of No. 9-278816, Cangben ethidium Resin of the reactor, the impact of benzene which was organic before ~ 10,000ppm was easy to cause the flowability of styrene to the south and the ethidium resin group. It has been hoped to break through the number of stains attached to the wall. The bulletin proposes a four-functional method, and the impact resistance of the ethylene-based tree resin made of oxide is an issue. Too high too much. ‘The aromatic’ difunctionality is improved to form, fat, and impact resistance ’and the resistance is familiar to the molecular weight frame of the aromatic monoethyl’ monofunctional type and resistance. It is not easy to get the low level of organic peroxygen. The purpose of stress cracking & technology is to provide a rubber-modified styrene-based resin = to provide a rubber-modified styrene-based resin that has both good impact resistance and flow * 4 Edge f; the present invention provides a rubber-modified styrene-based resin composition, which is composed of a styrene-based copolymer (A) as a continuous phase and rubber particles (B) as a dispersed phase, and benzene The ethylene-based copolymer (A) is composed of 50 to M, parts by weight of a stupid vinyl-based monomer, (i-2) 10 to 50 parts by weight of a nitrile vinyl-based monomer, and (i-3). 4 parts by weight of other copolymerizable ethylene-based monomers, a total of 100 parts by weight of the above (i-1), (i-2), and (i_3), and 0. 0 0 0 5 to 1 · 0 parts by weight of polyfunctional maleimide imide-based monomer copolymerized; 'rubber modified styrene resin composition contains rubber

1242577

1242577 V. Description of the invention (4) Acid S, etc. Among them, butyl vinegar is preferred. Specific examples of fluorenyl acrylate monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, Cyclohexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, diethylaminoethyl methacrylate, ethylene dimethyl acrylate (Ethylene dimethacrylate), neopentyl dimethacrylate, etc. Among them, methyl methacrylate and butyl methacrylate are preferred. The monofunctional maleimide imide monomer means that the monomer contains only a single maleimide imine functional group, and specific examples thereof include: maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide Amine, N-Cyclohexylmaleimide, N-Phenylmaleimide, N-2-Phenylmaleimide, N-2, 3-Dimethylphenylmaleimide , N-2,4-Dimethylphenylmaleimide, N-2, 3-diethylphenylmaleimide, N-2,4-diethylphenylmaleimide Amine, N-2,3-dibutylphenylmaleimide, N-2,4-dibutylphenylmaleimide, N-2,6-dimethylphenylmaleimide Amine, N_2,3-dichlorophenylmaleimide, N_2,4-dichlorophenylmaleimide, N-2, 3-dibromophenylmaleimide or N-2, 4-Dibromophenylmaleimide and the like, of which N-phenylmaleimide is preferred. In addition, other copolymerizable vinyl monomers, such as acrylic monomers (eg, acrylic acid, methacrylic acid), anhydrous maleic acid, anhydrous methyl maleic acid, anhydrous methyl fumaric acid Fumaric acid

1242577 V. Description of the invention (5) acid), itaconic acid (itac ο nicacid) and other unsaturated carboxylic acid compounds and their esterification monomers (such as dimethyl fumarate, dibutyl itaconic acid), Acetylene, Acrylic, 1 ~ Butylene, 1-pentene, 4-methyl-1-pentene, ethylene chloride, ethylene chloride fork, ethylene tetrafluoride, ethylene chlorotrifluoride, hexafluoride Propylene, butadiene, allylamine, isobutyleneamine, vinyl acetate, ethyl vinyl ether, methyl ethyl ketone, triallyl isocyanate (tr 丨 a 1 1 y 1 i socyanate), etc. The total amount of (i-1), (i-2), and (i-3) is 100 parts by weight. The amount of the other copolymerizable ethylene-based monomer of the present invention is 0 to 4 parts by weight, and preferably 34 parts by weight. , More preferably 3 to 30 parts by weight. The polyfunctional maleimide imide monomer used in the present invention refers to a compound containing at least two maleimide imine functional groups, for example, two or three or more maleimide imide functional groups compound of. Among them, bismaleimide-based monomers are preferred, and the structural formula can be expressed by general formula (1). 〇 〇

[Wherein 'X is alkylene, arylene, arylene, carbonyl gr0Up, 1 ~ 10 carbon number, -S02-, -SO-, -〇-, -0-R -0- (R may be alkylene, arylene)], specific examples are: N, n, -4,4,-(3,3'-dimethyldiphenylmethane) bismaleamidine Imine [n, N'-4,4,-(3,3'-dimethyl diphenyl me thane) bisma1eimide], N, N,

Page 9 1242577 V. Description of the invention (6)

-4, 4 '-(3, 3'-diethyldiphenylmethane) bismaleimide [N, N'-4, 4'-(3,3'-diethyl diphenyl methane) bisma1eimide], 1 "-4,4'-diphenylmethane bismaleimide (1 ^," -4,4'-diphenyl methane bismaleimide), N, N'-4,4'-2,2-diphenyl Propylene bismaleimide S & imine (N, N '-4,4'-2,2-diphenyl propane bismaleimide), ^ "-4,4'-diphenyl ether bismaleimide (^ "-4,4'-diphenyl ether bismaleimide), N, N'-3,3'-diphenylsulfonium bismaleimide (N, N '-3,3'-diphenyl sulfone bismaleimide), N, N'-4,4'-diphenylisobismaleimide (N, N'-4,4'-diphenyl su 1 fone bismaleimide), N, N, -4,4, -dibenzylimide Said bismaleimide (N, N -4,4'-diphenyl sulfoxide bismaleimide), N, N '-4, 4'-benzophenone bismaleimide (n, N' -4, 4'-benzophenone bismaleimide), N, N, -1,3-phenylene bismaleimide (N, N'-l, 3-phenylene bismaleimide), where ^ 『-4,4'- 二benzene Methane bismaleimide (PEI) ^ '- 1,3-phenylene bismaleimide (PEI) is preferred. Based on the total of 100 parts by weight of (i-1), (i-2), and (i_3) described above, the amount of the polyfunctional maleimide-based monomer of the present invention is 0.0 0 0 5 to 1. · 0 parts by weight, preferably 0. 〇〇 丨 ～ 〇 · 3 parts by weight, more preferably 0.03 ~ 0 · 15 parts by weight. If the amount of the polyfunctional maleimide imide monomer is more than 1.0 part by weight, the viscosity of the polymer will increase sharply during the polymerization of the styrene copolymer (A), and high molecular cross-linking foreign substances and stain. The method for producing the styrenic copolymer (A) of the present invention can be carried out by a general block or solution polymerization reaction, an emulsion polymerization reaction, or a suspension polymerization.

Page 10 1242577 V. Description of the invention (7) The reaction is completed; among them, block polymerization or solution polymerization is preferred. The aforementioned reactor may include: a column flow reactor (PFR), a complete mixing reactor (CSTR), or a reactor including a static mixer. The number of reactors may be one or two or more may be used in combination, preferably three or more. When more than two reactors are used, the first reactor is preferably a fully mixed reaction (C S T R), and the final reactor is preferably a column flow reactor (PFR). When the styrene-based copolymer (A) of the present invention is produced, the production method is such that the raw material solution for the reaction is continuously fed into the reactor for reaction, and a polymerization initiator may be added to the reaction. In the production of the styrene-based copolymer (A) of the present invention, a polymerization initiator may be usually added. Based on the total of 100 parts by weight of (i-1), (i-2), and (i-3) above, the amount of the polymerization initiator used is 0 to 1 part by weight, and preferably 〇〇i ~ 0 · 5 parts by weight, the usable polymerization initiator may be a monofunctional polymerization initiator or a polyfunctional polymerization initiator, and the specific monofunctional polymerization initiator is, for example, benzoyl peroxide peroxide), dicumyl peroxide, t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide ( cumene hydroperoxide), t-butyl-peroxy benzoate, bis-2-ethy lhexy 1 peroxy dicarbonate, third butyl Tert-butyl peroxy isopropyl carbonate (BPIC), cyclohexanone peroxide, 2, 2-azo-bis-isobutyronitrile (2, 2-azo-bis -isobutyronitrile)

1242577 V. Description of the invention (8), 1,1'-azo-biscyclohexane-1-carbon itrile, 2,2'-azo-bis -2- amidinobutyronitrile (2, 2-azo-bis-2-methyl butyronitrile) and the like. Among them, diphenylphosphonium peroxide and diphenylisopropyl peroxide are preferred. Specific examples of the polyfunctional polymerization initiator are: 1,1-bis-t-butyl peroxy cyclohexane (l, l-bis-t-butyl peroxy cyclohexane), 1,1-bis-third Butyl peroxide-3,3,5-trimethylcyclohexane (1,1-1 ^ 3 -t-butylper〇Xy-3, 3,5-trimethyl cyclohexane, TX -29A for short), 2, 5 -Dimethyl-2, 5-bis- (2-ethylhexanoxy peroxy) hexane [2, 5-dimethyl-2,5-bis- (2-ethylhexanoxy peroxy) hexane], 4- (third Butylperoxycarbonyl) -3-hexyl-6- [7- (third butylperoxy) heptyl] cyclohexyl {4- (t-butyl peroxy carbony1) -3-hexyl-6- [ 7- (t-buty 1 peroxy carbonyl) heptyl] cyclohexane}, di-t-butyl-diperoxyazelate, 2,5-difluorenyl-2,5— Bis (Benzamidine peroxidation) -hexane [2, 5-dimethyl-2, 5-bis- (benzoyl peroxy) hexane], di-third butyl peroxy-hexahydro-terephthalate (di -t-butyl peroxy-hexahydro-terephthalate (abbreviated as ΒΡΤΤΗ), 2,2-bis (4,4-di-third-butylperoxy) cyclohexylpropane [2, 2-bis- (4,4-di- t-butyl peroxy) cyclohexyl propane , Referred to as PX-12], multifunctional monoperoxycarbonate (for example, manufactured by ATOF I NA Company, trade name Luperox JWE), etc .; TX-29A and PG-12 are preferred. The reaction temperature of the above-mentioned reactor is controlled at 20 to 300 ° C, preferably 60.

, 1242577 to 2 5 0 C, more preferably 80 to 240 ° C, the pressure of the reactor is controlled between 0 kg / cm2; and in order to control the molecular weight of the polymer, a chain transfer agent can be used in the present invention, Based on the above-mentioned (1-D, (1-2), (1-3)) x total 500,000 parts by weight, the amount of chain transfer agent used is 0 ~ 2 parts by weight, and preferably 100,000 parts by weight; The chain transfer agent used may be a monofunctional chain transfer agent or a polyfunctional chain transfer agent, and specific monofunctional chain transfer agents include: 1) Mercaptans: methyl mercaptan, n-butane Methyl mercaptan, cyclohexyl mercaptan, n-dodecyl mercaptan, stearyl mercaptan, t-dodecyl mercapta η, TD Μ) , N-propyl mercaptan, n-octyl mercaptan, third-octyl mercaptan, third-nonyl mercaptan, and the like. 2) Alky 1 amines: monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, di-n-butylamine, Tri-n-butylamine and the like. 3) Other examples: pentaphenylethane, α-methyl styrene dimer, terpinolene, among which n--12 in thiols Alkyl mercaptan and tertiary-dodecyl mercaptan are preferred. Polyfunctional chain transfer agents are, for example, isopentaerythritol tetrakis (3-mercaptopropionate) [pentaerythritol tetrakis (3-mercapto propionate)], isopentatriol tetrakis (2-mercaptoacetate) [pentaerythritol tetrakis ( 2-mercapto acetate)], tri- (2-mercaptoacetate) trimethylolpropane [trimethylolpropane tris (2-mercapto acetate)], tri- (3-mercaptopropionic acid) trimethylolpropionate [

Page 13 1242577

trimethyl olpropane tris (3-mercapto propionate) (TMPT for short), tri- (6-mercaptohexanoate) trihydroxypropylpropyl ester [trimethyl〇1 — propane tris (6-mercapto hexanate)], etc .; those listed above, Tris- (3-mercaptopropionic acid) trishydroxypropylpropyl is preferred. The above-mentioned method for preparing the styrene-based copolymer (A) is to continuously introduce the raw material solution into the reaction device for reaction. After all the monomers in the raw material solution reach a predetermined conversion rate, the polymer solution is continuously passed from the reaction device It was taken out and introduced into a devolatilizing device to remove unreacted monomers and volatile components, and then granulated. The final monomer conversion rate of the general polymerization reaction is 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more. —General Degassing device can use decompression degassing tank device or extruded degassing device. After that, unreacted monomers or volatile components are recovered by a condenser, and if necessary, the water in the recovered liquid can be removed and used again as a raw material solution. In the production of the stupid ethylene copolymer (A), a solvent can be added as needed. Based on the total of 100 parts by weight of (i-1), (i-2), and (i-3) above, the use of the solvent The amount is 0 to 100 parts by weight, preferably 0 to 60 parts by weight, and more preferably 1 to 50 parts by weight. The solvents that can be used can be benzene, toluene, ethylbenzene, p-toluene, o- Dimethylbenzyl, m-xylene, and glutamate, scorch, and cyclohexanone are the same as methyl ethyl ketone, acetone, and methylbutane 1. The weight average molecular weight of the styrene-based copolymer (A) of the present invention is usually between 60,000 and 145,000, preferably between 650,000 and 120,000, and more preferably 70, Between 000 and 115,000; when the weight average molecular weight of the copolymer (a) is less than 60,000, the impact resistance of the modified styrene resin composition of rubber is not good. The weight average molecular weight is higher than

Page 14 1242577 V. Description of the invention (11) 14 5 0 0 0, the fluidity of the rubber-modified styrene resin composition is insufficient. The weight average molecular weight of the copolymer (A) can be controlled by the copolymerization of the copolymer (A), the choice and amount of the chain transfer agent, the choice and amount of the polymerization initiator, the choice and amount of the solvent, and the polymerization temperature. , Polymerization time, or reactor choice. The MFR of the styrene-based copolymer (A) of the present invention measured at a temperature of 200 ° C and a load of ikg is MI (g / 10 minutes), measured at a temperature of 200 ° C and a load of 10 kg. The MFR is HMI (g / 10 points), and its MIR (= HMI / MI) is usually between 21.5 and 30.0, preferably between 21.8 and 29.0, and more preferably between 22.0 and 28.0; where 'MFR means Melt flow index, this index is a functional polymerization starting rate measured by the astm D-1 238 method. Two of them are stress-resistant substances.

Got. The M IR value control method of the copolymer (A) can be achieved by the following method or several methods. That is, during the copolymerization of the copolymer (A), the amount and timing of the addition of the polymaleimide-based monomer, the selection and amount of the polyfunctional initiator, the choice of the reactor, and the final conversion of the monomer. The above (H) styrene-based diluent monomer is early; it can be achieved by adding a part of the amount of the monomer or polyfunctional polymerization initiator to the second and subsequent polymerization reactors. It is cost-effective, and has good impact resistance and fluidity, good cracking, and less modified rubber-modified styrene-based resin. Composition 7 satisfies the present invention. 0) Styrene-based copolymer (a) Polymerization inversion: The amount of the functional maleimin-based monomer is in the range of from 0.5 to 10. The MIR of the ethylene-based copolymer (A) is between 2 1. 5 and 3 0. 〇. Wuming's rubber changed Zeng Xishu, and Gu Ma j + the original vinyl fluorene resin composition, the phenethyl λκ (A) as a continuous phase, and the phase, the shell phase rubber particles (B) as the dispersed phase While

1242577 V. Description of the invention (12) It is obtained that the content of the rubber component is usually 40% by weight, preferably 3 to 35% by weight, and more preferably 5 to 30% by weight. If the content of the rubber component of the present invention is between 1 and 40% by weight, the balance between fluidity and impact resistance of the rubber-modified styrene resin composition is better. In the method for producing a modified styrene-based resin composition of the rubber of the present invention, a rubber component can be added to the polymerization reaction process of the styrene-based copolymer (A) to participate in the reaction (hereinafter referred to as the simultaneous grafting method). Alternatively, a rubber component (such as a general rubber or a rubber graft copolymer, especially a rubber graft copolymer) is directly mixed with the styrene copolymer (A) of the present invention and extruded. Said). The simultaneous grafting method can be generally performed by a block polymerization method, a solution polymerization method, an emulsion polymerization method or a suspension polymerization method. The method for producing the rubber graft copolymer can be generally completed by an emulsion polymerization method or an emulsion block polymerization method, and among them, an emulsion polymerization method is preferred. The method for producing a modified styrene resin composition of the rubber of the present invention is described below by two methods: <Method 1: Simultaneous Grafting Method> Method 1 The rubber of the present invention can be obtained by using block or solution polymerization. Modified styrene resin composition. The reactor used in the method 1 may include: a column flow reactor (PFR), a completely mixed reactor (CSTR), or a reactor including a static mixer. The number of reactors may be one or two or more may be used in combination, preferably three or more. When used. When there are more than two reactors, the first reactor is preferably a fully mixed reactor (CSTR), and the final reactor is preferably a column flow reactor (pFR). The method of making is to first modify the styrene ethyl rubber which is satisfied with the present invention.

Page 16 1242577 V. Description of the invention (13) The raw material solution (containing rubber component) of the olefin resin composition is continuously fed into the reactor for reaction, and the reaction temperature is controlled at 30 ~ 30 (PC, compared to: 25 0 c, more preferably 80 ~ 24 0 ° c, and the pressure of the reactor is usually protected: made between 10kg / cm2; and in order to control the molecular weight of the polymer, this = manufacture of acetamyl resin composition In the process, a port initiator or a chain transfer agent can be used as needed. Material-capacity t η :: quality styrene resin composition is prepared by reacting the original device when the raw material solution is completely continuous. After the conversion rate of hydrazone, the polymer solution was removed from the reaction device to remove the unreacted monomers and volatile components into flavira :: granulation 'to obtain a styrene-based copolymer (Α). As the tree gum composition composition glue 11 (2) The rubber modified styrene as a dispersed phase is more than / 0 °, the final monomer conversion rate of the general polymerization reaction is 50 wt. 〇wt% or more, more preferably 70wt% or more.-Then use a decompression device or extrusion. Gas device. In the liquid collection afterwards: T unreacted monomers or volatile components are collected. 'If necessary, it can be returned to Γ: after removal' and reused as a raw material solution. Shape or solvent; Zhangzhong 'rubber modified stupid vinyl Block amount of resin composition = Feed solution used contains: (Η) 5. Weight, (1-3). ~ 4. Weight 2 may 4 = = parts of nitrile vinyl monomer, parts by weight The total of (Bu 2) and (1-3) is 100 weights, 100 weights, and + + 〇 Lixi Luneng maleimide-based monomers, 0 to weight 6 solvent and 0.5 to 25 Parts by weight of rubber; of which styrene

1242577 V. Description of the invention (14)-Monomer, Nitrile, Acrylic Mouth—Ah _ Nao Jujube Body, Other Copolymerizable Ethylene Monomers, Multi-Monthly B-Malaysian Malayan Disc Sub-Monomers , Solvent and polymerization cheese added as needed. The specific description of the type and amount of the two / bond transfer agent is the same as that for the production of the styrene: polymer (A) ❺ raw material solution, which is not described here. ^ In the first method mentioned above, an emulsion polymerization reaction can also be used to prepare a rubber-modified styrene-based resin composition. The method for preparing the emulsion polymerization reaction is the same as the method for preparing the rubber-like graft copolymer (B ') described below, but the amounts of monomers and rubber are as described in Method 1. The styrenic resin composition modified by Ben Maoming is lumpy or soluble. During the polymerization reaction, the a / valley fluid of the single limbs such as rubber, styrene monomer, and nitrile vinyl monomer is polymerized. In the initial stage, the rubber phase exists as a continuous phase. However, with the graft polymerization of rubber, the conversion rate of monomers such as styrene-based monomers and nitrile vinyl fluorene monomers gradually increases, and is accompanied by reaction stirring. The rubber component is gradually surrounded by monomers such as styrene-based monomers, nitrile vinyl-based monomers, and their polymers, and is transformed into a dispersed particle state (dispersed phase). On the other hand, the ethylenic monomers, nitrile Monomers such as vinyl monomers and their polymers are transformed into continuous phases. Finally, a rubber particle phase is formed. The weight-average particle diameter of the rubber particles is 0.05 to 10, preferably 0 to 5 and more preferably 0.1 to 2 // m. Specific examples of the rubber component in the method 1 are: diene rubber , Polyolefin rubber (example ethylene-propylene rubber), polyacrylate rubber, polyoxoxane rubber, etc. The aforementioned diene rubber is a polymer in which the glass transition temperature of the diene monomer component is below Q ° c after polymerization, and specific examples of the diene rubber. Butyl ~ rubber, isoprene-rubber, gas Butadiene rubber, epdm

Page 18 1242577 V. Description of the invention (15) Rubber, styrene-diene rubber, acrylonitrile-diene rubber, etc. Among them, butadiene rubber has high cis (Hi-Cis) content and low cis (Low-Cis) content in two types; in high cis rubber, the typical weight composition of cis (C is) / vinyl (V i ny 1) is (9 4 ~ 9 9%) / (0 ～ 5% ), The rest of the composition is a trans (Trans) structure; its Mooney viscosity is between 20 and 120, and its molecular weight range is preferably 100, 0 0 to 8 0, 0; 0; in low-cis rubber, cis The typical weight composition range of formula / vinyl is (20 ~ 40%) (eight 6 ~ 20%), the rest is trans structure, its Mooney viscosity is between 20 ~ 120, and its molecular weight range is 1 0 0,0 0 0 to 8 0 0, 0 0 0 is preferred; specific examples of the styrene-diene rubber are styrene-butadiene rubber, styrene-isoprene rubber, etc., which may be block copolymers, A regular copolymer or a copolymer whose composition is gradually increasing / tapering. Among them, the range of weight ratio of styrene in ethylene / butadiene rubber is preferably 50% by weight or less, and the molecular weight range is preferably 50,000 (600,000); but the above rubber is made of butadiene rubber and styrene / Butadiene rubber is preferred. <Method 2: Graft-kneading method> Method 2 'can be carried out by mixing the styrene copolymer (A) and the rubber graft copolymer (B') and extruding to obtain the modified rubber of the present invention. In the second method, the styrene-based copolymer (A) and the rubber graft copolymer (B ') are usually dry-blended with a commonly used Hanschel mixer, and then The scholars extrude the mixer such as a machine, kneader or banbury mixer, and then extrude the pellets. The method for producing the rubber graft copolymer (B,) is generally a block. Or dissolved

1242577 V. Description of the invention (16) Liquid polymerization, emulsion polymerization or suspension polymerization. Among them, the rubber graft copolymer (B,) is produced by a block or solution polymerization reaction in which a raw material solution is subjected to a graft polymerization reaction. The raw material solution is: (i -1) 50 to 90 parts by weight of a styrene-based monomer, (i-2) 10 to 50 parts by weight of a nitrile vinyl monomer, and (i-3) 〇 to 40 parts by weight Of other copolymerizable ethylene-based monomers, a total of 1,000 parts by weight, 0 to 100 parts by weight of a solvent, 0.5 to 25 parts by weight of rubber, and a polymerization initiator 'chain added as necessary Transfer agent; the raw material solution usually does not contain a polyfunctional maleimide imide-based monomer. If a polyfunctional maleimide imide-based monomer is used, its amount must be below the lower limit of the amount used in the present invention. Among them, styrene-based monomers, nitrile vinyl-based monomers, other copolymerizable vinyl-based monomers, solvents, and polymerization initiators as needed, and the specific descriptions of the types and amounts of chain transfer agents are the same. A raw material solution for producing a styrene-based copolymer (A), and a specific example of the composition of the rubber component will be described in the same way as in the first method. Mixed names of monomers such as ethylenic monomers exist in the state of continuous phase. The monomers such as ethylenic monomers and nitrile ethylene are accompanied by the stirring of the reactor. The monomers such as vinyl monomers and their states (dispersed phase), another ^ Monomers such as polymers and their polymers. The weight average of the rubber particles is more preferably 0.1 to 2 // m. In the rubber graft copolymer (B,) of the present invention, the 'rubber and styrenic monomer, nitrile B', and the valley liquid are at the initial stage of polymerization. The conversion rate of monomers such as monomers is gradually increasing, and the glue component is gradually surrounded by styrene-based monomers and nitrile polymers, and transformed into dispersed particles: It is a continuous phase. In the end, the rubber particles are separated from each other by 〇. 〇5〜1 〇〆m, preferably 〇. 〜1 ～ "冚 1242577 V. Description of the invention (17) --- In addition, the rubber graft copolymer (B,) can also be borrowed It is produced by emulsifying p-8 ′. The method is to make rubber latex 4 0 ~ 90 weight parts (completely solidify the olefinic monomer 1 5-95% by weight, nitrile vinyl-based monomer 5-5). Beta-copolymerizable monomers 0 to 35% by weight, monomers or monomers mixed by weight%, parts by weight, and emulsifiers, starting ^ two products 6 〇 ~ 10 0 repeat graft polymerization as needed Reaction to obtain a rubber graft copolymer 1 ^ bond transfer agent into the graft copolymer emulsion through coagulation, dehydration, drying and other steps 2 ', and then the rubber graft copolymer (B,) required by the foregoing invention. ^', , Ϊ́Α 'to obtain a specific example of the rubber component in the aforementioned rubber emulsion, a description of the rubber component, of which diene rubber is preferred. Di = the method of manufacturing the liquid in Method 1, can be a diene monomer (such as Butadiene = 100 to 50% by weight of rubber emulsion and 0 to 50 heavy denier / monoene monobenzene with other copolymerizable monomers Ethylene, acrylonitrile, (fluorenyl) acrylate, etc. can be copolymerized and blended. For example: Polymerization to polymerize to a weight average particle diameter of 0.05 to 0. 6 // m. Eribei et al. Can polymerize the aforementioned monomers by emulsion polymerization. The weight is obtained by the method; all; = 0.20 // m small-diameter diene rubber emulsion, and then the average particle diameter of the cold Λ is 0.2 2 ~ 0 · 6 // m of large particle size two Ethylene rubber liquid, ready for further step-by-step graft copolymerization reaction; among them, the additive used in the additive hypertrophy method may be: acetic anhydride, hydrogen chloride, sulfuric acid and other acids ^ biological shellfish 'or sodium chloride, chlorine Potassium chloride, calcium chloride and other basic substances, and (3-based) acrylic acid (fluorenyl) acrylate copolymer (such as: methacrylic acid-acrylic acid butyrate copolymer, methacrylic acid-ethyl acrylate copolymerization Polymer) and other polymer coagulants containing carboxylic acid groups.

1242577 V. Description of the invention (18) Various additives can be added to the rubber-modified styrene resin composition of the present invention, such as: antioxidants, lubricants, ultraviolet absorbers, ultraviolet stabilizers, antistatic agents, The coloring agent and the like can be added at the polymerization stage or the kneading extrusion stage of the styrene-based copolymer (A) or each rubber-modified styrene-based resin composition. The amount of the additive is usually 6 parts by weight or less based on 100 parts by weight of the rubber-modified styrene-based resin composition. Other additives such as flame retardants and impact modifiers can also be added as needed. Based on 100 parts by weight of rubber-modified styrene resin composition, the amount of additives such as flame retardants and impact modifiers is usually 30. Part by weight or less. In the rubber-modified styrene-based resin composition of the present invention, a resin other than the styrene-based copolymer (A) may be mixed as necessary. That is, the rubber-modified styrene-based resin composition may contain various polymers other than a styrene-based copolymer (A) in a continuous phase. The polymer may be acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-α methylstyrene resin, acrylonitrile-styrene-methylpropionate methyl acetate Resin, Acrylonitrile-styrene-N-phenylmaleimide resin, Styrene-anhydrous maleic acid resin, Styrene-N-phenylmaleimide resin, Polymethyl methacrylate, Poly Carbonate resin, styrene-methacrylic resin, methacrylic acid-butadiene-styrene resin, acrylonitrile-butadiene-N phenylmaleimide-styrene resin, polyamine resin, polymer Ester resin, polyphenylene ether resin, acrylonitrile-acrylate rubber-styrene resin, acrylonitrile- (ethylene-propylene diene rubber) -styrene resin, acrylonitrile-silicone-styrene resin, and other resins, the The resins can be used individually or in combination. Based on 100 parts by weight of a rubber-modified styrenic resin composition, the amount of the polymer used is usually 80 parts by weight.

Page 22 1242577 Fifth, the invention description (19). [Examples and Comparative Examples] The foregoing and other technical contents, features, and effects of the present invention will be clearly understood from the following description of the examples and comparative examples. [Synthesis example of styrenic copolymer (A)] Synthesis example a Synthesis of stupid ethylene copolymer (A-1)

In three series reactors, the first and second reactors are completely mixed reactors (hereinafter referred to as CSTR), and the third reactor is a column flow reactor (hereinafter referred to as PFR). Body (hereinafter referred to as SM) 64.5 parts by weight, acrylonitrile monomer (hereinafter referred to as AN) 35.5 parts by weight, N, N'-4,

4 '-Diphenylmethane bismaleimide imine monomer (hereinafter referred to as BMI) 0. 02 5 parts by weight, polymerization initiator dibenzidine peroxide (hereinafter referred to as BPO) 0.02 parts by weight, chain transfer Dodecyl mercaptan (hereinafter referred to as TDM) 0.4 parts by weight and 25 parts by weight of solvent ethylbenzene (hereinafter referred to as EB) were continuously supplied to the first reactor for polymerization at a flow rate of 36 kg / hour. Reaction; introducing the polymer solution obtained from the first reactor into the second reactor, and continuously supplying a mixed solution of 100 parts by weight of SM and 0.22 parts by weight of BMI to the second reactor at a flow rate of 2 kg / hour The reactor is subjected to a polymerization reaction; the polymer solution obtained by the second reaction is introduced into the third reactor, and a mixed solution of 1 part by weight and BM I 0.4 part by weight is flowed at a flow rate of 2 kg / hour. Continuously supplied to the third reactor for polymerization; wherein the volumes of the first, second, and second reactors were 40, 40, and 75 liters, respectively, and the temperatures of the reaction tanks were 95, 105, and 135 C, respectively. , The stirring rate is 12 (), 90, 35rpm

III

fA

Page 12 1242577

The final monomer conversion at the reactor exit was 72% by weight. After the polymerization is over, Tongdang 9 bamboo chrysanthemum takes 4H and Guangdao X π 4 condolences will be the common water obtained from the reaction of the younger three reactors> Valley fluid &amp; enter the devolatilization device. Stem P; L „The devolatilization device such as a decompression devolatilization device or an extruded devout temple: u This device removes unreacted monomers and other volatiles; and ΪΓΪΠ hydrates the molten material and pellets it to obtain Styrene-based co-fine An; The styrene-based diene copolymer (A_n) and its physical properties are listed in Table 1. Synthesis Example b The combination of stilbene-based fine copolymer (A-2) in three series reactions Reactors are the first and second reactors are CSTR, the third reactor is PFR, SM 65 · 5 parts by weight, an 34.5 parts by weight, BM I 0 · 0 2 2 parts by weight, polymerization initiator 丨, 丨 -bis-third butyl peroxide-3,3,5-dimethylcyclohexyl;!: End (hereinafter referred to as τχ — 29A) 〇〇〇 重量 parts, TD Μ 0 · 4 parts by weight, Ε Β 2 5 parts by weight of the mixed solution was continuously supplied to the first reactor at a flow rate of 37 kg / hour for polymerization; the polymer obtained in the first reactor was dissolved Introduce the second reactor, and continuously supply a mixed solution of $ M 100 parts by weight and BM I 0 · 15 parts by weight at a flow rate of 3 kg / hour to the second reactor for polymerization reaction; The polymer solution obtained from the two reactors is introduced into the third reactor for polymerization reaction, wherein the volumes of the first, second, and third reaction states are 40, 40, and 75 liters, respectively, and the temperature of the reaction tank is 95, 105. , 1 35 ° C, stirring rates were 20, 90, and 35 rpm; the monomer conversion rate at the exit of the reactor was 74% by weight. After the polymerization was completed, the copolymerization obtained by the reaction in the third reactor was the same as in Synthesis Example a. The benzene solution can be devolatized, extruded, and granulated to obtain benzene.

Page 24 1242577 V. Description of the invention (21) Ethylene and ethylene copolymers (A-2); The manufacturing formula of this stupid ethylene copolymer (A-2) and its physical properties are listed in Table 1. The copolymer (A-3) was synthesized in four reactors in series, the first and second reactors were CSTR, the third and fourth reactors were PFr, SM 64. 5 parts by weight, AN 35 5 parts by weight, 0.007 parts by weight of BMI, polymerization initiator 2,2-bis (4,4-di ~ third-butylperoxy) cyclohexylpropane (hereinafter referred to as PX-12) 0.5 parts by weight The mixed solution of TD Μ 0 · 4 parts by weight and EB 2 5 parts by weight was continuously supplied to the first reactor for a polymerization reaction at a flow rate of 36 kg / hour; the polymer solution obtained from the first reactor was introduced In the second reactor, a mixed solution of 100 parts by weight of SM, 0.06 parts by weight of BMI, and 54 parts by weight of τχ-29A 0.50 was continuously supplied to the second reactor at a flow rate of 2 kg / hour. During the polymerization, the polymer solution obtained in the second reactor was introduced into the third reaction tank, and a mixed solution of 1,000 parts by weight of SM and 0.013 parts by weight of TX-29Δ was continuously supplied at a flow rate of 2 kg / hour. Go to the third reactor for polymerization; and then introduce the polymer solution obtained from the third reactor into the fourth reactor ΪΊPolymerization reaction: Among them, the first, third, third, and fourth reactions i ^ 2:, 4 0, 4 0, 7 5, 7 5 liters, the temperature of the reaction tank is 0, 1 3 5 C ' The mixing rates were 1 2 0, 9 0, 3 8 and ΓPIΪ1 ^ times 1 and the monomer conversion rate at the reactor outlet was 76% by weight. Qiu Yan: After the same as in the Synthesis Example &amp;, the fourth reactor was used for devolatilization, extrusion, granulation and other steps, g just arrived at benzene (A-3); the stupid ethylene-based copolymer (A-3) Manufacturing

1242577 V. Description of Invention (22) Fang and its physical properties are listed in Table 1. Synthesis Example d Synthesis of stupid ethylene copolymer (A-4)

In three reactors in series, the first and second reactors are CSTR, the third reactor is PFR, SM 64. 5 parts by weight, AN 35.5 parts by weight, BMI 0. 0 2 8 parts by weight PX- 1 2 0. 0 0 6 parts by weight, TDM 0.4 parts by weight, EB 2 5 parts by weight of the mixed solution was continuously supplied to the first reactor for a polymerization reaction at a flow rate of 36 kg / hour; The polymer solution obtained from the first reactor was introduced into the second reactor, and a mixed solution of 100 parts by weight of SM and butyl X -29A 0.03 3 parts by weight was continuously supplied to the first reactor at a flow rate of 2 kg / hour. Polymerization reaction is performed in the two reactors; the polymer solution obtained in the second reactor is introduced into the third reactor, and the SM 100 weight part solution is continuously supplied to the third reactor at a flow rate of 2 kg / hour. Polymerization is performed; wherein the volumes of the first, second and third reactors are 40, 40, and 7 5 liters, respectively, and the temperature of the reaction tanks are 9 5, 10, 5 and 15 ° C, respectively. The rates were 120, 90, and 35 rpm, respectively; the monomer conversion at the exit of the final reactor was 71% by weight.

After the polymerization is completed, the copolymer solution obtained by the reaction in the third reactor is subjected to steps such as devolatilization, extrusion, and granulation in the same manner as in Synthesis Example a to obtain a styrene copolymer (A-4): the styrene copolymer The manufacturing formula of the compound (A-4) and its physical properties are listed in Table 1. Synthesis Example e Synthesis of Styrene Copolymer (A-5) In three reactors in series, the first and second reactors are

Page 26 1242577 V. Description of the invention (23)

CSTR 'The third reactor is PFR, a mixed solution of SM 64 · 5 parts by weight, AN 35.5 parts by weight, BMI 0.022 parts by weight, BPO 0.02 parts by weight, TDM 0.4 parts by weight, and EB 2 5 parts by weight A flow rate of 36 kg / hour was continuously supplied to the first reactor for polymerization; the polymer solution obtained from the first reactor was introduced into the second reactor, and SM 100 parts by weight, BMI 0.2 parts by weight, τχ-29A 0.08 parts by weight of the mixed solution is continuously supplied to the second reactor for polymerization at a flow rate of 2 kg / hour; the polymer solution obtained from the second reactor is introduced into the third reactor, and The SM 100 parts by weight solution was continuously supplied to the third reactor for polymerization reaction at a flow rate of 2 kg / hour; wherein the volumes of the first, second, and third reactors were 40, 40, and 7 5 respectively. Liter, the temperature of the reaction tank is 95, 105, 135 ° C, the stirring rate is 120, 90, 35 rpm respectively; the monomer conversion rate at the exit of the reactor is 72% by weight. After the polymerization is completed, the copolymer solution obtained in the third reactor is subjected to steps such as devolatilization, extrusion, and granulation in the same manner as in Synthesis Example a to obtain a styrenic copolymer (A-5): the styrenic copolymer The manufacturing formula of the substance (A-5) and its physical property analysis are listed in Table 1. Synthesis Example f

The synthesis of stupid ethylene-based copolymer (A-6) is the same as the operation method of Synthesis Example b. The difference is that the amount of monomer used in the feed mixed solution of the brother-reactor is adjusted to SM 60, respectively. Parts by weight, AN 34 parts by weight, 6 parts by weight of fluorenyl acrylate (hereinafter referred to as MMA), and the monomer conversion rate at the exit of the final reactor was 74% by weight; the manufacturing formula of the styrenic copolymer (A-6) Its physical properties are listed in Table 1.

Page 27 1242577 V. Description of the invention (24) Synthesis of synthetic copolymer (A-7), operation method of synthesis example b, the difference is that the feed of the first reactor and the solution used in the solution The amount of monomers was adjusted to 61 parts by weight, 39 parts by weight of AN, and the amount of TDM was adjusted to 0.5 parts by weight. The monomer conversion rate at the outlet of the reactor after taking was 72% by weight; The manufacturing formula of the copolymer (A-7) and its physical properties are listed in Table 1. Synthesis ijjj] Depolymer (A-8) is synthesized in two reactors in series, the first and second reactors are CSTR, the third reactor is PFR, SM 73.0 parts by weight, AN 27. 〇 重 BΜΙ 〇.〇66 66 parts by weight, TX-29A 0.01 parts by weight, TDM 0.3 = parts by weight, EB 25 parts by weight of the mixed solution, at a flow rate of 37 kg / hour, ... The reactor performs polymerization reaction. · The first reactor solution is introduced into the second reactor, and 100 parts by weight of SM and 〇 · = parts by weight of the mixed solution are continuously fed at a flow rate of 3 kg / hour. Polymerization is performed in the second reactor; the second = substance = liquid obtained in the second reactor is introduced into the third reactor to perform the polymerization reaction; wherein the volumes of the first and second reaction states are 40 and 4, respectively. 0,7 5 liters, the temperature of the reaction plug is 95, 105, l35t, the stirring rate is 12o, 3o rpm; the final monomer conversion rate of the reactor outlet is 73% by weight. After the polymerization is completed, the copolymer solution obtained from the reaction in the third reactor is subjected to the steps of devolatilization, extrusion, and granulation in the same manner as in Synthesis Example a to obtain an ethylene-based copolymer (A-8); Preparation of copolymer (A-8)

Page 28 1242577 V. Description of the invention (25) Fang and its physical properties are listed in Table 1.

Synthesis Example I Synthesis of the copolymer (A-9) in two reactors in series, the first and second parts are 68 parts by weight SM, 32 parts by weight AN, 0.4 parts by weight BPO, and 2.5 parts by weight eb Parts of the mixed solution! 'The polymer solution obtained by continuously supplying the first reactor to the polymerization reactor is introduced into the second reactor' The volumes of the first and second reactors are 4 ^^ The temperature is 丨 2 〇 ,! 20%, the monomer conversion rate at the exit of the final reactor was 5 2% by weight. After the end of σ, the copolymer solution such as the first copolymer solution was devolatilized, extruded, and pelletized. -9) • The styrene prostitutes and their physical properties are listed in Table 1. … Comparative Synthesis Example i The same operation method as in Comparative Synthesis Example 1, except that the mixed solution is fed, and the monomer conversion rate h of the BMI 〇01 heavy exit is added, and the weight is f / G, The formula of Haiben Ethylene and its physical properties are listed in Table 1. The synthesis method of the comparative synthesis example k olefin series i) is the same as that of the comparative synthesis example 1. The different reactors are CSTR, 02 parts by weight, TDM, and the reaction is carried out at a flow rate of 40 kg / hour; then the first reaction is carried out for polymerization reaction; It is 40 liters and the reaction tank type is 120 and 90 rpm. 〇 Two reactor reaction steps, you can get benzene (A-9). The preparation is made by the first reaction amount, and finally the reactor is copolymerized. (A-10) is the first reaction

Page 29 1242577 V. Description of the invention (26) To the feed mixed solution of the device, add divinylbenzene monomer (hereinafter referred to as DVB) 0. 0 3 5 parts by weight, and adjust the amount of TDM to 0.5 parts by weight The final monomer conversion rate at the exit of the reactor was 54% by weight; the manufacturing formula of the styrenic copolymer (A-1 1) and its physical properties are listed in Table 1. 6 重量 份 Comparative Synthesis Example 1 The synthesis of stupid ethylene copolymer (A-12) was performed in the same manner as in Synthesis Example b, except that the amount of TDM in the feed mixed solution of the first reactor was adjusted to 0.6 parts by weight. The final monomer conversion rate at the exit of the reactor was 72% by weight: The manufacturing formula of the styrenic copolymer (A-12) and its physical properties are listed in Table 1. 1 重量 份 Comparative synthesis Example m The synthesis of stupid ethylene copolymer (A-13) is the same as that of Synthesis Example b, except that the amount of TDM in the feed mixed solution of the first reactor is adjusted to 0.1 parts by weight The final monomer conversion rate at the exit of the reactor was 73% by weight. The manufacturing formula and physical properties of the styrene-based copolymer (A-1 3) are listed in Table 1. Comparative Synthesis Example η The synthesis of stupid ethylene copolymer (A-1 4) is the same as that of Comparative Synthesis Example 1. The difference is that the feed mixed solution of the first reactor is added to BM I 1.5 weight During the reaction, the viscosity of the reaction system increased sharply, and the hue of the reaction product became worse, resulting in many high molecular weight bridging foreign matters and stains, which caused the polymerization reaction to continue, and the reaction product was taken out to determine the flow coefficient. The MIR of the instrument analysis was 32.5.

Page 30 1242577 V. Description of the invention (27) [Synthesis example of rubber graft copolymer (B, — 丨)] ^ In four reactors in series, the first to fourth reactors are all CSTR, and SM 6 ^ Parts by weight, AN 32 parts by weight, butadiene rubber (hereinafter referred to as BD) 7 stomach 0, parts by weight, βP0 0.03 parts by weight, TDM 0.3 parts by weight, EB 35 parts by weight 1 part mixed solution, 40kg The flow rate per hour is continuously supplied to the first reactor for the polymerization reaction. Among them, the volumes of the first, second, third, and fourth reactions are all 40 liters, and the temperatures of the reaction tanks are respectively 〇〇〇, 105 ° C, 130 ° C. The stirring rates were 300, 2000, 150, and 90 rpm, respectively; the monomer conversion rate at the exit of the reactor was 65% by weight. After the polymerization is completed, the copolymer solution obtained in the fourth reactor is subjected to the steps of devolatilization, extrusion, and granulation in the same manner as in Synthesis Example a to obtain a rubber graft copolymer (B'-1). The rubber component content 10% by weight. [Synthesis example of rubber graft copolymer (B,-2)] [Table 2] Ingredients by weight 1.3-butadiene 150.00 potassium persulfate solution (].% &Gt; 15.00 potassium oleate 2.00 distilled water 190.00 ethylene glycol di I ^ m 的 methacrylate 0.13 was reacted at a reaction temperature of 65 ° C for 14 hours according to the above formula in Table 2 to obtain a conversion rate of 94%, a solid content of about 36%, and a weight average particle size of about 0.1 ^ m Synthetic rubber emulsion. [Table III]

1242577 V. Description of the invention (28) Ingredients--parts by weight-»v.Au \ .Λ 4 _______ 'Butyl acrylate __ 90.00 Methacrylic acid _ _ 10.00 Potassium perthiosulfate solution (1%) __ _ 0.50 12 Sodium alkyl sulfate solution (10%) 0.50 η-dodecyl alcohol 1.0 Distilled water 200.00

According to the formula in Table 3 above, the reaction is performed at a reaction temperature of 75 ° C for 5 hours. The reaction rate is about 95%, and the polymer coagulant emulsion containing carboxylic acid group has a pH value of 6_0.

^ Thereafter, 3 parts by weight (dry weight) of a carboxylic acid group-containing polymer coagulant was used to enlarge 100 parts by weight of a synthetic rubber latex, and the pH value of ^ obtained was 8. 5 1, Guang Congda Λ Ti Ling Ling d η, the average particle size of furniture weight s is about 0.3 1 // m. According to the formula in Table 4 below, the hypertrophic rubber emulsion was polymerized according to the formula in Table 4 below, and the polymerization was performed to produce ^ @ 7 with a styrene-acrylonitrile copolymer [Table 4 ] Clothing ^ rubber graft copolymer (B, -2).

1242577 V. Description of the invention (29) Ingredients by weight _ Fattening rubber emulsion [dry weight] 100.0__ Phenylhexene monomer 75.0 Propylene, eye carcass 25.0 Thirty-two dodecyl mercaptan 2.0__ Argon over gasified isopropyl Benzene 3.0 ferrous sulfate solution (0_2%) 3.0 formaldehyde sodium sulfoxylate solution (10%) 0.9 ethylenediamine tetraacetic acid solution (0.25%) 3.0 The rubber graft copolymer emulsion prepared according to the formula in Table 4 Chlorinated # 5 is coagulated, and then dehydrated and dried to less than 2% to obtain a rubber graft copolymer (B'-2) (rubber content 50% by weight, rubber weight average particle size 0.31 // m) . [Examples and Comparative Examples of Rubber-Modified Styrene Resin Compositions] Simultaneous Grafting Method Example 1

In four reactors in series, the first and second reactors are CSTR, the third and fourth reactors are PFR, SM 65 · 5 parts by weight, AN 34.5 parts by weight, and BD 8.0. 5 parts by weight, BMI 0. 022 parts by weight, TX-29A 0. 0 4 parts by weight, TD M 0.4 parts by weight, plasticizer butyl stearate (hereinafter referred to as BS) 1.5 parts by weight, EB 35 parts by weight The mixed solution was continuously supplied to the first reactor at a flow rate of 37 kg / hour for polymerization reaction; the polymer solution obtained in the first reactor was introduced into the second reactor, and SM 100 parts by weight and BM I 〇 · 15 parts by weight of the mixed solution is continuously supplied to the second reactor for a polymerization reaction at a flow rate of 3 kg / hour;

Page 121242577

== Polymer solution is introduced into the third reactor for the polymerization reaction; and the first: • The polymer solution served is introduced into the fourth reactor for the polymerization reaction =, 4 n 'Di, 1, 2, 3, and 4 reactions The volume of the reactor is 75 liters, the temperature of the reaction tank is 100, 105, and 115 g C, and the stirring rates are 300, 2000, 150, and 90 rpm. 75% by weight. After the 4 wf polymerization is completed, the same synthesis example a 胄 is used to carry out steps such as devolatilization, extrusion, and granulation from the fourth reactor. The content of the rubber component is 10% by weight. • The rubber-modified styrene-based resin composition is dissolved in tetrahydrofuran. 1 The continuous phase of stupid ethylene-based copolymer (A) is obtained, and its weight average is measured. It is 103, 711, and the value of MIR is 24.2. The rubber-modified styrene: resin formulation and its physical properties are listed in Table 5. / 、 Comparative Example j In: a series reactor '-is the first-, the second reactor is the first, the fourth reaction is PFR, the SM 68 parts by weight, AN 32 parts by weight, BD 8. 0 parts by weight The mixed solution of BMI 〇. 0 0 0 2 parts by weight, τχ_29Α 0j4 parts by weight, TDM 〇4 parts by weight, BS 15 parts by weight, Εβ π parts by weight, is continuously supplied to the first — $ 应The reactor carries out the polymerization reaction; "In the first, second, third, and fourth reactors, the volumes are 40, 40, 75, and 75 liters, respectively, and the temperature of the reaction tank is 100, 105, 115, 130t, with stirring rates of 300, 2000, 150, and 90 rpm, respectively; the monomer conversion rate at the exit of the reactor was in weight percent. At the end of the polymerization [same as in Synthesis Example a)

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Copolymer = liquid for devolatilization, extrusion, granulation and other steps to obtain a rubber-modified styrene-based resin composition with a rubber component content of 0.3% by weight; the rubber-modified styrene-based The resin composition was dissolved in a tetrahydrofuran solution to obtain a continuous phase of a styrenic copolymer (A), and its weight average molecular weight was determined to be 101, 2 2 4, and the value of M IR was 2 1.1; The manufacturing formula of the styrene resin composition and its physical properties are listed in Table 5. Example 2 for branching and kneading 20 parts by weight of the rubber graft copolymer (B'-1), 30 parts by weight of the rubber graft copolymer (B'-2), 50 parts by weight of the styrene-based copolymer (A-1), and Ethylene bisstearamide (hereinafter referred to as EBS) 0.3 parts by weight, dry-mixed with a Hanschel mixer, and then with a raw material tank temperature of 2000 ~ 2 2 0 ° C, die temperature 2 2 0 ° C biaxial extruder with exhaust port melt-kneaded, can produce pellets (pe Π et) rubber modified styrene resin composition, rubber content 17% by weight • The manufacturing formula of this resin composition and its physical properties are listed in Table 6. Multiple Example 3 30 parts by weight of a rubber graft copolymer (B,-2), 50 parts by weight of a styrene-based copolymer (A-2), and 20 parts by weight of a rubber-modified styrene-based resin composition of Example 1 Parts &amp; EBS 0.3 parts by weight, in the same extrusion conditions as in Example 2, a pellet-shaped rubber modified styrene resin composition can be obtained, with a rubber component content of 17% by weight; the The manufacturing formula of the resin composition and its physical properties are listed in Table 6.

1242577 V. Description of the invention (32) 34 parts by weight of a rubber graft copolymer (B'-2), 66 parts by weight of a styrene-based copolymer (A-1), and 0.3 parts by weight of EBS, the same as in Example 2 Under the extrusion conditions, a pellet-shaped rubber modified styrene-based resin composition can be obtained with a rubber content of 17% by weight; the manufacturing formula of the resin composition and its physical property analysis are shown in Table 6. . Examples 5 to 1 1 are operated in the same manner as in Example 4, except that the type and amount of the styrene-based copolymer (A) are adjusted; the rubber-modified stupid vinyl-based resin composition is formulated and Its physical properties are listed in Table 6. Comparative Example 2 The method of operation is the same as that of Example 2, except that the type of styrene-based copolymer (A) is changed; the manufacturing formula of the modified styrene-based resin composition modified by rubber and its physical properties are listed in Table six. Than car damage U 3 ~ 7 The operation mode is the same as that in Example 4, except that the type of the styrene-based copolymer (A) is changed; the manufacturing formula of the rubber-modified styrene-based resin composition and Its physical properties are listed in Table 6. [Evaluation method]

1 · MIR The MFR measured at a temperature of 2000 ° C and a load of 1 kg is the MI (g / 10 minutes) measured at a temperature of 200 ° C and a load of 10 kg. The MFR is HMI (g / 10 points), and the MIR is the ratio of ΗMI / MI. Among them, MFR is a melt flow index, which is measured by the ASTM D-1 2 38 method. 2. Weight average molecular weight

Page 1212577

The stupid ethylene copolymer (A) described above was dissolved in a solvent of tetrahydrofuran, and then analyzed by a gel dialysis chromatography (GPC, manufactured by Waters Corporation), and polyethylene was used as an analysis standard. The analysis conditions of the above gel dialysis chromatography are:

Column: KD-806M Detector: Water RI — 2410 Mobile phase: THF (flow rate 1.0 / min) 3. Rubber content: Fourier transform infrared ray produced by Nico let, model Nexus 4 70

Spectrometer (Fourier Transform Infrared Spectrometer) test. unit weight% . 4. Financial Impact As measured by the A STM D-2 56 method, the size of the test piece is 1/4 inch with a notch ◦ Unit ·· kg-cm / cm. 5. Liquidity

The rubber-modified styrene-based resin composition was injection-molded on a Zhenxiong 90 injection molding machine. The injection conditions were: injection temperature of 2000 ° C, injection pressure of 100 kg / cm2, and mold temperature of 50. ° C, the mold used is a spiral flow (spiral flow) mold (2mmt), the flow length is used as the basis for fluidity evaluation. Unit: mm.

〇: 2 3 0 mm or more Δ: 215 to 2 30 mm X: 215 mm or less stress crack resistance Page 37 1242577 V. Description of the invention (34) Place a test piece with a diameter of 100 mm x 12.7 mm x 3 mm at a radius of curvature of 165 mm The fixture was immersed in a 50% alcohol solution, and the time to cracking of the test piece after the immersion was measured. The longer the time, the better the financial stress cracking. 〇Δ X Stain for more than 48 hours 2 4 ~ 4 8 hours 24 hours Take 10 grams of the rubber-modified styrene resin composition described above and press it with a hot press into a round shape with a diameter of 200 mm and a thickness of 0.3 mm After thinning, observe the number of stains. 〇 Δ 0 ~ 1 point 2 ~ 4 points

Page 42 1242577 Schematic illustrations Page 39

Claims (1)

1242577 VI. Scope of patent application1. A rubber modified styrene resin composition composed of a styrene copolymer (A) as a continuous phase and a rubber particle (B) as a dispersed phase, and stupid ethylene The copolymer (A) is composed of (i-1) 50 to 90 parts by weight of a styrene-based monomer, (i-2) 1 to 50 parts by weight of a nitrile vinyl monomer, and (i 3 ) 〇 ~ 40 parts by weight of other copolymerizable ethylenic monomers' above (i-1), (Bu 2), (i-3) in total 100 parts by weight, and 0.0005 to 1.0 parts by weight of polyfunctional It is obtained by copolymerization of maleic imide monomers; among them, the rubber content of the stupid vinyl resin composition modified by rubber is 40% by weight; The MFR measured at a temperature of 200 ° C and a load of 1 kg is MI (g / 10 minutes), and the MFR measured at a temperature of 200 ° C and a load of 10 kg is HMI ( g / l0 points), its MIR (two HMI / MI) is between 21.5 ~ 30. 0, and its weight average molecular weight is between 6 0,0 0 ~ 1 45,0 0. Page 40