TWI242578B - Rubber modified styrene system resin composition for extrusion molding - Google Patents

Abstract

This invention is one kind of rubber modified styrene system resin composition for extrusion molding having large output quantity of extrusion plank and the molded plank with superior stress cracking resistance, few stains, and excellent processing characteristic of vacuum moldability and blow molding moldability 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 250 DEG C with load weight of 1 kg is MI (g/10 minutes), the measured MFR at temperature 250 DEG C with load weight of 10 kg is HMI (g/10 minutes), its MIR (=HMI/MI) is between 22 to 33, and its weight average molecular weight is between 150000 to 450000.

Description

1242578 V. Description of the invention (T). [Technical field to which the invention belongs] The present invention provides a grease composition, which has excellent cracking properties, less stains, and processing characteristics. [Previous technology] The general thermoplastic styrene has a good evaluation in terms of its properties, and its characteristics are a major feature, as well as automotive parts. Generally, it is processed by a molding method such as thermoplastic molding. The vacuum molding method or blow molding is first extruded into a sheet and then the required molded products are made. The resin must have a high level to maintain a good 3 6 6 1 9 and special opening 2 after molding. 〇 (Π-2 0 7 0 1 5 amount, it will cause stress cracking of fluid materials, such as poor cracking, etc. It is proposed that polyfunctional ethylene such as aromatic monoethylene divinylbenzene and its impact properties However, there are too many diethyl groups, and the reactor wall has too many rubber-modified styrene-based trees. The amount of extruded styrenic trees is large, and the post-molded sheet has excellent vacuum moldability and blow molding resin. Processing moldability, good appearance and gloss of machinery, especially molded products, are widely used in electronics and electrical appliances_ Stupid vinyl is also required by special law, and then. For melting and strong meat thickness, it will be exposed and dropped. Fine-based alkylene compound benzene makes the south resin can be processed into a product 'Vacuum molding into a vacuum forming degree, that is, ten years, such as r, but in general injection molding, you need to change the method or type or blow Shuyue Zhiyue Bente The output volume of the plate from the high tree is the same as the way of polymerizing the reactants in the Japanese Patent Application No. Heiping 2, which is changed to the molecular weight that is easy to cause the copolymer to cross the foreign body. Kaiping 10 0-lipid molecule reduction and plate 1 8 2 7 1 1, adding good moldability and reaction and finally

Page 5 1242578 V. Description of the invention (2) Excessive stains on stupid vinyl resin So how to get a large amount of extruded sheet and stress resistance of sheet

Si} 1 Λ. ^:.. Stupid vinyl resin composition with less soil and stains is a subject that has long been hoped to break through for those who are familiar with this technology field. [Summary of the Invention] The main purpose of the present invention is to provide an extruded sheet with a large size, good stress cracking resistance, less stains, and excellent air formability and blow molding. Stable vinyl-based resin composition modified by rubber for extrusion processing.

Because of this, the present invention provides a rubber-modified styrene-based resin composition, which is composed of a stupid ethylene-based copolymer (A) as a continuous phase and rubber particles (B) as a dispersed phase, and styrene The copolymer (a) is composed of (丨 一 工) 50 = 90 parts by weight of a styrene-based monomer, (i_2) 10 to 50 parts by weight of a nitrile ^ dilute monomer, and (i-3) 〇 ~ 40 parts by weight of other copolymerizable ethylene-based monomers' (1-1), (1-2), (i-3) totaling 1,000 parts by weight, and 0.005-5 ~ 1.0% by weight of a polyfunctional maleimide-based imide monomer copolymerized; wherein the rubber content of the rubber-modified styrene-based resin composition is 40% by weight: styrene-based copolymerization (A) The MFR measured at a temperature of 250 ° C and a load of 1.0 kg is MI (g / 10 minutes), the temperature measured at a temperature of 250 ° C and a load of 10 kg is HMI (g / 10 points), the MIR (two HMI / MI) is between 22 and 33, and its weight average molecular weight is between 150,000 and 450,000. The rubber-modified styrene-based resin composition of the present invention is composed of a specific styrene-based copolymer (A) as a continuous phase and rubber particles (b) as a dispersed phase. The composition has thermal stability and impact resistance. Strength, fluidity, etc.

1242578 V. Description of the invention (3) Excellent mechanical properties, large extruded sheet output, good resistance to cracking after forming, and uniformity of meat thickness during vacuum forming and blow molding. [Embodiment] Specific examples of (1 -1) styrenic monomers used in the present invention are: styrene, α-methylstyrene, p-tert-butylstyrene, p-methylstyrene, ortho- -Fluorenylstyrene, m-fluorenylbenzylethylene, 2,4-dimethylstyrene, ethylstyrene, "α-fluorenyl-p-fluorenylstyrene and bromostyrene, etc. Ethylene or α-methylstyrene is preferred. Each of the above compounds can be used alone or in combination. Based on the total of (1-1), (i-2), and (1-3) 100 parts by weight, the styrene-based monomer of the present invention is used in an amount of 50 to 90 parts by weight, preferably 5 5 to 8 5 parts by weight, more preferably 5 8 to 80 parts by weight. (1-2) used in the present invention, the nitrile vinyl-based monomer may be acrylonitrile, α-fluorenyl acrylonitrile, etc., of which acrylonitrile is preferred. Based on the total of 100 parts by weight of the above (i-1), (i-2), and (i-3), the used amount of the nitrile vinyl monomer of the present invention is 10 to 50 parts by weight, preferably 15 to 50 parts by weight. 45 parts by weight, more preferably 20 to 4 2 parts by weight. The (i-3) other copolymerizable ethylene-based monosystem used in the present invention means that it has a vinyl group and is compatible with the (1- -1) styrene-based monomer and (1-2) nitrile ethylene of the present invention. Specific examples of monomers copolymerized with monomers are acrylate monomers, fluorenyl acrylate monomers, and monofunctional maleimide imide monomers. Among them, specific examples of acrylic acid monomers are: methyl acrylic acid, ethyl acrylate, isopropyl acrylate, butyl acrylate, and polyethylene glycol dipropylene.

Page 7 1242578 V. Description of the invention (4) Polyethylene glycol diacrylate, etc. Among them, butyl acrylate is preferred. Examples are: propyl methacrylate, butyl butyl methacrylate, hexyl methacrylate, methacrylic acid, 2-hydroxyethyl cyclohexenoate, propyl propyl ethyl ester, ethylene dimethyl propyl), difluorenyl Neopentyl acrylate, in which the specific vinegars of methacrylic acid and methacrylic acid ester monomers, methacrylic acid ethyl ester, methacrylic acid, and methacrylic acid phenyl methacrylic acid ester, methacrylic acid vinegar, and methacrylic acid Acid dodecyl @, propylene methacrylate, ethylene di methacrylate S (neopentyl dimethacrylate) and other esters, butyl butyl acrylate is preferred. Monofunctional The maleimide imide monomer means that the monomer contains only a single maleimide functional group, and specific examples are: maleimide, N-fluorenylmaleimide, N-iso Propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N -Cyclohexylmaleimide, N-phenylmaleimide, N-2-fluorenylmaleimide, N-2,3-dimethylphenylmaleimide, N- 2 , 4-dimethylphenylmaleimide, N-2, 3-diethylphenylmaleimide, N-2,4-diethylphenylmaleimide, N- 2,3-dibutylphenylmaleimide, N-4-dibutylphenylmaleimide, N-2, 6dimethylphenylmaleimide, N-2, 3 -dichlorophenylmaleimide, N-2,4-dichlorobenzylmaleimide, 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, fluorenyl) Acrylic acid), anhydrous maleic acid, anhydrous fluorenyl

1242578 V. Description of the invention (5) Unsaturated diacid compounds such as maleic acid, anhydrous fumaric acid, fumaric acid, itac nicacid, and the esterification thereof Monomers (eg dimethyl fumarate, dibutyl itaconic acid), ethylene, propylene, 1-butane, 1-pentane, 4-methyl-1-pentane, ethyl chloride , Vinyl chloride fork, ethylene tetrafluoride, monogas ethylene trifluoride, propylene hexafluoride, butadiene, allylamine, isobutyleneamine, vinyl acetate, ethyl vinyl ether, fluorenyl vinyl ketone, triethylene Allyl isocyanate (tr 1 a 1 1 y 1 isocyanate) and the like. Based on the above 100 parts by weight of (i-1), (i-2), and (i-3), the use amount of (1-3) other copolymerizable vinyl monomers of the present invention is 0 to 4 0 parts by weight, preferably 1 to 34 parts by weight, and more preferably 3 to 30 parts by weight. The polyfunctional maleimide imide-based monomer used in the present invention means a compound containing at least two maleimide imine functional groups, for example, a compound having two or three imine functional groups. Among them, bismaleimide imine monomer is preferred, and its structural formula can be expressed by general formula (1) 0 ″ -k 0

N

X

Λ, -Ν I

General formula (l) [where X is an alkylene group having 1 to 10 carbon atoms, ary 1 ene group, carbonyl group group, one S02—, one SO— , -0-, -〇-R-0- (R may be alkylene, arylene)], specific examples are: N, N'-4,4 '-(3, 3'-dimethyldi Phenylmethane) bismaleimide [N, N'-4,4 '-(3

Page 9 1242578 V. Description of the invention (6), 3'-dimethyl diphenyl inethane) bismaleimide], N, N'-4, 4 '-(3, 3'-diethyldiphenylphosphonium) bismaleate Fluoreneimine, [N, N'-4,4,-(3,3'-diethyl diphenyl niethane) bismaleiinide], N, N'-4,4'-diphenylphosphorane bismaleimide ( N, N '-4, 4' -diphenyl methane bismaleimide), N, N'-4,4'-2,2-diphenylpropanyl bismaleimide (N, N'-4,4 ' -2,2-diphenyl propane bismaleimide), N, N'-4,4'-diphenyl ether bismaleimide (N, N, -4,4 '-(1101161 ^ 16VII) 161'1 ^ 311131611111 (16), 1 『-3,3'-Dibenzyl maple bismaleimide (N, N '-3,3'-diphenyl sulfone bis in a leimide), ^『-4,4' -Dibenzyl maple bismaleimide (^^ -4,4, -diphenyl sulfone bismaleimide), N, N, -4,4, -diphenylimide bismaleimide (N, N '-4, 4' -diphenyl sulfoxide bismaleimide), N, N '-4,4' -benzophenone bismaleimide (N, N '-4, 4J -benzophenone bismaleimi de), N, M, 1,3-phenylene bismaleimide (N, N'-1,3-phenylene bismaleimide), in which N, N '~ 4,4, -diphenyl Pinane bismaleimide imine, n, N, -1,3-benzylidene bismaleimide imine are preferred. Based on the above (i-1), (i-2), (i-3) A total of 100 parts by weight, the use amount of the polyfunctional maleimide-based monomer of the present invention is 0.005 to 5. .0 parts by weight, preferably 0.001 to 0.3 parts by weight, more preferably When the amount of the polyfunctional maleimide-based imine-based monomer is higher than 1.00 parts by weight, the polymerization process of the stupid ethylene copolymer (A) is The viscosity of the polymer will rise sharply, and it is easy to produce high molecular bridging foreign bodies and stains. The manufacturing method of the ethylene fluorene copolymer (A) of the present invention can be obtained by a

Page 10 1242578 V. Description of the invention (7) Block or solution polymerization, emulsification polymerization, suspension polymerization are generally used to form ′. Among them, block or solution polymerization is preferred. The reactor used in the foregoing reaction may include: a column flow reactor (PFR), a fully 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 two or more reactors are used, the first reactor is a completely mixed reactor (CSTR). ) Is preferred, and the final reactor is preferably a 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 stiff ethylene copolymer (A) of the present invention, a polymerization initiator may be usually added during production. Based on the total of (i-1), (i-2), and (i-3) above 100 parts by weight, the amount of the polymerization initiator used is 0 to 1 part by weight, and preferably 〇〇〇1 ~ 0 · 5 parts by weight. The usable polymerization initiator may be a monofunctional polymerization initiator or a polyfunctional polymerization initiator. The specific monofunctional polymerization initiator is, for example, diphenylhydrazine peroxide. Acid (be η ζ 〇y 1 per ο X ide), dicumyl peroxide, di-butyl peroxide, t-butyl peroxide, t-butyl hydroperoxide (t- butyl hydroperoxide), cumene hydroperoxide, t-butyl-peroxy benzoate, bis-2-ethylhexyl peroxydicarbonate (bis- 2-ethylhexyl peroxy di carbonate), tert-butyl peroxo isopropyl carbonate (BPIC), cyclohexanone peroxide, 2

Page 11 1242578 V. Description of the invention (8), 2'-azo-bis-isobutyronitrile (2,2'-azo-bis-isobutyronitrile), 1,1 '-Acetocyclocyclohexane_ 1 -Wei Nitrile (1,1 '-a ζ ο-bis cyclohexane-1-carbonitrile), 2,2'-azo-bis-2-methylbutyronitrile (2, 2'-azo-bis-2-methyl butyronitrile) Wait. Among them, dibenzoxyl peroxide and diphenylisopropyl peroxide are preferred. Specific examples of polyfunctional polymerization initiators are: 1,1-bis-t-butyl peroxy cyclohexane (TX-22), 1,1- Bis-third butyl peroxy-3, 3, 5-trimethylcyclohexane (1,1-bis-t-butylperoxo-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-ethyl hexanoxy peroxy) hexane], 4- (Third butylperoxy group) -3-hexyl-6- [7- (Third-butylperoxydynyl) heptyl] cyclohexyl {4- (t —butyl peroxy carbonyl) — 3- hexyl—6— [7 — (t-butyl peroxy carbony1) hepty1] cyclohexane} third butyl _ diperoxy azelaate ((1b 1; -1) 1 ^: ^ 1- (11 口 61 ' 0 \ 丫 & 261316), 2,5-dimethyl-2,5-bis (phenylarsinic acid peroxidation) -hex :): end [2,5-dimethyl-2,5-bi s- (benzoy 1 peroxy hexane], di-t-butyl peroxy-hexahydro-terephthalic acid (di-t-butyl peroxy-hexahydro-seven 6 plant 6 mouth 111 ± & 13 seven 6, abbreviated 8? 11but11), 2,2-bis (4,4-di-third-butyl peroxide Cyclohexyl propane [2, 2-bis- (4, 4-di-t-butyl peroxy) cyclohexyl propane (PX-1 2 for short), multifunctional monoperoxycarbonate (multifunctional monoperoxycarbonate, listed as the United States AT0FINA company, trade name Luperox JWE), etc .;

Page 12 1242578

Tertiary butyl peroxide-3, 3, 5-trimethylcyclohexane, di-tertiary butyl peroxide-hexahydro-terephthalate, and 2, 2-bis (4, 4 -di- Third butylperoxy) cyclohexylpropane is preferred. The reaction temperature of the above-mentioned reactor is controlled at 200 ~ 300 ° C, preferably 60 ~ 250 ° C, more preferably 80 ~ 240 ° C, and the pressure of the reactor is controlled at 1 ~ I 〇kg / cm2; and in order to control the molecular weight of the polymer, a chain transfer agent may be used in the present invention, based on 100 parts by weight of the total of the above (! -1), (H), (Bu 3), The use amount of the chain transfer agent is 0 to 2 parts by weight, preferably 0.00 to 1 part by weight. The used chain transfer agent may be a monofunctional chain transfer agent or a polyfunctional chain transfer agent, and Specific monofunctional chain transfer agents are: (1) Mercaptans: mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, n-dodecyl mercaptan, stearyl fluorenyl Thiaery mercaptan, t-dodecyl mercaptan (TDM), n-propyl mercaptan, n-octyl mercaptan, third-octyl mercaptan, Third-nonyl mercaptan and so on. (2) Alkylamines (a 1 ky 1 amines): monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, di-n-butylamine Amine, tri-n-butylamine and the like. (3) Other examples ... Pentaphenylethyl :): pentaphenylethane, α-methyl styrene dimer, terpinolene, among which thiols Among them, n-dodecyl mercaptan and third-dodecyl mercaptan are preferred. The polyfunctional bond transfer agent is, for example, isopentaerythritol tetrakis (3-mercaptopropionic acid g) [pentaerythritol tetrakis (3-mercapto propionate

Page 13 1242578 V. Description of the invention (1 0))], isopentaerythritol tetrakis (2-mercapto acetate) [pentaerythritol tetrakis (2-mercapto acetate)], tris- (2-mercaptoacetic acid) Trimethylolpropane tris (2-mercapt〇acetate), trimethylolpropane tris (3-mercaptopropion tris (3-merapto propionate, TMPT)), tri- (6 -Weiylhexanoic acid) trimethylol-propane tris (6-mercapto hexanate)]; etc .; of the above, tris-(-mercaptopropionic acid) trimethylolpropyl is preferred. The above-mentioned method for preparing the styrene-based copolymer (A) is to introduce the raw material solution into the reaction device for reaction. When all the monomers in the raw material solution have reached a predetermined conversion rate, the polymer solution is removed from the polymer solution. The reaction device continuously takes out the cup: In: Select the device to remove unreacted monomers and volatile components. After that, the final monomer conversion rate of the above reaction is 50% by weight. u or more, more preferably 70% by weight or more. Generally, the devolatization device can use a decompression degassing tank device, and then use a condenser to recover unreacted monomers. Zhijun Receive liquid: remove the water, and use it as the original again ;; :: make: the solvent can be reconstituted if necessary The styrene copolymer (A) of the present invention is used in two. Bu 3) The total amount of 100 parts by weight of the solvent used is 0 ~ 00 parts by weight, compared to: 0 ~ 60 parts by weight; the usable solvent is 2 ^ 0 ~ 60 parts by weight, more preferably xylene, o Xylene, m-xylene, Benzene, A, and Methyl ethyl are the same. Based on the above (Bu1), (1 ~ 2) ..., you can add as needed, benzene, ethylbenzene, p- and pentane, The styrene-based copolymers of the present invention (such as octane, cyclohexane, acetone, and butanone) have a weight average molecular weight between

1242578 V. Description of the invention (11) 150, 000 ~ 450,000, preferably 150, 000 ~ 350, 000, more preferably 160, 000 ~ 300, 000; when the weight average molecular weight of the copolymer (A) is less than 1 5 0,0 0 0:, the sheet after molding of the rubber-modified styrene resin composition is not good at stress cracking. If the required molding is made by vacuum molding or blow molding, There is a draw down phenomenon, and the uniformity of the meat thickness becomes worse; when the weight average molecular weight of the copolymer (A) is higher than 450, 0 0 0 ', the rubber modified styrene resin composition The improvement effect of extruded sheet is reduced, and the stress cracking resistance of the sheet after molding is not good. The weight average molecular weight of the copolymer (A) can be controlled by the copolymerization of the copolymer (A). The selection and amount of the agent, the selection and the amount of the polymerization initiator, the selection and the amount of the solvent, the polymerization temperature, the polymerization time, or the choice of the reactor can be used. The MFR of the styrene-based copolymer (A) of the present invention measured at a temperature of 250 ° C and a load of 1 kg is MI (g / l0 minutes), measured at a temperature of 2 50 ° c and a load of 10 kg The MFR is HMI (g / l0 points), and its MIR (Z; HMI / MI) is usually between 22 3 3 'Che Fu Jia is between 2 2 · 5 ~ 3 2 and more preferably 2 3 ~ 3 1; among them, μ FR refers to the melt flow index, which is measured by the method of AST.MD—238. The M IR value control method of the copolymer (A) can be achieved by one or more of the following methods. That is, during the copolymerization of the copolymer (A), the amount and timing of addition of the polyfunctional maleimide-based monomer, the selection and amount of the polyfunctional polymerization initiator, the choice of the reactor, and the final monomer Conversion rate, such as the above (i -1) part of the amount of styrene-based monomer, polyfunctional maleimide-based monomer or polyfunctional polymerization initiator is moved to the second or second This is achieved by adding subsequent polymerization reactors. One

Page 15 1242578 ~ --- 5. Description of the invention (12) In order to reach the cost of the invention, the extruded sheet has good resistance to stress cracking and dimensional stability, 1 = large, empty formability and blow molding of the formed sheet.性 的 处理 # Defect: 乂 and has excellent polymerization of true (1) styrene copolymer U) :: Requirement ^ meet the amount of the amine monomer of the present invention is between 0. 0 0 0 5 q 何 日^ The MIR of the functional maleamidine subpolymer (A) is between 22 and 33. 'Weight S parts' (2) Styrene-based rubber modified styrene ethyl greenene copolymer (A) of the present invention is used as a continuous phase. The content is usually 35 weight% as the dispersed phase, and more preferably 5 to 30% by weight. ^ 'It is preferably 3 to. If it is between 1 and 40% by weight, the balance of the rubber processing and impact resistance 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 abbreviated as the simultaneous grafting method). Or the rubber component (such as general rubber or rubber graft copolymer, especially rubber graft copolymer is preferred) is directly mixed with the stupid ethylene copolymer (A) of the present invention to be extruded. Abbreviated). The aforementioned simultaneous grafting method can be generally completed by a block polymerization method, a solution polymerization method, an emulsification, polymerization method or a suspension polymerization method Z. The aforementioned method for producing a rubber graft copolymer can generally be completed by an emulsion polymerization method or an emulsion block polymerization method, and among them, an emulsion polymerization method is preferred. · The production method of the rubber, modified stupid vinyl fluorene resin and composition of the present invention, the following two methods are used to explain:

1242578 V. Description of the invention (13) <Method 1: Simultaneous grafting method> Method 1 can use block or modified styrene resins to include: columnar flow reactor (PFR or Conversely, when two or more reactors are used in combination, (CSTR) is preferred, and the final reverse) is preferred. The manufacturing method is to first carry out the reaction in the raw material reactor of the olefin resin composition, and the reaction temperature is 250 ° C, more preferably 80 ~ 2 40 ° C between 1 ~ 10 kg / cm2; High quality vinyl resin polymerization initiator or chain transfer agent. The above-mentioned rubber-modified styrene solution was continuously introduced into the reaction unit monomer to achieve a predetermined conversion rate, continuously taken out, introduced into the devolatilization device 'after', and then granulated to form a continuous phase, and the rubber particles were a resin composition. In general polymerization, 0/0 or more, preferably 60% by weight, the general devolatilization device can use a reduced pressure solution polymerization reaction product. Method 1), completely hybrid reactor, etc. The reactors are preferably three or the first reactors in order to use the columnar liquid (containing the rubber component) satisfying the present invention. I is controlled to 30 to 3 0 0 and the pressure control polymer of the reactor In the manufacture of the component composition, after the olefinic resin is reversed, the unreacted product is included as the dispersion reaction, and the composition of the air tank device should be used. The monomer is preferably 70, or the number of reverse reactors used in the present invention can be three, and the continuous mixed-type reverse rubber can be changed to 0 ° C, the force, the flux, and the visible method of the raw material solution and the volatile system. Modified copolymer rubber conversion rate by weight% Out of air out of the rubber reactor can be wrapped (CSTR), as one, on. When the combined reactor (PFR-quality styrene is fed into the reaction, the reaction is preferably 60%). It is often necessary to control the present invention. The use of the styrene as the total reaction device component removal (A) in the original solution is 50%. Above the weight. A device. No. 1242578 V. Description of the invention (14) Then use the refrigerator to recover the water in the recovery liquid and remove the η early body or volatilize it. • If necessary, the aforementioned method-medium, L: ?: Used as a raw material solution. The styrene resin composition is used in a bulk or styrene resin composition made by a solution or solution polymerization method (the feed solution contains: (Η) 5 &quot;. Weight 3). ] 0 parts by weight of J1; 10 to 50 parts by weight of nitrile vinyl monomer, glutamate amount), and 0,0 0 0 5 to 1.0 parts by weight in total Polyfunctional maleimide-based monomer, 0 to 100 parts by weight of solvent, and 0.5 to 25 parts by weight of rubber; among them, styrene-based monomer, nitrile vinyl-based monomer, and other copolymerizable ethylene Monomers, polyfunctional maleimide imide monomers, solvents, and polymerization initiators as needed: types of chain transfer agents and The specific description of the amount of use is the same as that of the preparation: styrene-based copolymer ⑴ "material solution, which is not repeated here .... In the above method 1 φ, it is also possible to use emulsion polymerization to obtain rubber modification. Preparation method of emulsion polymerization reaction: = The same method of preparation, but monomers and rubber IK; liquid polymer ΐ ϊ 象 象: styrene of f: a mixed solution of block or soluble monomer in a fat composition Take 5 stupid vinyl monomers, nitrile vinyl monomers and other states exist, but with: The initial stage rubber phase is a continuous phase of nitrile vinyl monomers and other monomers: graft polymerization: should ', Stirring of vinyl monomers and devices, the conversion rate of rubber components: gradually increased, and accompanied by the reaction of monomers and pots such as surrounded by stupid vinyl monomers, nitrile vinyl monomers &quot; pounds, and changed In the state of dispersed particles (dispersed 1242578

V. Description of the invention (15) In the aspect, mono-J, such as stupid vinyl monomer, nitrile vinyl monomer, etc., is transformed into continuous phase. The final rubber particle phase shape ::: 4Vr i Π nr 1 η + 1% particle weight 1 〇.Η㈣ · 〇5〜1〇, more preferably 〇, the rubber component in the standard * Specific examples include: diene rubber, poly (ethylene-propylene rubber), polyacrylate rubber, rubber, etc. The aforementioned dilute rubber is as follows: the dilute monomer is fine in composition: the body A turns = the degree is 0. . The following polymers include dibutyl rubber, butadiene rubber, isoprene rubber, air butadiene rubber, glycerin 1 styrene-diene rubber, acrylonitrile-diene rubber, etc. :, 丄 = diene rubber has high cis (Hl-Ci 〇 content and low cis aow ″ Us) 3 amount difference; in high cis rubber, its cis (Cis) / vinyl (Vmyl) The typical weight composition is (94 ~ 99%) / (〇 ~ 5%), and the remaining composition ^ • is a trans structure; its Mooney viscosity is 20 ~; [20, the molecular weight range is 1 0 0,0 0 0 ~ 800,00 0 is preferred; the typical weight composition range of \ 丨 member / vinyl in low-cis rubber is (20 ~ 40%) / (6 ~ 20%), and the rest It has a trans structure, with a Money viscosity of 20 to 120, and a molecular weight range of 100'000 to 800,000. Preferably, styrene-diluted rubber Specific examples are stupid ethylene butadiene rubber, styrene-isoprene rubber, etc., which may be block copolymers, random copolymers, or copolymers whose composition gradually increases / decreases (taper). / Butyl Ether in Ding Erfu Rubber The weight ratio range is preferably 50% by weight or less, and the molecular weight range is preferably 50,000 to 600,000. The above-mentioned rubbers are butadiene rubber and styrene / butadiene. Rubber is preferred. <Method_ • Grafting Method>

Page 19 1242578

V. Description of the invention (16) Method two, the styrene-based copolymer (A) and the rubber graft copolymer (B ') can be mixed and kneaded: the rubber-modified styrene-based resin composition of the present invention is extruded. In the second method, the styrene copolymer (A) is usually grafted with rubber? τ, substance (B '), dry mix with a general-use Hanschel mixer, and then mix with a mixer such as an extruder mixer, a kneader, or a Banbury mixer, etc. Extrude pellets.

The method for preparing the rubber graft copolymer (B ') can be generally completed by using a block or solution polymerization reaction, an emulsion polymerization reaction or a suspension polymerization reaction. Among these, the method for producing the "rubber graft copolymer (B,) in a block or solution polymerization reaction" is a graft polymerization reaction of a raw material solution. The raw material solution is: (9 σ9 parts by weight of stupid vinyl monomer, (i-2) 10-50 parts by weight of nitrile vinyl monomer, and (i-3) 0-40 parts by weight Other copolymerizable vinyl monomers, total 100 parts by weight, 0 ~ 100 parts by weight of solvent, and 0.5 ~ 25 f parts of rubber; the raw material solution usually does not contain polyfunctional maleimide If the “system monomer” is a polyfunctional maleimide-based monomer, the amount used must be below the lower limit of the amount used in the present invention. A specific example of the composition of the rubber component is described in the first method.

Block or solution polymerized stone of the rubber graft copolymer (B ') of the present invention: monomers such as rubber, stupid vinyl monomers, waxed vinyl monomers, etc. In the initial stage of polymerization, the rubber phase It is continuous = &quot; to ^ ^ raak 彳 dagger as the rubber; the rate is gradually increasing, and with the reactor's stirring, it is gradually understood that monomers such as stupid vinyl monomers, nitrile vinyl monomers, etc. ^

1242578 V. Description of the invention (17) Surrounded by polymer, J Huang 纟 | 纟 is eight, and the escape is the state of knife scattered particles (dispersed phase,,, cloth monomer, nitrile vinyl monomer, etc. B 'Other-side becomes continuous phase' Finally, the rubber particle phase is formed. :: Its polymer conversion particle size is .05 ~ 10 ... preferably.r: 50% == weight to the amount average .... · 1 ～ 2 // m In addition, the rubber graft copolymer (B,) can also be emulsified by humans. The manufacturing method is to make the rubber emulsion 4Q 9G weight 'mouth ^ to complete the binding single core ~ 95% by weight, nitrile ethylene System monomers 5 to 5 (^ =) and styrene B: copolymerized monomers 0 to 35% by weight &quot; 62 or "parts" in the body or monomer mixture, as well as emulsifiers and lifting weights that are currently required, are grafted Polymerization reaction to obtain the rubber graft copolymer emulsion = f to carry out the graft copolymer emulsion through coagulation, dehydration, drying and other steps to: :: f graft the required rubber graft copolymer (B,). The specific examples of the rubber components in the aforementioned rubber emulsion are the same as those described above. Among them, a dilute rubber is preferred. Series monomers (such as butadiene) or two-mouth saliva ... ~ 卞 limb q 王 里 卞 岣 particle size 0 · ~ 0 · 2 0 &quot; m small-diameter diene rubber emulsion, then frozen and enlarged Dehydration method, mechanical hypertrophy method or additive hypertrophy method, the aforementioned small particle size diene rubber emulsion is enlarged to a weight average particle size of 0.22 to 0.06 m large particle size diene 彳 H emulsion for further preparation. A graft copolymerization reaction is performed; among which, 100 to 50% by weight of the additive fat body and 0 to 50% by weight of other copolymerizable monomers, such as early copolymerization of early styrene, acrylonitrile, and (fluorenyl) acrylate, etc. Polymerization to polymerize to a weight-average particle diameter of 0.05 ~ 0. 6㈣ # diene; rubber: milk can also be prepared by emulsification polymerization of the aforementioned monomers with a weight-average particle diameter of 0 / 〇5 2 0 vm of small particle size diene After the rubber emulsion is used,

Page 21 1242578 V. Description of the invention (18) The additives used in Dafa may be acidic substances such as acetic anhydride, hydrogenated gas, sulfuric acid, or basic substances such as sodium chloride, potassium gasified, and calcium gasified. , And (fluorenyl) acrylic acid (meth) acrylate copolymers (such as fluorenyl dienoic acid-butyl acrylate copolymer, methacrylic acid-ethyl acrylate copolymer) and other polymer coagulants containing carboxylic acid groups ° 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, colorants, etc. At the polymerization stage or the kneading extrusion stage of the stupid ethylene-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 stupid vinyl 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 3 〇Parts by weight or less.

In the rubber-modified stupid vinyl-based resin composition of the present invention, a resin other than the present ethylenic copolymer (A) may be used if 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-stupid ethylene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-α-methenyl ethylene resin, acrylonitrile-benzyl ethylene-fluorenyl methyl acrylate resin, Propyl-benzyl-N-benzylmaleimide imide resin, styrene_anhydrous ^ maleic acid: = Taken ^ ethylene-N-benzylmaleimide imide resin, polymethyl acrylate, polycarbonate Ester resin, stupid ethylene-methacrylic resin, methacrylic acid

Page 22 1242578 V. Description of the invention (19) Dilute-styrene resin, acrylic meal · ene-Nphenylmaleimide-styrene resin, polyamide resin, polyester resin, polyphenylene ether Resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile- (ethylene-propylene diene rubber) -styrene resin, acrylonitrile-silicone-styrene resin, and other resins, which can be used alone or in combination . The polymer is usually used in an amount of 80 parts by weight or less based on 100 parts by weight of the rubber-modified styrene resin composition. [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 styrenic copolymer (A-1) in three fully mixed PFR), N, N, 4, and dialkyl are polymerized Sulfur kg / hour; will be the first and the amount of melamine, continuous reactor reaction rate reactor reactor (CSTR), the first styrene monomer 64.5 weight, 4'-diphenyl 0,1 parts by weight of diphenyl fluorenyl peroxide, and a flow rate of B, which are continuously supplied to the olefin monomer 1 0 0 parts by weight of the monomer and 0.22 parts by weight to the reactor. The polymer solution 'from the second reaction was a three-reactor portion, and 30 parts by weight of total propylene malene 0 · 0 3 5 benzene was fed to the first polymer solution and the N, N' -4 mixed solution was introduced into the polymerizer. The third first and second reactions are columnar flow-type transenenitrile monomers, 35.5 amine monomers, 0.02 5 parts by weight, and chain-transfer parts in a mixed solution reactor for polymerization introduction into the second reaction, 4 '- Diphenyl hydrazone reacts at 1.4 kg / small; then the reactor is used as a complete reactor (parts by weight part by weight transfer agent ten, reacted at 25 combinations) Reactor, Alkanes

1242578

Parts, Ν, Ν, -4,4,-monomer 1 body 〇 · 〇 4 is supplied to the second reaction type is 90, and finally the polymer is dissolved in the desulfurized formulation, and the deoxidized ethylene formula and 0 parts by weight are used. The contents of the three reactors, 103, should be 'out of the polymerization final liquid introduction, etc., and the polymerized mixed solution of the polymerized copolymer should be accumulated at a temperature of 4 125 ° C. After the stirring monomers are turned, Usually the devolatilization device is used to transfer the molten material (A-1); the analysis is listed in the table, and the reaction rate is 40%, the drop rate is 7 3, and it will be removed by the devolatilizer. The stupid ethyl benzyl 4kg / small; 75 liters are weight percent, respectively. The third flow rate of the reversed-reaction monomer to produce granulated olefinic co-fired bismaleimide is continuously, the first, Second, the temperature of the reaction tank is 120, 90, 35 rpm; 〇 co-volatilization device or extruded and other volatiles obtained from the reactor reaction; and the production of the polymer (A-1) of the present invention can be obtained

口 成例 b Synthesis of styrenic copolymer (A-2) Eight in three reactors in series. The first and second reactors are completely mixed reactors (CSTR), and the third reactor is 0 Columnar flow reactor (FR) will be 65.5 parts by weight of styrene monomer, 34.5 parts by weight of acrylonitrile monomer, ―4, 4 '—diphenylphosphorane bismaleimide monomer 0.0 22 parts by weight &gt; | Co-initiator 1: [-bis-third butyl peroxy_3, 3, 5-trimethylcyclohexyl t 0,015 parts by weight, chain transfer agent dodecylsulfide Alcohol 0.001 parts by weight and 30 parts by weight of the mixed solution were continuously supplied to the first reactor for a polymerization reaction at a flow rate of 25 kg / hour; the reaction product obtained by the reaction in the first reactor: a mouth solution Into a second reactor, and 100 parts by weight of styrene monomer

$ H —4,4'-Diphenylphosphorane bismaleimide monomer 0.15 parts by weight of 4 dagger / valley fluid 'is continuously supplied to the second at a flow rate of 2.1 kg / hour reaction

1242578 V. Description of the invention (21) Polymerization is carried out in the reactor; the second reactor is introduced into the third reactor for polymerization; wherein the volume of the first reactor is 40, 40, and 7 5 liters, respectively. The temperature was 9 5, 10, 130 ° C, and the stirring rates were 73% by weight of the monomer conversion at the outlet of the reactor after 120. After the polymerization is completed, in the same way as in Synthesis Example a, the third copolymer solution is devolatilized, extruded, and granulated. The styrene-based copolymer (A-2), which is invented in the steps; In Table 1. Synthesis Example c Synthesis of styrene-based copolymer (A-3) in four reactors in series, the first and second reactors are completely mixed reactors (CSTR), and the third and fourth reactors, respectively. For a column flow reactor (PFR), 64.5 parts by weight of a styrene monomer, 35.5 parts by weight of an acrylonitrile monomer, and N, N′-4,4′-diphenylphosphonium bismaleate Fluorene imine monomer 0.0 0 parts by weight, polymerization initiator 2-bis (4,4-di-tert-butylperoxy) cyclohexylpropane 0.01 parts by weight, chain transfer agent dodecane A mixed solution of 0.1 part by weight of mercaptan and 30 parts by weight of ethylbenzene was continuously supplied to the first reactor for a polymerization reaction at a flow rate of 25 kg / hour; the polymerization obtained by the reaction in the first reactor was polymerized. The polymer solution is introduced into the second reactor, and the temperature of the first reaction tank of the polymer solution obtained from 100 weight of styrene monomer is 90 and 35 rpm, respectively; -2) parts by weight, 0.066 parts by weight of Ν, Ν'-4, 4 'phenylmethane bismaleimide monomer, polymerization initiator 1,1-bis-tertiary butyl peroxide-3 , 3, 5 -Trimethylcyclohexane of 0.01 to 4 parts by weight of the mixed solution was continuously supplied to the second reactor for a polymerization reaction at a flow rate of 1.4 kg / hour; and the second reactor was reacted to obtain the obtained polymerization. Product solution is introduced into the third reactor, and stupid ethylene monomer

Page 25, 1242578 V. Description of the invention (22) 100 parts by weight of 5-three-phase tri-reaction is 4 0 130 The co-invented synthetic fluorenyl cyclohexyl, a continuous reactor reaction; of which, &gt; 40, 75, 1 3 5 ° C, styrene formulation and example d at the outlet of the polymer in the polymerization final polymer solution and the polymerization initiator 1,1-bis-third butyl peroxide-3,3, alkane · 0.30 parts by weight of the mixed solution was supplied to the third reactor at a rate of 1.4 kg / hour for the polymerization reaction; and the polymer solution obtained in the first was introduced into the fourth reactor to polymerize the first, second, and third. The volume of the fourth reactor is 75 litres, the temperature of the reaction tank is 95, 103, the stirring rate is 120, 90, 38, 35; rpni; the final monomer conversion rate is 78% by weight. After that, in the same way as in Synthesis Example a, the reaction obtained from the fourth reactor was subjected to steps such as devolatilization, decantation, and granulation to obtain the present copolymer (A-3): the styrene copolymer (A-3) Its physical properties are listed in Table 1. Ethylene copolymer (A-4) is synthesized in three fully mixed PFR), N, N '-4, polymerized from 0. 0 1 weight 3 0 parts by weight of the starting agent 2, 2-double (4, 4 parts by weight are mixed into the first reactor feed solution to introduce the first polymerization initiator 1,1--0. 0083. First, it is a columnar enenitrile monoamine monomer-based peroxy alcohol 0.01. 4 kg The flow reactor chain transfer solution, the polymerization reaction; the first two reactors, and the styrene monomer bis-third butyl peroxide-3, 3, 5- parts by weight of the mixed solution to 1. 4 kg A tandem reactor (CSTR) styrene monomer 64 / 4'-diphenylmethyl reactor 'is 5 parts by weight of the third reactor, and the third agent of propane bismaleimide is ten The dialkyl sulfide was supplied with a reaction volume of 25 kg / hour as a complete reactor (35.5 parts by weight and 0.02 parts by weight) of cyclohexylpropene and ethylbenzene, which were continuously supplied to the reaction. 100 parts by weight, trimethylcyclohexane flow rate, continuously

sill

Page 26 1242578 V. Description of the invention (23). It is supplied to the second reactor for polymerization; the polymer solution obtained from the reaction in the second reactor is introduced into the third reactor, and the weight of the styrene monomer is 100 weight. Parts of the solution were continuously supplied to the third reactor for polymerization at a flow rate of 1.4 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 was 95, 103, and 130 ° C, the stirring rates were 120, 90, and 35 rpm, and the monomer conversion rate at the outlet of the reactor was 71% 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 the styrene copolymer (A-4) of the present invention: the benzene The manufacturing formula of the ethylene-based copolymer (A-4) and its physical properties are shown in Table 1. Synthesis Example e Synthesis of styrene-based copolymers (A-5) in two series-connected reactors: the first and second reactors are completely mixed reactors (CSTR), and the third reactor is columnar. Flow reactor (PFR) · A mixture of 64.5 parts by weight of styrene monomer, 35.5 parts by weight of acrylonitrile monomer, N, N '-4, 4' -diphenylphosphonium bismaleate 0,2 2 parts by weight of fluorene imine, 0.03 parts by weight of dibenzoyl peroxide, a polymerization initiator, 0.01 part by weight of dodecyl mercaptan, and 3 parts of ethylbenzene A part by weight of the mixed solution is continuously supplied to the first reactor at a flow rate of 25 kg / hour for polymerization: the polymer solution obtained from the reaction of the &lt; reactor is introduced into the second reactor, and the stupid ethylene monomer 100 parts by weight of body, Ν, Ν'-4, 4'-diphenylphosphorane bismaleimide monomer 0.2 parts by weight, polymerization initiator 1,1-bis-third butyl peroxide -3, 3, 5-trimethylcyclohexane 0.02 parts by weight of the mixed solution was continuously supplied to the second reactor at a flow rate of 1.4 kg / hour for polymerization reaction.

1242578 V. Description of the invention (24) should; the polymer solution obtained from the reaction in the second reactor is introduced into the third reactor, and a solution of 100 parts by weight of styrene monomer is used at a flow rate of 1.4 kg / hour , Continuously supplied to the third reactor for polymerization; wherein the volumes of the first, second, and third reactors are 40, 40, and 75 liters, respectively, and the temperatures of the reaction tanks are 9 0, 1 0 3, 130 ° C, the stirring rate is 120, 90, 35; rpm; the monomer conversion rate at the exit of the reactor is 71% 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 the styrene-based copolymer (A-5) of the present invention; The manufacturing formula of the ethylene-based copolymer (A-5) and its physical properties are shown in Table 1. Synthesis Example f The synthesis method of styrene copolymerization (A-6) is the same as that of Synthesis Example b. The difference is that the amount of monomer used in the feed mixed solution of the first reactor is adjusted. 0 5 重量 份 ， Finally the reactor is 60 parts by weight of styrene monomer, 35 parts by weight of acrylonitrile monomer and 5 parts by weight of methyl methacrylate, and the amount of chain transfer agent dodecyl mercaptan is adjusted to 0.05 parts by weight. The monomer conversion rate at the exit was 73% by weight: The manufacturing formula of this styrenic copolymer (A-6) and its physical properties are listed in Table 1. Synthesis Example g The styrene-based copolymer (A-7) was synthesized in the same manner as in Synthesis Example b, except that the feed of the first reactor was mixed. The amount of monomer used in the mixed solution was adjusted. , Respectively, 61 parts by weight of styrene monomer and 39 parts by weight of propylene wax monomer, and the monomer conversion rate at the exit of the reactor was 72% by weight: the manufacturing formula of the styrenic copolymer (A-7) and Its physical properties are listed in Table 1. Synthesis Example h Synthesis of stupid vinyl copolymer (A-8)

Page 28 1242578 V. Description of the invention (25) The operation method is the same as that of Synthesis Example b, except that the amount of monomers used in the mixed feed solution of the first and second reactors is adjusted, respectively. 〇7 重量 份 ， 第 The seventh part by weight of a reactor, 72 parts by weight of styrene monomer, 28 parts by weight of acrylonitrile monomer, and N, N′-4,4′-dibenzylmethanebismaleimide monomer, 45, parts by weight of N, N'-4,4'-diphenylmethane bismaleimide monomer in the two reactors, and the monomer conversion rate at the exit of the final reactor was 70% by weight; the styrene copolymerization The manufacturing formula of the compound (A-8) and its physical properties are listed in Table 10. Comparative Synthesis Example i Synthesis of styrene-based copolymer (A-9) In two reactors in series, the first and second reactors All are fully mixed reactors (CSTR), 68 parts by weight of styrene monomer, 32 parts by weight of acrylonitrile monomer, 0.03 parts by weight of dibenzoyl peroxide peroxide, chain transfer agent dodecane A mixed solution of 0.01 parts by weight of mercaptan and 25 parts by weight of ethylbenzene was continuously supplied to the first reaction at a flow rate of 28 kg / hour. Polymerization reaction is carried out in the reactor; the polymer solution obtained from the reaction in the first reactor is introduced into the second reactor for polymerization; wherein the volumes of the first and second reactors are 40 and 40 liters, respectively, and the temperature of the reaction tank The temperature was 9 5 and 115 ° C, the stirring rates were 120 and 90 rpm, and the monomer conversion rate at the exit of the reactor was 53% by weight. After the polymerization is completed, the copolymer solution obtained in the second reactor is subjected to the steps of devolatilization, extrusion, and granulation in the same manner as in Synthesis Example a, to obtain the styrene-based copolymer (A-9) of the present invention: the benzene The production formula of the ethylene-based copolymer (A-9) and its physical properties are listed in Table 1. Comparative Synthesis Example j Synthesis of Styrene Copolymer (A-1 0)

Page 29 1242578 V. Description of the invention (26) The operation mode is the same as that of Comparative Synthesis Example i, except that the feed mixed solution of the first reactor is added with N, N '-4,4' -dibenzyl 0.01 parts by weight of methanebismaleimide monomer, and the polymerization initiator was changed to 1,1-bis-third-butylperoxy-3, 3,5-trisylcyclohexane 0.01 weight The reaction rate of the second reactor is 53. The gravimetric analysis column compares the feed of the synthesizer and the temperature of the chain transfer tank is changed to 1 2 5 ° C. Finally, the monomer at the outlet of the reactor is converted to 0). Material ° / 〇: The styrene-based copolymer (A-1 is shown in Table 1. Example k Styrene-based copolymer (A-1 is the same as that of Synthesis Example i.), Without adding a solution, add divinyl The dosage of dodecyl mercaptan was adjusted and the monomer conversion rate at the outlet of the reactor was adjusted to 54% by weight (Al 1). The manufacturing formula and its physical properties are listed in Comparative Synthesis Example 1. Styrene-based copolymer (A-1 2 The same thing in the synthesis of the three fully mixed formula 1) is that the first reaction benzene monomer 0.03 5 parts by weight is adjusted to 0.5 parts by weight, the most: the styrene copolymerization Material Table-〇PFR), .N, -4, 4,-starter solution was used to polymerize the inverse di-reactor-based pinane double kg / hour reactor reactor (CSTR) in series, The first styrene monomer 76 weight diphenylmethane bismaleic oxide diphenyl hydrazone 0.01 1 8kg / hour flow rate should be; the first reactor, and the styrene monomer maleimide imide monomer 0 The flow rate is continuously supplied for 5 parts of the three reactors, a single part by weight of acrylimide, and 100 parts by weight of the continuous reaction to 15 parts by weight to the second) The synthesis of the first and second reactors is complete Cylindrical flow reactor (24 parts by weight of nitrile monomer, N, 0.6 parts by weight of body, 10 parts by weight of polymerized ethylbenzene, and a mixture of polymer solution supplied to the first reactor is introduced into the first part, N, Polymerization of a mixed solution of Ν '-4, 4'-dibenzene in a 2: 1 reactor

Page 30 1242578 V. Description of the invention (27) • Then, the polymer solution obtained from the reaction in the second reactor is introduced into the third reactor for polymerization; wherein the volumes of the first, second and third reactors are respectively 40, 40, 75 liters, the temperature of the reaction tank was 90, 98, and 110 ° C, the stirring rates were 丨 20, 90, and 35 r pm, respectively; · the final monomer conversion rate at the reactor outlet was 73 weights % 〇 After the end of the contract, the copolymer solution obtained 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 the styrenic copolymer of the present invention (A- 1 2 ); The manufacturing formula of this stupid ethylene-based copolymer (A-1 2) and its physical properties are listed in Table 1. Comparative Synthesis Example m: Three fully-mixed reactions (PFR) in three strings, Bengyi, N, N, -4, 4, ~ Polymerization initiator peryl mercaptan 0.3 kg / hour flow; the first The reaction is then polymerized in the second reaction; 40, 40 &gt; 75, stirring rate, split conversion rate 70, weight is at the end of the polymerization, styrene-linked reactor (CSTR), olefin monomer 65, diphenylphosphonium oxide, dibenzyl oxide The amount of parts and the amount of B, in the reactor reaction chamber of the continuous reactor, the first liter, otherwise it is 120% by volume. After that, the homopolymer (A-1 reactor, respectively, the third reactor • 5 parts by weight, propane bismaleimide methylene chloride 0.30 parts by weight benzene 30 parts by weight were supplied to the first 5 的 伤 伤 The polymer is dissolved in the polymer, and the temperature of the first reaction tank is divided into 90, 35 rpm; 3) the synthesis of the first. The two reactors are complete columnar flow reactors (34. 5 weight injury) Amine monomer 0 · 0 1 parts by weight, parts, chain transfer agent twelve-burner mixed solution, polymerization reaction was carried out in 18 reactors and introduced into the second reactor; the liquid was introduced into the third reactor and the volume of the second reactor was different. For 90, 100, 1 10, the final reactor outlet

Synthesis example a will be obtained from the reaction in the third reactor

1242578 V. Description of the invention (28) The copolymer solution of devolatilization, extrusion, granulation, etc. can be used to obtain the stupid ethylene copolymer (A-1 3) of the present invention; the styrene copolymer (A- 13) The manufacturing formula and its physical properties are listed in Table 1. Comparison: Synthesis Example η Synthesis of Styrene Copolymer (Α-14). The operation method is the same as Comparative Synthesis Example i, except that the feed mixed solution of the first reactor is added with N, N '-4 1, 4 parts by weight of 4'-diphenylmethane bismaleimide monomer; during the reaction, the viscosity of the reaction system was urgent

The increase in tritium is accompanied by deterioration of the hue of the reaction product, and many high molecular weight bridging foreign bodies and stains are generated, resulting in the inability of the polymerization reaction to proceed. The M I R of the reaction product taken out and analyzed by the flow coefficient analyzer is 35. [Synthesis example of rubber graft copolymer (B'-1)] In four reactors in series, the first to fourth reactors are completely mixed reactors (CSTR), and 72 parts by weight of styrene monomer 2, acrylonitrile monomer, 8 heavy injuries, butadiene rubber, 5.5 parts by weight, polymerization initiator dibenzyl peroxide, 0.2 parts by weight, chain transfer agent dodecyl mercaptan, 0. The mixed solution of 12 parts by weight and 20 parts by weight of ethylbenzene was continuously supplied to the first reactor at a flow rate of 40 kg / hour for polymerization; the first reactor reaction station was

Zhizhi κ compound bath is introduced into the second reactor for polymerization; the polymer solution obtained from the reaction in the second reactor is introduced into the third reactor for polymerization, and the polymer solution obtained in the second reactor is polymerized The re-introduction of the fourth reaction is to carry out the polymerization reaction. Among them, the volumes of the first, second, third, and fourth reactors are all 45 liters, and the temperatures of the reaction tanks are 9 0, 丨 〇〇, 丄 ^ 〇, 120 t: the stirring rates are 300, 2000, 50, and 90 rpm; the monomer conversion rate at the exit of the reactor is 51% by weight.

1242578 V. Description of the invention (29) The granulation obtained by the reaction in the fourth reactor and other steps can obtain the content of the rubber component 10% by weight. After the polymerization is completed, the copolymer solution of the synthesis example is devolatilized and extruded. Synthesis Example of Rubber Graft Copolymer (B,-1) Rubber Graft Copolymer (B,-2)] Ingredients by Weight U-Butadiene. 150.00 Potassium Persulfate Solution (1%) 15.00 Oleic Acid Bell 2.00 Distilled water 190.00 Ethylene glycol dimethacrylate 0.13 According to the above formula, it is reacted at a reaction temperature of 65 ° C for 14 hours, and the conversion rate is 94%, the solid content is about 36%, and the weight average particle size is about 0. 1 # m of synthetic rubber emulsion. Ingredients by weight butyl acrylate 90.00 methacrylic acid 10.00 potassium persulfate solution (1%) 0.50 sodium dodecylsulfosulfate solution (10%) 0.50 Γ1-dodecyl mercaptan 1.0 distilled water 200.00 according to the above table formula in 7 The reaction was carried out at a reaction temperature of 5 ° C for 5 hours, and a carboxylic acid group-containing polymer coagulant emulsion having a conversion rate of about 9 5% and a pH value of 6.0 was obtained. After that, the polymer was aggregated with 3 parts by weight (dry weight) of a carboxylic acid group-containing polymer.

Page 1212578

Latex V. Description of the invention (30) The agent was used to hypertrophy 100 parts by weight of synthetic rubber latex. The ρ Η value of the obtained rubber was 8.5, and the average weight of the rubber was about 0 1 1 U m. . Finally, the aforementioned enlarged rubber emulsion is formulated according to the following Table J, and the aforementioned enlarged rubber emulsion is polymerized with styrene-acrylonitrile copolymer to produce a rubber graft copolymer (B,- 2 ). Weight fraction of ingredients ~ Masticated rubber emulsion (dry weight :) 100.0 'Styrene monomer 75.0 Acrylonitrile monomer 25.0 — Thirty-two alkyl. Thiols — Cumene hydroperoxide 3.0 — Ferrous sulfate Solution (0.2%) 3.0 Formic acid sodium hypophosphite solution (10%) 0.9 ^ Ethylenediamine tetraacetic acid solution (0.25%) 3.0 — According to the formula in the table above, react at 7 5 ° C for 5 hours to obtain After the carboxylate group-containing polymer coagulant having a J conversion rate of about 95% and a pH value of 6.0 was turned over at night, 3 parts by weight (dry weight) of a polymer containing acid acid and a suspicious tincture were used to enlarge 100 By weight of synthetic rubber latex, the obtained rubber has a pH of 1 $. The average weight of the rubber is about 0.3! ^ 液 1 M 1U. Finally, the above-mentioned enlarged rubber emulsion is subjected to graft polymerization with a styrene-acrylonitrile copolymer according to the formula shown below to produce a rubber graft copolymer (B ').

1242578 V. Description of the invention (31) Ingredients parts by weight Hypertrophic rubber emulsion (dry weight) 100.0 Styrene monomer 75.0 Propylamine monomer 25.0 Thirty-two fluorenyl mercaptan 2.0 Hydrogenated cumene 3.0. Sulfuric acid Ferrous solution (0.2%) 3.0 Formic acid sodium hyposulfite solution (10%) 0.9 Ethylenediamine tetraacetic acid solution (0-25%) 3.0 The rubber graft copolymer emulsion prepared according to the above table was chlorinated Calcium is coagulated, and then dehydrated and dried to less than 2% to obtain the rubber graft copolymer (B'-2) required by the present invention (rubber content 50% by weight, rubber weight average particle diameter 0 · 3 1 & quot m) ° Simultaneous · Grafting [Synthesis example of rubber-modified styrene resin (C-1)] In four reactors in series, the first and second reactors are completely mixed reactors, respectively. (CSTR), the third and fourth reactors are columnar flow reactors (PFR), the styrene monomer 65. 5 parts by weight, acrylonitrile monomer 34.5 parts by weight, butadiene rubber 5. 5 parts by weight, Ν, Ν '-4, 4'-diphenylmethane bismaleimide monomer 0 · 0 2 2 parts by weight, polymerization initiator 1, 1 -bis-s Tributyl peroxy-3, 3, 5 -trimethylcyclocyclohexane 0.5 parts by weight, chain transfer agent twelve :): Endyl mercaptan 〇. 0 0 7 5 parts by weight and ethylbenzene 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 solution obtained by the reaction in the first reactor was introduced into the second reaction

Page 35 1242578 V. Description of the invention (32) reactor, and continuously supplying the flow rate of styrene monomer alkanemaleimide monomer 0.0 to the polymerization reaction obtained from a reactor reaction; and the third The reactor reactor performs the polymerization reaction; the volume of the reactor is 40, 40 is 100, 105, 115, 125 1 50, 90 rpm; after the polymerization is completed, the same copolymer solution is devolatilized. 10% by weight of modified styrene ethyl rubber: The modified rubber is listed in Table 2. 100 parts by weight, N, U parts by weight of the second reactor was mixed to carry out the compound solution into the polymer obtained in the first, the first, second, 75, 75 liters, ° C, the stirring rate of the outlet of the separator Example of monomer conversion synthesis a The solution of the olefinic resin (C-1) N'-4, 4, ~ from the first, extruded, granulated, etc., is redirected with the solution of the three polymerization reactor, the third, the reaction tank is 3 0 0, chemical conversion rate 72 heavy four reactor steps, that is, the rubber made of B-based resin (C-1 diphenylmethyl 3kg / hour; then the first polymerization into the fourth anti-four reaction temperature respectively 2 0 0, the amount of%. The content obtained by the reaction can be obtained in the content of the formula [comparative synthesis example of the rubber modified benzyl resin (C-2)] In four reactors in series, the first The second and second reactors are completely mixed reactors (CSTR), and the third and fourth reactors are columnar flow reactors (PFR), which are made up of 65 · 5 parts by weight of styrene monomer and 34 晞 of propionitrile monomer. Parts by weight, 5.5 parts by weight of butadiene rubber, Ν, Ν '-4, 4' -dibenzyl bismaleimide Body 0 · 0 0 0 2 parts by weight, polymerization initiator 1,1-bis-third-butylperoxy-3,3,5-trisylcyclohexyl :): end 0.005 parts by weight, The mixed solution of the chain transfer agent dodecyl mercaptan 0 · 0 0 7 5 parts by weight and 25 parts by weight of ethylbenzene was continuously supplied to the first reactor for a polymerization reaction at a flow rate of 37 kg / hour; The polymer solution obtained by the reaction in the first reactor is introduced into the second reaction

1242578 V. Description of the invention · (33) The reactor performs the polymerization reaction; the polymer solution obtained from the reaction in the second reactor is introduced into the second reaction tank for the polymerization reaction; and the polymer solution obtained from the reaction in the third reactor is introduced into the first reactor. Four reactors carry out the polymerization reaction; wherein the volumes of the first, second, third, and fourth reactors are respectively 40, 40, 75, and 75 liters, and the temperatures of the reaction tanks are respectively 丨 〇〇, 丨 〇 5, ri 5, 1 25 ° C, the stirring rates are 3 0 0, 2 0 0, 1 50, 9 0 r pin respectively; the final monomer conversion rate of the reactor outlet is 70% by weight.

After the polymerization is completed, the copolymer solution obtained in the fourth reactor is subjected to steps such as devolatilization, extrusion, and granulation in the same manner as in Synthesis Example a, so that the rubber-modified styrene-based resin of the present invention (C-2 ), The rubber component content is 10% by weight; the manufacturing formula of the rubber modified stupid vinyl resin (C-2) is shown in Table 2. Grafting and kneading method example 1 20 parts by weight of a rubber graft copolymer (B'-1), 30 parts by weight of a rubber graft copolymer (B '~ 2), and styrene-based copolymer (a-1) 50 parts by weight and a processing aid of ultra-high molecular weight methyl methacrylate polymer (P-530A sold by Mitsubishi Ray ο η) 2.0 parts by weight, dry-blended with a Hanschel mixer, and then The temperature of the raw material tank is 22 0 ~ 240 ° C, the die temperature is 240 ° C, and the twin-shaft extruder with an exhaust port is melt-kneaded to produce a pelletized (pe 丨 1 et) rubber modified stupid vinyl system. The resin composition contains 17% by weight of the rubber component; the manufacturing formula of the resin composition and its physical properties are listed in Table III. Example 2 A rubber graft copolymer (B ′-2) 1 7 · 5 parts by weight, rubber modified benzene

Page 37 1242578 V. Description of the invention (34) Processing aid of vinyl resin (C-1) vinegar polymer, same as the modified styrene resin of Example 1; Example 3 of the resin composition will be 64 parts by weight of rubber grafting total (A-1) and extrusion conditions of working aids (Mitsubishi Ray ο η) can be used to prepare dilute resin compositions, and the manufacturing formulas and examples 4 to 10 of the same as in Example 3 Production formula of one kind of object (A) and its comparative example 1 Production formula of one kind of object (A) as in Example 1 and its comparative examples 2 to 6 • The same thing as in Example 3 (A ) As a kind of manufacturing formula and its 82.5 parts by weight and ultra high molecular weight methacrylic acid formaldehyde (Mitsubishi 1 ^ 乂 〇11 sold? -53 (^) 2.0 parts by weight of the conditions, can be produced with particles (pe 1 1 et) -like rubber resin composition with a rubber content of 17% by weight The manufacturing formula and its physical properties are listed in Table 3. Polymer (B '-2) 36 parts by weight, styrene-based copolymer High-molecular-weight fluorenyl acrylate polymer added P-5 3 0A) 2.0 parts by weight, the same as in Example 1 to obtain particles (pe 1 1 et) rubber modified styrene content of 17% by weight: The analysis of the properties of the resin composition is shown in Table 3. The operation mode is different from the adjustment of styrene copolymerization; The analysis of the properties of the styrene-based resin composition is shown in Table 3. The operation method is different in that the styrene-based copolymerization is changed; the analysis of the properties of the rubber-modified styrene-based resin composition is shown in Table 3. The operation method is different in that The styrene-based copolymerization was changed; the physical properties of the rubber-modified styrene-based resin composition are listed in Table III.

Page 1212578

Comparative Example 7 The operation method of Example 2 is the same as that of Example 2. The difference is that the type of the rubber modified stupid ^ dilute resin is changed to (C-2); the manufacturing formula of the rubber modified stupid vinyl resin composition Its physical properties are listed in Table III. [[Application Example of Vacuum Forming] ^ The rubber-modified stupid vinyl resin composition prepared in the above Examples 3, 5 and Comparative Example 2 was a uniaxial extruder (45mm diameter) manufactured by Shizhou Machinery Co., Ltd. in The raw material tank temperature is 2 0 ~ 24 Ot, the mold temperature is 24 0 ° C. · The sheet is pressed out, and then vacuum formed at 160 ° C by a vacuum forming machine; its composition and physical properties are shown in Table IV.

[Application Examples of Blow Molding] X. The rubber-modified stupid vinyl resin composition prepared in the above Examples 3, 4 and Comparative Example 2 was made with a spiral diameter of 100 mm manufactured by Feng Kee Iron Works Co., Ltd., L / D = 24, Accumulation Sampling Hollow Molding Machine (Model FK / ABI-100) for Extruder with Die Diameter 300mm, Blow Molding. Extrude the molding embryo in the barrel of the extruder at a temperature of 180 ~ 195 ° C, mold temperature of 195 ° C, and a spiral return speed of 40 rpm; then hold the mold in a mold, and maintain the temperature at 50 ×: pressure 6 Gpa, molding cycle 6 A minute blow-molded article; its composition and physical properties are listed in Table 4. [Evaluation method]

1. MIR The stupid ethylene-based copolymer (A) is measured at a temperature of 250 ° C and a load of 1 kg. The measured value of 1? Is MI (g / l0 minutes) at a temperature of 250 ° C and a load of l. The MFR measured by 0 kg is HMI (g / 10 points), and the ratio of MIR to HMI / MI. Where / MFR refers to the melt flow index, which is measured by ASTM D — 丨 2 38 method

Page 39 1242578

To get. 2 · Weight-average molecule ^ 1 Daoding dissolves the aforementioned styrene-ethylated copolymer (A) in Sigu, and then uses a gel dialysis chromatograph (GPC, manufactured by Waters) to dissolve the solvent, where ' ϋ The analysis standard was classified as Jubenyi. : Analytical measurement The analysis conditions are: ^ ^ dialysis chromatograph

Column: KD-8 0 6M Detector: Water RI-2410 Mobile phase: THF (flow rate io / mm) 3. Rubber content is based on Fourier transform infrared of Nicuslet model No. 4 70 Spectrometer (Fourier Transform Infrared Spectr〇niete; r

)test. unit weight% . 4. Impact resistance IZ0D is measured according to A S T M D-2 5 6 method. Unit ·· kg-cm / cm. 5. Draw down phenomenon The above rubber-modified styrene-based resin composition is molded on a hydraulic molding machine (made by Ota Hydraulics Co., Ltd., model ZETN-10), and formed into 150mmx at 23 ° C 150mmx 2 mm thick molded pieces, then cut into 2〇ιβπιχ 150 mm X 2 mm thick test pieces' placed vertically in an oven, the temperature was maintained at 180 ° C, after 10 minutes, the test piece was taken out to measure the length change rate ( (LL.) /! ^: LQ is the original length of the test piece, and L is the length after the test piece is tested) ^: 4% or less △: 4 to 8%

Page 40 1242578 V. Description of the invention (37) X: 8% or more 6. Extruded and discharged The above-mentioned rubber-modified styrene resin composition was used in a uniaxial extruder (45mm diameter) manufactured by Shizhou Machinery Co., Ltd. 2 3 0 ° C Extrude a plate of 300 mm X 300 mm x 2 mm thick, extrude the plate to weigh 10 m i ns, and find out the amount of it. Unit: g / in 1 η ° 7. Stress crack resistance Place a test piece of 100min X 12. 7mm x 3 in m on a jig with a radius of curvature of 1 65mm, then immerse it in the magic spirit, and measure The time when cracks occurred in the test piece after immersion. The longer the time, the better the stress crack resistance. 〇: 48 hours or more Δ: 2 4 to 4 8 hours X • 2 to 4 hours 8. Stain β Take 10 grams of the rubber-modified styrene-based resin composition described above and press it with a hot press to a diameter of 200 mm and a thickness 〇 · 3mm round sheet, observe the stain 〇: 0 ~ 1 point △ ... 2 ~ 4 points X ... 5 points or more (including 5 points)

9 ·· Uniformity of vacuum formed meat Thickness of the above-mentioned rubber modified uniaxial extruder (diameter 45mm) in X 2 in in thick flat plate, and then empty the inner wall of the refrigerator. The molded olefin-based resin composition was extruded at 300_.x 300 at 2 30 C. The molding machine was molded at 160 ° C to measure the thickness of the meat at 10 points on the refrigerator.

Page 41 1242578 V. Description of the invention (38) The difference between the large value and the smaller 11 L. The difference is 0 · 3 5mm or less Δ The difference is 0 · 35 ~ 0 • 5mm X The difference is 0.5 m 11 ] The thickness uniformity of the above blow-molded plastics will improve the above-mentioned rubber modified stupidity. The thickness uniformity is good. The thickness uniformity is poor. The thickness uniformity is poor. The thickness is poor. Machine accumulation (100)) blow molding. The extruder extruded the molding embryo at the center of 190 t. The mold was extruded at a mold speed of 6 GPa, the molding cycle was 6 minutes, and the shape of the 3icui was blow molded. Find the difference. [Description of attached table] Vinyl-based resin with a diameter of 100 for hollow molding cylinders is supplied at 195 ° C, held at a temperature of 5 mm and held at a thickness of 5 mm. The composition of this molded product is 5 cm. _ ， 1 ^ / 1) two 24 'die head machine (model FK / ABI-feed part temperature is 180 ° C screw return speed 4 0 rp in keep at 50 ° C, pressure, 180cm height, diameter upright Take 1 point from each direction to measure the meat

Table 1 shows the reaction conditions, manufacturing formula, and physical property analysis of the synthesis examples and comparative synthesis examples of the stupid ethylene-based copolymer (A) of the present invention. Table 2 shows the reaction conditions, manufacturing formula, and physical properties of the rubber modified styrene resin of Example 1 and Comparative Example 1 prepared by the simultaneous grafting method. Table 2 shows the manufacturing formulas and physical properties of the examples and comparative examples of the present invention prepared by the graft-kneading method;

Table 4 shows the composition and physical properties of the examples and comparative examples of the present invention in molding applications.

1242578 on page 42 Brief description of the diagram on page 43 1242578 R1, R2: CSTR R3, R4: plug flow SMAN ^ SP0 MMA, ^ 1¾¾ 烨 f 龆 驷 鵾 BMI N, N '-4,4' I 舛 ^ if ^ mJF axe siw 漭 驷 * DVB l · ^ »^ 舛 BPO &amp; ^^ 舛 啲 TX-29A 1, 1-^-¾ WT: i &amp; 4J (T-3, 3, 5-wf _3fc ^ 荈 PX -12 2.2-continued (4.4-Bu- depending on w T) ¾ p & wing TDM + l · ^^^ ® EB £ Analysis of the weight of the polyester copolymers of polyester and polyester (Λ) Average molecular weight (R4) Reactor fourth reaction (R3) Reactor third reaction (R2) Reactor second reverse drip QMC a / tc I Feed flow (kg / hr) Stirring speed (rpm) Temperature (° c) Composition Feed | Feed Flow (kg / hr) 丨 Feeding Speed (rpm) 1 Temperature ct) Composition 1 Feed tw 1φ 3 Feed Feed Flow ir (kg / hr) Feed Speed (rpill) d 1 Start Agent 1 | Polymerization | at Polymerization 1 s Each chain transfer initiator polymerization from 1 DVB | CO &gt; t (parts by weight) Type I (parts by weight) I (parts by weight) (parts by weight) Type 1 (parts by weight) ] I (parts by weight) I (parts by weight) | (weight ） Type 1 (parts by weight) 1 Type I (parts by weight) | I (parts by weight) | (parts by weight) 1 (parts by weight) 1 I (parts by weight) | ΓΟ cn CD 238783 1 1 1 1 1 | 0.04 g CO CJI DO ΟΊ 1 1 | 0.22 gg CD CO 0.01 -3 s 0.035 § 1 | 0.025 1 i oo ΟΊ ΟΙ CX) CJ 1 C \ D 0 * 1 ΓΟ CD ① o Qb 25. 1 237908 1 1 1 I 1 1 1 1 oo cn GO o 1 1 | 0. 15! Gr ° CO CD CD CO 0.01 s: 0.015 TX-29A 1 | 0.022 | 1 CO QJ \ C7D • CJI 〇l tO CJI oo CD CO cn ro cr s C \ 0 228726 1 OJ 〇Ί 〇〇cn 0.003 TX-29A 丨 g CO oo CO CD 0.014 TX-29A | 0.066 1 c〇① os CO oo ο 0. 01 s 0. 01 PX-12 i | 0.007 1 CO O 1 O 1 cp ο ί [o QJ \ LO CD CO cn CO o t &gt; o 241140 1 1 1 1 1 1 CD CO ΟΊ CO CD 0.0083 TX-29A 1. CD g CD GO oo 〇 &gt; 0.01 0.01 | PX-12 I 1 | 0.028 1 1 CO • cn CJ * I s Ol END ΟΊ ΓΟ CD CO ΟΊ 1 CL · IND cn 252688 1 1 1 1 1 1 CD CO CJI CO o 0.02 TX-29A 〇IX) CD g CD CO CO Q CZ) CD CD ◦ CO § i. 10. 022 I 1 CO CJI CJI cp ro u \ to CD CO CD 1 οι ° eg 187936 1 1 1 1 1 1 i 1 CO ΟΊ i --I GO CD 1 1 | 0. 15 1 gr ° CO CD CD OO 0.05 mesh; 0.015 TX-29A 1 0.022 ΟΊ GO ΟΊ s VO cn g CO cn 1 CD IND CJ1 230589 1 1 1 1 1 1 1 1 CO ΟΊ OO CD 1 1 | 0. 15 1 1- * CD r ° g CD OO CO o 0.01 01 mesh 0.015 TX-29A 1 0.022 1 oo CD at) DO CJI 1-A t &gt; oo CO cn aq 29.6 290245 1 1 1 1 1 1 1 1 1 CO cn GO CD 1 1 | 0.45 ί CZ) CD tO g 〇CO oo ¢ 0 0. 01 0. 015 TX-29A 1 0.07 I ΓΌ CO ΓΟ CJI oo CD CJD CJI 1 CO zr t &gt; o • 222003 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 CO CD ai DO ΟΊ 0.01 s: 0.03 D3 -do 1 CD 1 CO ro ① oo DO CO DO CT) CO cn t CO 1 rr life tsD 223091 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 CJD ◦ T \ D ◦ Ί ro CJI 0. 01 0.01 TX-29A 1 1 0.01! CO LND CD CO ro CO ro Q CO ◦ 1 A-10 23.8 219605 1 1 1 1 I 1 1 1 1 1 1 1 1 1 I 1 CJI [ND ΟΊ • o cn £ CD Q CO S 0.035 1 1 oo DO ⑦ CO IND CO oo CD CJD cn A- ll 30.4 468515 1 1 1 1 1 1 1 1 1 CO Ol CD 1 1 CD μ-a Ο 1 r ° g CO oo 1. 1 • —i 0.01 〇1 0.06 1 1 &gt; Q CO ro CD g A-12 22.4 1 108791 CO ΟΊ CD CO CD oo CO CD o CO TDM 0.03 cd S 1 0.01 1 CO ai CD • ej i OI OO ro CD ◦ CD, A-13 III 1242578 [Table 2] Synthesis example of rubber modified styrene resin Comparative example of rubber modified styrene resin C-1 C-2 Reaction conditions First reactor (R1) Temperature rc) 100 100 Stirring speed (rpm) 300 300 Feed flow rate (kg / hr) 37 37 Feed composition SM (parts by weight) 65.5 65.5 ΛN (parts by weight) 34.5 34. 5 BD (parts by weight) 5.5 5. 5 BMI (parts by weight) 0.022 0.0002 Polymerization initiator type TX-29A TX-29A C parts by weight) 0.005 0. 005 Chain transfer agent type TDM TDM C parts by weight) 0.075 0.0075 EB (parts by weight) 25 25 Second reaction (R2) temperature rc) 105 105 stirring speed (rpm) 200 200 feed flow (kg / hr) 3 3 feed composition SM (parts by weight) 100 100 BMI (parts by weight) 0. 15 0. 15 third reaction (R3) temperature (° C) 115 115 stirring speed (rpm) 150 150 fourth reactor (R4) temperature (° C) 125 125 mixing speed rpni) 90 90 The results rubber content (wt%) 10 10 Weight average molecular weight (Ben vinyl copolymer (A) a continuous phase) 181549 178566 MIR (Ben vinyl copolymer (A) a continuous phase) 24.3 21.2

Rl, R2: CS l R: R3, R4: plug How 1242578 Physical properties Extrusion conditions Physical property analysis composition (parts by weight) Stupid vinyl resin composition modified by bad glue Stain stress cracking resistance Extrusion output (g / min ) Vertical flow phenomenon IZOD (kg-cm / cm) Extruder die temperature (° c) Extruder raw material tank temperature (° c) Rubber content (% by weight) P-530A Styrene resin modified by rubber Copolymer (A) Rubber Graft Copolymer (B ') ο to η 1 丨 A · 13 1 A-12 1 &gt; L ^ 19 A-9 Lam A-7 La- · 5 ^ 14 LalJ L ^. &gt; CD 1 1 〇〇〇〇〇1— ^ CD 〇35.5 oo CD 220-240 ΓΟ on END-i Example 〇〇〇〇〇) _! CO ο CO CD ro ΓΟ 1 82.5 1 〇π IND 〇〇CO 1 --A Cn〇ο 35.4 丨 * ~ * ΙΌ CD OJ CO 〇〇GO CD CJl ο GO c_n tsD CO cr ^ 〇〇ΓΟ CO ο CO CO CND DO CJD CO CD 〇1 〇〇CD ο CO GO i ~ 1 CO cp oo CTj CD 〇〇CO CD ο CO —a 1 ~ ^ ΓΟ S CO CD —J 〇〇DO CD CD ο 1 CO oo CO [N D s CO CD 〇〇〇〇 CO CD CO ο oo CO 1- ^ —J tSD a ^ &gt; CO CD CO 〇〇CO CsD CZ) ο CJl II CnD CJD A CO CJ ^ 1-i. 〇X IND 〇〇to X CO oo 1 ~ 1 i ~ · * ΓΟ CJl LND 1-ί Comparative Example 〇X IND oo X OJ tND CD Η— »CO OJ CD tND 〇X tND OO oo t &gt; oo r ° oo k— ^ t &gt; o CO CD CO X &gt; DO OO ΟΊ ο 32.5 t— l &gt; 0 OO c ^) D &gt; [&gt; CO cn ο CO oo CJl '1-k CO CO OD cn 〇X CO GO CD X JMJ IND CD oo CD CD 〇X OO oo cn &gt; [&gt; 33.8 t— ^ IND 82.5 17.5 [»w] fslrs ~ 舛 谛 许 赛 Sai Hong 1242578 Physical Thickness Uniformity Extrusion Conditions Physical Property Analysis Composition (parts by weight) Ethylene resin composition Extruder die temperature (° c) Extruder raw material tank temperature (° C) Rubber content (% by weight) P-530A Silly ethylene copolymer rubber graft copolymer (B ') 1 A- 13 1 A-12 丨 A-ll 1 A-10 I A-9 A-6 A-5A ± J &gt; OJ &gt; to &gt; B'-2 〇IND CD 220-240-DO s CO CD CO Example Vacuum Forming Γχ) s CO CD cn X IND CD CO CO ϋ〇 Comparative Example 〇CNO CD 220-240 ΓΟ CD CO CO CO Example Blow Molding 0J__L ΓΟ CD CO CD 仏 X-ΓΟ σ ^) CO CJO CnD Comparative Example

Claims (1)

1242578 1. A kind of modified modified rubber for extrusion molding is composed of styrene-ethylene copolymer ⑴ as a continuous phase and a sub-particle (1 is composed of a dispersed phase ') and a stylized ethylenic copolymer (A) is composed of (ι —丨 5 ~ As a monomer, (10) parts by weight of nitrile ethylene early limbs. (1-3) 040 parts by weight of other copolymerizable vinyl monomers, the above (1 1 ), (Ι-2), (Bu 3) were obtained by copolymerizing 10Q parts by weight and 5,000 to 1C by weight of a polyfunctional maleimide-based monomer; The rubber content of the rubber-modified styrenic resin composition was measured at 40% by weight. The styrene-based copolymer (A) was measured at a temperature of 250 ° C and a load of 1.0 kg. The obtained MFR is MI (g / l0 minutes), the temperature is 25 ° C, and the measured MFR is 10 kg (H / g), and the MIR (= HMI / MI) is between 22 and 33. , And its weight average molecular weight is in the range of 150,000 to 4500. Page 44