TWI247021B - Flame retardant styrenic resin composition - Google Patents

Abstract

The present invention provides a flame retardant styrenic resin composition, which has the advantages of anti-stress-cracking, excellent impact resistance and flame retardancy, low smudge, and unlikely to form dripping during burning. The invented composition is composed of 100 wt parts of a rubber-modified styrenic resin (I) and 1 to 40 wt parts of a flame retardant (II), in which the rubber-modified styrenic resin is obtained by copolymerization of 50 to 90 parts by weight of styrenic monomer (i-1), 10 to 50 parts by weight of acrylonitrilized vinyl monomer (i-2), and 0 to 40 parts by weight of other copolymerizable vinyl monomers (i-3), based on totally 100 parts by weight of mentioned monomer units, and 0.0005 to 1.0 parts by weight of a multifunctional maleimide monomer. In which, the rubber-modified styrenic resin (I) contains 1 to 40 wt% of rubber, and less than 1.25 wt% of bimmers or trimers derived from styrenic monomer and acrylonitrilized monomer. Furthermore, the styrenic copolymers (A) has a MFR of MI (g/10 minutes) when measured at 200 DEG C with a load of 1 kg, a MFR of HMI (g/10 minutes) when measured at 200 DEG C with a load of 10 kg, and a MIR (=HMI/MI) of 21.5 to 30.0.

Description

1247021 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) Technical Field of the Invention The present invention relates to a flame-retardant styrene-based resin composition, particularly for providing a stress crack resistance, impact resistance and flame retardancy. Excellent, less stained', and hard-to-burn styrene resin composition that is less prone to drenching when burning 'Materials 0' [Prior Art] ^ General electrical equipment, office equipment, auto parts, household goods, etc. ·: In the process of forming and molding, the widely used styrene-based resin material has the disadvantage of being easy to burn. For example, when the flame approaches the molded product, the molded article of the shell J starts to burn, and even if the fire source is removed, the flame does not immediately extinguish. &Years, for the safety of fire, the requirements for flammable styrene resin are becoming more and more stringent, especially for electrical equipment, office equipment and other parts that must meet the US UL (Underwriters Ub〇rat〇ries, US Security Laboratory) The 叽-94v〇 specification, and the 叽-94V〇 specification test item +: requires that there must be no dripping. In the past, a method of igniting a stupid vinyl resin is described in Japanese Laid-Open Patent Publication No. Hei 10-12 0863, JP-A-2000-129, and is an organic bromine compound, a compound, or the like. It is difficult to burn, or it is mixed with a flame retardant additive such as a trioxide record. However, the above method cannot effectively prevent the /first drop phenomenon, so the obtained styrene resin cannot pass the 吖-90 〇+ check test, and the resin is resistant to impact due to the mixing of a large amount of the flame retardant. Sexual decline. In the case of the present invention, the flame retardant resin of the conventional flame retardant resin is also inferior in chemical stress cracking resistance. For the flame retardant ABS resin, the improvement method is generally 1247021. 5. The invention description (2) is to improve the chemical stress cracking resistance of the cyanide vinyl resin in the ABS resin, but how to improve the method Good impact strength: flame retardant and other flame retardant thermoplastics with good crack resistance to pharmaceuticals, etc., are familiar with this technology and have long been a breakthrough. [Inventive content] = The purpose of Ming T is to provide a flammable styrene-based resin composition 1 'Specially to provide a stress crack resistance, impact resistance and flame retardant and is not easy to produce dripping when burning Flame-retardant styrene-based resin The composition of the flame-retardant styrene-based resin is composed of the rubber modified by the rubber, which consists of 100 parts by weight and a flame retardant (^丨~^ parts by weight). The rubber-modified styrene-based resin (1) is a styrene-based monomer having a 5' 90 f portion, and (1 - 2) 10 to 50 parts by weight of a nitrile-based monomer. (i-3) 0 to 40 parts by weight of other copolymerizable ethylene-based precursors, the total of (i-1), (1-2), (1-3), 1 part by weight, and 〇 · 0 5 = . 共 by weight of a polyfunctional maleimide-based monomer copolymerization: the styrene-based copolymer (A) as a continuous phase and rubber particles (β) as a phase = composition; , rubber modified styrene resin (n's rubber $ containing 1 to 40% by weight, derived from styrene monomer and nitrile vinyl based on the second or third volume of the second or third body The content is 5% by weight or less of the rubber modified by the rubber-modified styrene-based resin (I); and the MFR measured by the styrene-based copolymer (Α) at a temperature of 200 ° C and a load of 1 kg is MI (g/ 10 points), temperature

country

Page 6 1247021 V. Description of invention (3) The MFR measured at 20 °C and 10 kg load is HMI (g/10 min), and its MIR (two HMI/MI) is between 21.5 and 30·30. between. [Embodiment] Specific examples of the (i-1) styrene monomer used in the present invention are: styrene, α-methylstyrene, p-t-butylstyrene, p-methylstyrene, O-nonylstyrene, m-nonylstyrene, 2,4-dimethylphenylethylene, ethylstyrene, fluorenyl-p-nonylphenylethylene and indimetharin, etc. Preferably, styrene or α-methyl styrene is used. The above compounds may be used singly or in combination. The (i - 1 ) styrene monomer of the present invention is used in an amount of from 50 to 90 parts by weight based on 100 parts by weight of the total of (i - 1 ), (i - 2 ), (i - 3 ) It is preferably 5 5 to 8 5 parts by weight, more preferably 5 8 to 80 parts by weight. Specific examples of the (i-2) nitrileated vinyl monomer used in the present invention are acrylonitrile, α-mercapto acrylonitrile, and the like, and acrylonitrile is preferred. The (1-2) nitrile vinyl monomer of the present invention is 10 to 50 parts by weight, based on 100 parts by weight of the total of (i-1), (i-2), and (i-3), preferably 15 to 45 parts by weight, more preferably 2 0 to 4 parts by weight. (i - 3 ) Other copolymerizable ethylene-based single system used in the present invention means a vinyl group which can be used together with the (i -1) styrene monomer of the present invention, (1 - 2 ) nitrileated ethylene The monomer which is a monomer-polymerized monomer, and a specific example is an acrylate type monomer, a methacrylate type monomer, and a monofunctional maleimide type monomer. Specific examples of the acrylate monomer include methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, and polyethylene glycol diacrylate. Among them, butyl acrylate is preferred.

1247021 V. INSTRUCTION DESCRIPTION (4) Specific examples of the methyl acrylate monomer are: methacrylic acid, ethyl methacrylate, methyl propyl acrylate, methacrylic acid Butan vinegar, phenyl decyl acrylate, hexyl methacrylate, cyclohexyl acrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, methyl Dimethylaminoethyl acrylate, ethylene dimethacrylate, neopentyl dimethacrylate, and the like, among which decyl methacrylate and butyl methacrylate are preferred. The monofunctional maleimide-based monomer means that the monomer contains only a single maleimine functional group, and specific examples thereof are: maleimide, N-methyl maleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmalamine Amine, N-cyclohexylmaleimide, N-phenylmaleimide, N-2-mercaptomaleimide, N-2,3-dimercaptophenylmaleimide , N-2,4-dimercaptophenylmaleimide, N-2,3-diethylphenylmaleimide, N-2,4-diethylphenylmalazone Amine, N-2,3-dibutylphenylmaleimide, N-2,4-dibutylphenylmaleimide, N-2,6-didecylphenylmale Amine, N-2,3-diphenylphenylmaleimide, N-2,4-dichlorophenylmaleimide, N-2,3-dibromophenylmaleimide or N-2,4-dibromophenylmaleimide or the like, among which N-phenylmaleimide is preferred. In addition, other copolymerizable possible vinyl monomers, such as acrylic monomers (eg, acrylic acid, methacrylic acid), anhydrous maleic acid, anhydrous methyl maleic acid, anhydrous methyl thiobutanic acid , fumaric acid (fumaric acid), itaconic acid (itac ο nicacid) and other unsaturated ferric acid compounds

1247021 V. Description of invention (5) and its esterification monomer f ^ ene, propylene, 1-but, / such as dimethyl fumarate, dibutyl itaconate), B, pentene, 4- Methyl-1-pentene, gasified ethylene, hydrazine ethylene, chlorotrifluoroethylene, hexafluoropropylamine, isobutylamine, ethyl acetate, ethyl ketone , (i-3), (i-3) other, (i, y, y, y, y, y, y, y, y, y, y, y) 1—2), (1-3), 1 part by weight of the hinge, this part is preferably 1 to 34, / the amount of the polymerized vinyl monomer is 0 to 40 by weight. It is a small amount of 2 Malay _ ^^ 夕一吕广性Malay & Ayurvedic singular scorpion, refers to the most above Malay 1 1 ^ ... amine functional compounds, such as 2 Or a compound of 3 or 3"" ^ functional groups. Among them, the f ^ _ imine monomer is L. Its structural formula can be expressed by the general formula (1)...

• General formula U) [wherein 'X is an alkylene group having a carbon number of 1 to 1 ,, an arylene group, a carbonyl group, -S02 -, -SO-, -0- , -0-R-0-(R may be an alkylene group, an arylene group), and specific examples are: N,N,-4,4, -(3,3'-dimethyldiphenylmethane) N,N,-4,4,-(3,3'-dimethyl diphenyl methane)bismaleimide, N,N, -4, 4' - (3,3'-diethyl Phenylmethane) bismaleimide [n, 『-4,

Page 9 1247021 V. Description of invention (6) 4' -(3, 3' -diethyl diphenyl methane ) bisma1eimide ), 1 "-4,4'-diphenyl. methane bismaleimide (1『- 4,4'-diphenyl methane bismaleimide), 1^1, "-4,4'-2,2-diphenylpropanin, bismaleimide (1^1, "-4,4'-2, 2-(11011611丫101'〇08116 bismaleimide), N,N'-4,4'-diphenyl ether bismaleimide (N,N' -4,4'-diphenyl ether bismaleimide), N, N'-3,3'-diphenyl sulphate (N, Ν' - 3,3'-diphenyl sulfone bismaleimide), N, N'-4, 4'-diphenyl hydrazine醯iimine (n,N' -4,4, -dipheny1 su1fone bisma1eimide), N,N,-4,4,-: Benki Sail Double Malay Feimine (N,N -4,4 - Diphenyl sulfoxide bismaleimide), N, N'-4, 4' benzophenone bimaleimide (n, N' -4, 4'-benzophenone bi sma 1 eimi de ), N, N, -1 , 3 - phenylene bismaleimide (N, N'-l, 3-phenylene bismaleimide), wherein 1 "-4,4,-diphenylnonane bismaleimide, ^" —1,3_Aben Preferably, the amount of the polyfunctional maleimide monomer of the present invention is based on a total of 100 parts by weight of the above (i-1), (丨_2), (i_3). 0· 0 0 05〜1· 0 parts by weight, preferably 〇. 0〇卜〇·3 parts by weight, more 0 0· 0 0 3~0 · 1 5 parts by weight. If polyfunctional Malayia When the amount of the amine-based monomer is more than 1.0 part by weight, the viscosity of the polymer of the stupid ethylene copolymer (Α) will rise sharply, and the polymer bridging foreign matter and stains are easily generated. The method for producing the styrene-based copolymer (A) can be carried out by a bulk or solution polymerization reaction, an emulsion polymerization reaction or a suspension polymerization reaction which is generally used; wherein the polymerization reaction is in the form of a block or a solution. ;

1247021

The device may include: a columnar flow (CSTR), or a static one, or may be used in combination. When a combined reactor reactor (PFR) is used in a manner of production, and the initial weight fraction of the polymerization of the present invention is poly-0.5 part by weight or a multi-agent initiator is oxidized bisphenyl CSTR) is preferred. It will be reversed to be a polystyrene. Starting, the energy can be aggregated as: propyl (dFR reaction (PFR), fully mixed reactor (reactor of the type mixer), etc. The number of reactors can be two or more. When three or more reactors are preferred, the first reactor is completely mixed, and the final reactor is used to produce the styrenic copolymer (A) of the present invention using a columnar flow. The applied raw material solution is continuously fed into the reactor to be fed into the reaction. The copolymer (A) is usually added to the above (i-1) 2), (i-3). The total amount of the catalyst is 0 to 1 part by weight, preferably 0. The polymerization initiator used for the 〇〇i may be a monofunctional polymerization starting initiator. Among them, specific monofunctional polymeric benzoyl peroxide, icumyl peroxide, tertiary butyl peroxide (t, tert-butyl hydroperoxide (t-butyl hydroperoxide) (cumene hydroperoxide), t-butyl-peroxy benzoate, di-2- Bis-2-ethy lhexy 1 peroxy dicarbonate, tert-bu ty 1 peroxy isopropyl carbonate (BPIC), cyclohexanone peroxide (cyclohexanone peroxide), 2,2'-azo-bis-isobutyronitrile, 1,1'-azobiscyclohexan-1-propionitrile (1,1 '-azo — bis

Page 11

1247021 V. Description of invention (8) 〇丫. 1〇1^义31^-1-0&1^〇1^1:1^16), 2,2,-azo-bis-2-methylbutyronitrile (2,2 -az〇-bis- 2-methyl butyronitrile) and the like. Among them, it is preferred to peroxidize one of the brewing and the diphenylisopropyl peroxide. Specific examples of the polyfunctional polymerization initiator are: 1,1 _bis-tert-butyl peroxycyclohexane::: (1,1-bis-t-butyl peroxy cyclohexane), 1, bu-double- 1,1-bis-t-butylperoxy-3,3,5-trimethyl cyclohexane (TX-29A), 2,5 - 2 Methyl-2,5-bis-(2-ethyl peroxygenated) calcined [2,5-dimethyl-2, 5-bis-(2-ethylhexanoxy peroxy) hexane], 4-(t-butyl Peroxycarbonyl)-3-hexyl-6-[7-(t-butylperoxy-Wilyl)heptyl]cyclohexene{4-(t-butyl peroxy carbonyl)-3-hexyl -6-[7- (t-butyl peroxy carbonyl) heptyl] cyclohexane}, di-t-butyl-diperoxyazelate, 2,5-dimethyl-2,5-bis(benzene Methotrexate - 2,5-dimethyl-2,5-bis-(benzoyl peroxy)hexane, di-t-butylperoxy-hexahydro-terephthalate (di-t- Butyl peroxy-hexahydro-terephthalate), 2,2-bis(4,4-di-t-butylperoxy)cyclohexylpropane [2,2-bis-(4,4-di-t-butyl peroxy) cyclohexyl Propane PX-12], a polyfunctional mono peroxy carbolic acid esters (m u 11 i f u n c t i ο n a 1 monoperoxycarbonate) (e.g. U.S. ATOFINA Co., Ltd., trade name Luperox JWE) and the like; wherein in TX-29A, PX-12 is preferred. The reaction temperature of the above reactor is controlled at 20 to 300 ° C, preferably 60 to 2 50 ° C, more preferably 8 0 to 2 40 ° C, and the pressure of the reactor is controlled at 1 to 1 0

1247021 ------------ V. Description of invention (9) ~ ---- between kg/cm2; and in order to control the molecular weight of the polymer, use chain transfer agent, based on the above -, (b 2), (b 3) person =, the chain transfer agent is used in an amount of 〇 2 parts by weight, preferably ° 〇. 〇〇 11 parts by weight; the chain transfer agent used may be a monofunctional bond transfer agent or a polyfunctional chain transfer agent, and the specific monofunctional chain transfer agent is: 1) Mercaptan (red rcaptan) class: A Thiol, n-yl mercaptan, cyclohexyl mercaptan, n-dodecyl mercaptan, stearyl keto alcohol "to order " mercaptan", tri-dodecyl mercaptan (t - d〇decyl Mercaptan (referred to as TDM), n-propyl mercaptan, n-simylene, third-octyl mercaptan, third-mercapto mercaptan and the like. Octyl "2" alkylamine (alky 1 amines) class: monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, di-n-butyl Other amines, such as pentapheny lethane, α-methyl styrene dimer, terpinolene Wherein n-dodecyl mercaptan and third-dodecyl mercaptan in the mercaptan are preferred. The polyfunctional chain transfer agent is, for example, isopentanol tetrakis(3 - mercaptopropyl) [pentaerythritol tetrakis (3-mercapto propionate)], pentaerythritol tetrakis (2-inercapto acetate), tris-(2-sulfoacetic acid) By trimethylolpropane tr is (2-mercapto acetate), trimethylolpropane tris(3-mercapto propionate)-

Page 13 1247021 V. Description of the Invention (10) - Trimethyl 〇 1 - pr〇pane tris (6-mercapto hexanate), etc.; It is preferred to use tris-(3-mercaptopropionic acid) trishydroxypropyl propyl ester. 1 The above-mentioned styrene-based copolymer (A) is produced by continuously introducing a raw material solution into a reaction apparatus to carry out a reaction, and when all the monomers in the raw material solution reach a predetermined conversion ratio, the polymerization solution is continuously continuous from the reaction apparatus. After taking out, the devolatilizer is introduced to remove unreacted monomers and volatile components, and then granulated. The final monomer conversion ratio in the polymerization reaction is generally 5% by weight or more, preferably 60% by weight or more, and more preferably 7% by weight or more. Generally, the devolatilizer can be used to remove the unreacted monomer or volatile components by using a vacuum degassing device or a degassing device. If necessary, the water in the recovered liquid can be removed and re-removed. Used as a raw material solution. In the production of the styrene-based copolymer (A) of the present invention, a solvent may be added as needed. The bathing agent is used in an amount of 〇~100 parts by weight, preferably 〇~6 基于, based on 1 part by weight of the total of (i-1), (i-2), and (i-3). The parts by weight are more preferably 1 to 50 parts by weight; the solvent which can be used may be benzene, toluene, ethylbenzene, phenylbenzene, o-xylene, dioxin, and pentane, octane, and cyclohexene. Methyl ethyl ketone, propylene g, and butyl sulfoxide are equivalent. The stupid ethylene copolymer (A) of the present invention has a MFR of MI (g/l〇) measured at a temperature of 2 Torr and a load of lkg, and a temperature of 2 〇 (rc, a load of 1〇1^). MFR is HMI (g/l〇), and its MIR (=HMI/MI) is usually between 215 and 3〇〇, preferably between 2 1 · 8 and 2 9. 0, more preferably 2 2. Between 0 and 2 8. 0; wherein MFR refers to the melt flow index, which is determined by the ASTM D_ 1 238 method. The MIR numerical control method of the copolymer (A) can be one of the following methods.

1247021

One or several kinds of sexual maleate initiators, for example, or an imine series or a second one is a Dye-forming lipid composition polymerization reaction 〇.0005-1 21·5~30· and used to achieve an imide system The monomer selection and the amount of the above (i~l or polyfunctional polymerization after the invention of the flammability phenomenon and dimension 'need to be full at the same time, polyfunctional 〇 〇 part by weight, between 0. ie copolymer (A) In the case of copolymerization, the amount of polyfunctional addition and the timing of addition, the polyfunctional polymerization 'reaction to be selected, the final conversion rate of the monomer, the styrene monomer, and the part of the polyfunctional maleic polymerization initiator The amount is transferred to the second reactor to join and the like. A flame-retardant styrene-based tree having excellent stress crack resistance, less stain, and excellent impact resistance when burned. (1) The styrene-based copolymer (A) is a maleic imine series. The amount of the body is between (2) the stupid ethylene copolymer 2MIR in the ^ & month rubber modified stupid vinyl resin (I), the styrene styrene copolymer (A) as the continuous phase, rubber The particle (b) is obtained as a dispersed phase, and the content of the rubber component is usually "weight v, preferably 3 to 35 wt%, more preferably 5 to 30 wt%. The rubber fraction of the present invention When the content is between 40% by weight and t, the balance between the flame retardancy and the impact resistance of the flame retardant styrene resin composition is preferred. The rubber-modified stupid vinyl resin of the present invention (j) The manufacturing method may be carried out by adding a rubber component to the polymerization process of the styrene copolymer (A) to participate in the reaction (hereinafter referred to as a simultaneous grafting method), or by grafting a rubber component such as a general rubber or rubber. a substance, especially a rubber graft copolymer, is directly mixed with the present ethylene-based copolymer (A) of the present invention. Was obtained (hereinafter abbreviated to graft-kneading method). While the grafting, generally recoverable

1247021 V. Description of invention (12) Blocky? Legal, &gt; trough liquid polymerization, emulsion polymerization or suspension polymerization is completed. The above-mentioned method for producing a rubber graft copolymer can be generally carried out by an emulsion polymerization method or an emulsion block polymerization method, and an emulsion polymerization method is preferred. The method for producing the rubber-modified styrene-based resin (I) of the present invention will be described below by two methods: <Method 1: Simultaneous grafting method>

In the first method, the rubber-modified stupid vinyl resin (I) of the present invention can be obtained by bulk or solution polymerization. The reactor used in the first method may include a columnar flow reactor (PFR), a fully mixed reactor (CSTR), or a reactor containing a static mixer, and the like. The number of the reactors may be one, or two or more, preferably three or more, in combination. When more than two reactors are used, the first reactor is preferably a fully mixed reactor (CSTR), and the final reactor is preferably a columnar flow reactor (pFR). In the production method, the raw material solution (containing rubber component) of the rubber-modified styrene resin (I) which satisfies the rubber of the present invention is continuously fed into the reactor for reaction, and the reaction temperature is controlled at 3 〇 3 〇〇 It is preferably 6 〇 to 2 5 〇. 〇' is preferably 8 0~2 4 0 °C, and the pressure of the reactor is usually controlled between 11 〇kg / c m2; and to control the molecular weight of the polymer, the uninvented rubber is modified In the production of the vinyl resin (I), a polymerization initiator or a key transfer agent may be used as needed. The rubber-modified styrene-based resin (I) is prepared by continuously introducing a raw material 'liquid mixture into a reaction apparatus to carry out a reaction, and when all the monomers in the raw material solution reach a predetermined conversion ratio, the polymer solution is further Reaction unit

Page 16 1247021

V. INSTRUCTIONS (13) Removal of monomer and volatile components, including styrene copolymer (A) as &amp; phase-shifted rubber modified styrene, final monomer conversion rate of 50% by weight Good for 70% reset. Generally take off or push out the degassing device. The volatile components are then evaporated and the recovered raw material solution can be used if necessary. The bulk liquid of the styrene resin (I) contains: (i-1) 50 to 90 parts by weight of a nitrile vinyl monomer, and (a vinyl monomer (the total of 1 〇〇i to 2) (i-3) a total of 100 weight of maleic imide monomer, 0 to parts by weight of rubber; wherein styrene may be copolymerized with a vinyl monomer, a solvent and, if necessary, a polymerization amount The specific description is the same as the manufacturing liquid, and the polymerization process is carried out to obtain a rubber modification reaction reaction method and the following rubber, but the amount of the monomer and the rubber is continuously taken out, and the introduction of the devolatilization device will not be described. After that, the granulation is carried out to obtain a continuous phase of the package, and the rubber particles (B) are known as the branching tree (I). Generally, the uppermost polymerization reaction is more than 60% by weight, and the degassing degassing tank can be used for the more volatile device. After the device recovers the unreacted monomer or the water in the liquid by the condenser, it is reused as the raw material solvated styrene monomer used in the rubber modification or solution polymerization method in the first method, (i - 2 ) 1 〇~5 0 i - 3) 0 to 40 parts by weight of other copolymerizable parts by weight), And relative to (i - 1 ), (parts of 0 · 0 0 0 5 ~ 1 · 〇 by weight of multifunctional 1000 parts by weight of the solvent, and 〇. 5~2 5 heavy monomer, nitrile vinyl series The polyfunctional maleic imine monomer, the initiator, the chain transfer agent, and the raw material of the styrene copolymer (A) are dissolved in the above method 1. Resin (I). Emulsified poly-linked, branched copolymer (B') is prepared in the same manner as in the first method. The block or solution of the rubber-modified styrene resin (I) of the present invention.

Page 17 1247021 V. INSTRUCTIONS (14) During the olefinic monomer and nitrile ethylene phase, the rubber phase is polymerized by agglomeration, and the styrene conversion rate is gradually increased, and it is converted with vinyl monomer and nitrile B. The rubber particle phase is formed by dispersing a particulate body and a nitrile vinyl monomer. 'preferably 0 · :1 to 5 // m, a monomer of a single continuous phase such as a monomer, a monomer such as a monomer such as a reactor olefinic monomer (dispersed phase) and a rubber particle thereof More preferably, 0. 1~ In the polymerization reaction, a mixed solution of rubber and a stupid body exists in the initial state of polymerization, but as the rubber is joined, the vinyl monomer and the like are mixed, and the rubber component is gradually The benzene monomer and its polymer are surrounded, and on the other hand, the styrene-based single polymer is converted into a continuous phase. The most weight average particle diameter is 0. 〇5~1 0 .// m 2 // m 具体 The specific examples of the rubber component in the method 1 are: diene rubber, polyolefin rubber (for example, ethylene-propylene rubber), polyacrylic acid Ester rubber, polyoxygenated rubber, and the like. The diene rubber is a polymer having a glass transition temperature of 二烯°c or less after polymerization of a diene monomer component, and specific examples of the diene rubber are butadiene rubber, isoprene rubber, and gas. Butadiene rubber, EPDM rubber, styrene-diene rubber, acrylonitrile-diene rubber, etc.; wherein 'Dingshao rubber has high cis (Hi-Ci s) content and low cis (l〇w —C is ) content; in cis-type rubber, the typical weight composition of cis (c丨s) / vinyl (Vinyl) is (94~99%) / (〇~5%), and the rest of the composition It is a trans (Trans) structure; its Mooney viscosity is between 20 and 120, and the molecular weight range is 1 0 0,0 0 0~8 0 0,0 0 0; in low cis rubber, cis The typical weight composition of /vinyl is in the range of (20~40%) / (6~20%), the rest is trans structure, the Mooney viscosity is between 20~120, and the molecular weight range is 100, 〇〇〇 ~80 0, 0 0 0 is better; stupid ethylene-diene rubber specific

Page 18 1247021 V. Description of the invention (15) Handle such as styrene-butadiene rubber, styrene-isoprene rubber, etc., which may be agglomerate, random copolymer or composition increasing/decreasing (taper) copolymer. Wherein the weight ratio of styrene in the styrene/butadiene rubber is preferably 50% by weight or less, and the molecular weight is preferably 5 Å, 〇〇〇~600, preferably ;; Butadiene rubber and stupid ethylene/butadiene rubber are preferred. <Method 1 · Grafting and kneading method> Method 2, the styrene-based copolymer (A) and the rubber graft copolymer (B') can be kneaded and extruded to obtain the rubber-modified stupor-based resin of the present invention (I) ). In the second method, the styrene copolymer (A) and the rubber graft copolymer (B') are usually dry-mixed by a commonly used Hanschel mixer, and then, for example, an extrusion mixer, a kneader or A mixer such as a Banbury machine is melted and mixed, and then granulated. The method for producing the rubber graft copolymer (B') can be generally carried out by using a bulk or solution polymerization reaction, an emulsion polymerization reaction or a suspension polymerization reaction. Among them, the rubber graft copolymer (B,) is produced by a bulk or solution polymerization reaction in which a raw material solution is subjected to graft polymerization. The raw material solution is: (1-1) 5 (^9/, the amount of the stupid vinyl monomer, (i-2) 1〇~5〇 part by weight of the nitrile vinyl monomer, (1 - 3 ) 〇 ~4 〇 parts by weight of other copolymerizable vinyl monomer: more than 1 〇〇 by weight, 〇~丨〇〇 by weight of solvent and 〇·5~ 2 5 heavy damage rubber, and added as needed a polymerization initiator, a chain transfer agent; the raw material solution usually does not contain a polyfunctional maleimide monomer, and if a polyfunctional maleimide monomer is used, the amount thereof needs to be used in the present invention.

1247021 V. Description of invention (1β) The lower limit of the amount. Among them, the ethylene-based copolymer (A) which can be copolymerized with a vinyl initiator "chain transfer agent" is the same as the first method. In the rubber of the present invention, the rubber and the styrene/gluten solution are in the initial stage of polymerization but with the rubber. The conversion rubber component of the graft monomer monomer is gradually surrounded by the styrene-butadiene polymer, and the surface-stirring vinyl monomer becomes a continuous phase. The final particle size is 〇. 05~1〇, and the other rubber grafting method is to make I, the rubber monomer 15~95% by weight of the copolymerized monomer 0~35 heavy' and, if necessary, add the polymerization reaction, and The copolymer emulsion is obtained by grafting the rubber emulsion required for coagulation with the raw material solution of the aforementioned rubber emulsion 'stupid ethylene single system monomer, solvent and kind and usage amount. The graft copolymer (B,) is a monomer, nitrileized B stage, the rubber phase is a polymerization reaction, the benzene ethyl ratio is gradually increased, and the olefinic monomer, nitrile is converted into dispersed particles, and the nitrile ethylene single rubber The particle phase formation is preferably 0.; 1~5 // m polymer (B ') may also be a monomer or a single added emulsifier, such as a rubber emulsion of 40 to 90 weight, a nitrile ethylene monomer amount, or the like. It acts as a rubber graft copolymerization, dehydration, and dry polymer (B'). The rubber component, the nitrile vinyl monomer, and the polymerization which are added as needed are specifically described in the same manner as in the case of a monomer or a solution polymerization reaction monomer which is a specific example of the composition of the stupid rubber component. In the state of the continuous phase, the ethylenic monomer and the nitrileated ethylene are stirred by the reactor, the monomer such as a vinyl monomer and the state thereof (dispersed phase), and the monomer such as the other monomer and the polymer thereof are transferred. The weight average of the rubber particles is more preferably from 0.1 to 2 //m. By emulsion polymerization, the parts (solid parts) and styrene body 5~5〇% by weight, other body mixture 6 0~1 〇 parts by weight of the starting agent and the chain transfer agent are subjected to the joint emulsion; And other steps to obtain the invention, the description of the same method.

Page 20 1247021 V. INSTRUCTIONS (17) Description of rubber composition, in which diene rubber is preferred. The method for producing a diene rubber emulsion may be 1 to 50% by weight of a diene monomer (for example, butadiene) or a diene monomer, and 0 to 50% by weight of other copolymerizable monomers, for example, styrene. The copolymerizable monomer such as acrylonitrile and (meth) acrylate is polymerized by emulsion polymerization to form a dibasic rubber emulsion having a weight average particle diameter of 0. 0 5 to 0. 6 // m; By the emulsion polymerization method, a small particle size diene rubber emulsion having a weight average particle diameter of 0. 0 5 〜0 · 2 0 // m is obtained, and then cold; Dongyueba Dafa, mechanical fertilizer method or additive fertilizer method will be used. The small particle size diene rubber emulsion is grown to a weight average particle diameter of 0.22 to 0.66 m of a large particle size diene rubber emulsion for further graft copolymerization; wherein the additive is hypertrophy The additives used in the method may be: an acidic substance such as acetic anhydride, hydrogen chloride or sulfuric acid, or a salt-based substance such as sodium carbonate, potassium carbonate or vaporized calcium, and (mercapto)acrylic acid-(fluorenyl)acrylic acid. Ester copolymer (such as methacrylic acid-acrylic acid butyl copolymer), mercapto propylene - ethyl acrylate copolymer) flocculant polymer containing carboxylic acid groups. In the rubber-modified styrene resin (I) of the present invention, the total amount of the di- or tri-dimer derived from the styrene monomer and the nitrile-vinyl monomer accounts for the rubber-modified styrene system. The resin (I) is 1.25 wt% or less, more preferably 1.10 wt% or less, still more preferably 0.95% by weight or less. In order to achieve the flame retardant styrene resin composition which is less likely to cause a drenching phenomenon during combustion of the present invention, it is necessary to simultaneously satisfy the polymerization reaction of the (1) styrene copolymer (A) of the present invention, and the polyfunctional Malay. The amount of the quinone imine monomer is between 0. 0 0 0 5~1. 0 parts by weight, and (2) the styrene copolymer (A) Μ IR is between 2 1. 5~3 0. 0 And (3) from styrene monomer and nitrile ethylene

Page 1247021

V. Description of invention (18)

The total content is below the rubber modification. The method for controlling the derivatization of the rubber-modified styrene-butadiene-based vinyl monomer can be achieved by the following amounts of the styrene-based copolymer (A), the polymerization temperature, and the polymerization time, for example, low-temperature polymerization. Treatment (extruder is added with defatted fat composition. The system is composed of rubber modified. The fat composition is usually a rubber agent (Π), which is melted and mixed by a commonly used Hancon mixer, kneader or Banbury. And re-extruding the granulated fat composition, based on the above-mentioned rubber parts by weight, 38 parts by weight of the flame retardant (Π) is more preferably 3 to 35 parts by weight to 1 part by weight, and the flame retardant benzene is a flame retardant. The amount of (Π) used is that the impact resistance of the resin composition may be a halogen-based flame retardant or a phosphorus-based two-component or three-component vinyl resin derived from, for example, tetrabromobisphenol A ^ monomer. (1) 1 / 25 wt%, one or several of the methods for the total content of the cloth-based resin (I) from the stupid vinyl monomer, the dimeric or triad, and is used to achieve Selection of agent and selection of ί = ί and method 3 χΚ Δ initiator Play) and reached. , σ strong off the flame retardant stupid styrene resin of the present invention (η ^ 细 糸 本 本 本 本 本 本 本 本 本 本 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰) and inflammable (-y) secret: machine; Mixing machine for East and East specialties. Difficulties of the present invention The modified styrene tree of the plastic is used in an amount of 1 to 40, 2, 2, and 1) 1 〇 0 parts. When the flame retardant is used, it is preferably 2 to 2, and the ethylene resin composition μ is used in a low amount of more than 4 parts by weight: insufficient flammability. The above-mentioned bismuth makes the flammable styrene difficult to burn. Agent, in which ^flammable agent (11) &quot;

IIM Page 22 1247021 V. INSTRUCTIONS (19), Carbonate oligomer of tetrabromobisphenol A, tetrabromobisphenol A bis(2,3-dibromopropyl ether), tetrabromobisphenol A double (2) -Ethyl bromide, tetrabromobisphenol A diglycidyl ether and epoxidized bisphenol addenda, tetrabromobisphenol A, tetrabromobisphenol A diglycidyl ether and tribromophenol addenda Derivatives, decabromodiphenyl ether, octabromodiphenyl ether, ethylene bistetrabromophthalimide, hexabromocyclododecane, 1,2-bis(pentabromophenyl)ethane, 2, Brominated aromatic compounds of 3-dibromopropyl pentabromodiphenyl ether, bis(2,4,6-tribromophenoxy)ethane, etc.; chlorinated guanidine, chlorinated naphthalene, full gas ring ten Five-burning, gasification of aromatic compounds, chlorinated alicyclic compounds, and the like. Among them, epoxy oligo, tetrabromobisphenol A diglycidyl ether and tribromophenol addenda of tetrabromobisphenol A, tetrabromobisphenol A diglycidyl ether and brominated bisphenol adduct are preferred. The above compounds may be used singly or in combination of two or more for the purpose. In the flame retardant styrene resin composition of the present invention, a flame retardant auxiliary may be added as necessary to increase the flame retardancy. The flame retardant auxiliaries used are oxides such as antimony trioxide, antimony pentoxide, and antimony pentoxide, and acid salts such as sodium citrate. Among them, the three oxidation records are preferred. The flame retardant auxiliary is used in an amount of 0 to 20 parts by weight, preferably 1 to 18 parts by weight, more preferably 3, based on 100 parts by weight of the rubber-modified styrene resin (I). ~1 5 parts by weight. Specific examples of the phosphorus-based flame retardant include tris(p-phenylene phosphate), tris(xylylene phosphate), phosphoric acid (p-phenyldiphenyl ester), triphenyl phosphate, and tris(isopropylbiphenyl) phosphate. Ester), trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tris(butoxyethyl) phosphate, octyl diphenyl phosphate, o-phenylphenol phosphate Pentaerythritol phosphate, neopentyl

Page 23 1247021 V. DESCRIPTION OF THE INVENTION (20) A diol-based phosphate ester, a substituted neopentyl glycol-based phosphate ester, a nitrogen-containing phosphate ester, and an aromatic phosphate ester represented by the following formula (2). In particular, it is preferred to use an aromatic phosphate ester represented by the formula (2).

(In the above formula, Ar1, Ar2, Ar3, and Ar4 are the same or different halogen-free aromatic groups, and X is a structure selected from the following formulas (3) to (5). (3) to (5) In the formula, R1 to R8 are the same or different hydrogen atoms or alkyl groups having 5 carbon atoms, and Y is directly bonded to 0, S, S02, C(CH3)2, CH2, CHPh; Ph is a phenyl group. In the formula (2), n is an integer of 0 or more, and k and m in the formula (2) are each an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less. The aromatic phosphate ester can also be used in combination with other aromatic phosphates of different structures.

η in the above formula (2) is an integer of 0 or more, and from the viewpoint of flame retardancy,

Page 24 1247021 V. Description of the invention, the upper limit of the η. value is preferably 40 or less; preferably ι 〇 or less, preferably 5 or less Ο :: is an integer of 0 or more and 2 or less, and k + m is 0 The above two or more j are more than k, m is 0 or more, and an integer equal to or less than i is preferably k * 々 1 ) r (in 5), "R1 to R8 are the same or different hydrogen atoms or carbon atoms". . Specific examples of the alkyl group of the carbon atom are as follows: !土新 a: n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, new? Base, third amyl group, etc. Among them, hydrogenogen +, methyl group and ethyl group are preferred, and gas atom is preferred. 】. , Ar3, Ar4 are the same or different non-halogen aromatic scented earthy aramid base may be a benzene group containing a benzene skeleton, a naphthalene skeleton, an anthracene skeleton, an anthracene or a skeleton. Among them, an aromatic group having a stupid skeleton or a naphthalene skeleton is preferred. The two-fragrance group can be replaced by an organic residue containing no tooth atom (preferably two or more carbon atoms), and the number of substituents is not particularly U, but preferably one. Specific examples are: base, cumene, ^^ dimethyl cage, a total of A i yl group ^ ^ ^ A 3 5 - fluorenyl, n-based, imprinted, fluorenyl, etc. . Among them, phenyl, tolyl, diyl, Cai! ::, especially phenyl, tolyl, xylene = most ^ market. Phosphoric acid S is intended to be: ρχ_2〇〇, ΡΧ-201, PX-l3〇, CR_733S, TPP, CR_741, cm7, Tcp, TXP, manufactured by Daeba Chemical Co., Ltd., one or more of them are used; and from PX_2 It is preferable to use one or two or more of ()(), TPP 'CR-733S, CR_741, and CR747; in particular, PX-200, CR-733S, and CR_741 are preferred. 1247021 V. INSTRUCTION OF THE INVENTION (22) In the flame-retardant styrene resin composition of the present invention, a polymerizable flame retardant auxiliary may be added as necessary to increase the flame retardancy. The polymerized flame retardant auxiliaries used are: polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene/hexafluoropropylene copolymer, tetramer ethylene/perfluoroalkylene vinyl ether copolymer, tetrafluoroethylene/ethylene Copolymer, hexafluoropropylene/propylene copolymer, poly-1,1-difluoroethylene, 1,1-difluoroethylene/ethylene copolymer, etc., among which polytetrafluoroethylene, tetrafluoroethylene/perfluoroalkylethylene Ether copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, poly(1,4-difluoroethylene); especially polytetrafluoroethylene, tetrafluoroethylene/ethylene copolymer is the best . The flame retardant auxiliary is used in an amount of 0 to 20 parts by weight, preferably 0. 0 2 to 10 parts by weight, based on 100 parts by weight of the rubber-modified styrene resin (I). Preferably, it is 0.1 to 5 parts by weight. In the flame retardant styrene resin composition of the present invention, various additives such as an antioxidant, a lubricant, an ultraviolet absorber, a UV stabilizer, a charge preventing agent, a coloring agent, etc. may be added as necessary, and the addition time may be benzene. The polymerization stage or the kneading stage of the ethylene-based copolymer (A) or the rubber-modified styrene-based resin (I) or the flame-retardant 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 flame retardant styrene resin composition. Other additives such as an impact modifier may be added as needed, and the amount of the additive based on 100 parts by weight of the flame retardant vinyl resin composition, the impact modifier or the like is usually 30 parts by weight or less. In the flame retardant styrene resin composition of the present invention, a resin other than the styrene copolymer (A) may be blended as necessary. That is, the flame retardant styrene resin composition may contain a continuous phase other than the styrene copolymer (A).

Page 26 1247021 V. INSTRUCTIONS (23) Various polymers. The polymer may be acrylonitrile-butadiene-styrene resin, acrylonitrile-benzene benzene resin, propylene fry-d-butyl-Q-methyl ethene resin, acrylonitrile-styrene-methyl methacrylate Ester resin, acrylonitrile-stupid ethylene-indole-based malimide resin, styrene-anhydrous maleic acid resin, stupid ethylene-fluorene-phenylmaleimide resin, polymethyl methacrylate, Polycarbonate resin, styrene-methacrylic resin, methacrylic acid-butadiene-phenylene resin, acrylonitrile-butadiene-indene phenyl maleimide-styrene resin, polyamine Resin, polyester resin, polyphenylene ether resin, acrylonitrile-acrylic acid rubber-styrene resin, acrylonitrile-(ethylene-propylene diene rubber)-styrene resin, acrylonitrile-ruthenium-styrene resin and Other resins which may be used singly or in combination. The polymer is usually used in an amount of 500 parts by weight or less based on 100 parts by weight of the rubber-modified styrene-based resin (I). [Embodiment and Comparative Example] The foregoing and other technical contents, features, and advantages of the present invention will be apparent from the description of the embodiments and the accompanying drawings. [Synthesis Example of Styrene-based Copolymer (A)] Synthesis Example a Synthesis of Stupid Vinyl Copolymer (A-1) In three series-type friend, the first and second reactors are completely mixed. a reactor (hereinafter referred to as CSTR), the third reactor is a columnar flow reactor (hereinafter referred to as PFR), styrene monomer (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 'di-p-decyl bis-maleimide monomer (hereinafter referred to as BM 丨) 0. 〇 2 5 parts by weight, polymerization initiator peroxide 2 Benzoquinone (hereinafter referred to as BPO) 〇. 〇 2 heavy

1247021

A mixture of 12 parts by weight of a chain transfer agent, t-alkyl mercaptan (hereinafter referred to as TDM), and 2 parts by weight of a solvent ethylbenzene (hereinafter referred to as EB), which are continuously supplied at a flow rate of 36 kg/hour. The polymerization reaction is carried out in the first reactor, and the polymer solution obtained in the first reactor is introduced into the second reactor, and a mixed solution of 100 parts by weight and a BMI of 0.22 parts by weight is continuously supplied at a flow rate of 2 kg/hour. The second reactor is subjected to a polymerization reaction; the polymer solution obtained in the second reactor is further introduced into the third reactor, and a mixed solution of SM 1 〇〇 parts by weight and BMI 0·04 parts by weight is used at 2 kg/hour. The flow rate is continuously supplied to the third reactor for polymerization; wherein, the second fifth, the invention description (24), the first and second reaction states have a volume of 40, 40, and 7 5 liters, respectively. The temperatures were 95, 1 〇 5, and 135 ° C, respectively, and the stirring rates were 12 〇, 〇曰, and 35 rpm, respectively; and finally, the monomer conversion at the outlet of the reactor was 72% by weight. After the end of the polymerization, the ruthenium copolymer bath obtained by the third reactor reaction is usually introduced into the devolatilization tank, and then the devolatilizer is introduced and introduced into the devolatilization aid (water) to remove the unreacted single unit. And devolatilized polymeric melt, which is extruded into granules to obtain a styrene-based copolymer (A-1); a formulation of the styrene-based copolymer (A-1) And its physical property analysis is listed in Table 1. Synthesis example b

Synthesis of the ethyl ruthenium copolymer (A-2) In the three series reactors, the first and second reactors are respectively 08 11?, and the third reactor is ?卩1?, 8 from 65.5 parts by weight, 8^|34 5 parts by weight, BMI 0.022 parts by weight, polymerization initiator 1,1-bis-tert-butylperoxy-3,3,5-trimethyl Cyclohexene (hereinafter referred to as ΤΧ-29Α) 〇· 〇 1 part by weight

Page 28 1247021 V. Inventive Note (25), TDM 0.2 parts by weight, and EB 25 parts by weight mixed solution, continuously supplied to the first reactor at a flow rate of 37 kg / hour for polymerization; the first reaction The polymer solution obtained by the device is introduced into the second reactor, and the SM 1 0 0 reset portion, the mixed solution of 0 Μ I 0 · 15 parts by weight, is continuously supplied to the second reaction at a flow rate of 3 g / hour. The polymerization reaction is carried out; the second, the polymer solution obtained in the reactor is introduced into the third reactor for polymerization; wherein the volumes of the first, second, and third reactors are 4 〇, 4 〇, and 75 liters, respectively. The temperature of the reaction tank was 95, 1 〇 5, and 1 35 volts, respectively, and the stirring rates were 120, 90, and 35 rpm, respectively; and the monomer conversion rate at the outlet of the reactor was %. After the end of the polymerization, in the same manner as in Synthesis Example a, the copolymer solution obtained by the third reactor reaction is subjected to a step of devolatilization, extrusion, granulation, etc., to obtain a stupid ethylene-based copolymer '(A - 2 ), which is The production formulation of the ethylene-based copolymer (a - 2 ) and its physical property analysis are shown in Table 1. The synthesis of the Kirch-based copolymer 丄人二3)' In the four series reactors, the first and second reactors are CSTR, the third and fourth reactors are PFR, and the SM 64·5 parts by weight An 35.5 parts by weight, BMI 〇·(10) 7 parts by weight, polymerization initiator 2,2-bis(4,di-t-butylperoxy)cyclohexylpropane (hereinafter referred to as PX-1 2)0· 〇〇5 a mixed solution of weight _ parts by weight, TD Μ 0 · 2 parts by weight, and EB 2 parts by weight, continuously supplied to the first reactor at a flow rate of 36 kg / hour for polymerization; the first reactor is obtained The polymer solution is introduced into the second reactor, and the SM 1 〇〇 parts by weight, BMI 0·06 6 parts by weight, TX-29A 0·054 parts by weight

Page 29 1247021 V. Inventive Note (26) The mixing bath 'polymerization is carried out continuously at a flow rate of 2 kg / hour; the second reactor is further obtained to the second reaction third reactor, and 100 parts by weight of SM and ~29A = 3 were dissolved, and the mixture was introduced into a mixed solution, and the polymerization was carried out at a flow rate of 2 kg/hour, continuously 妯·013 篁, and then the reaction of the third reactor was taken. The four-reactor reactor carries out a polymerization reaction; wherein, the volume of the first and second materials, the liquid-conducting reactor is 40, 40, 75, and 75 liters, respectively, and the second and fourth are respectively 95, 105, and 130, 135 t, stirring speed' rate of reaction tank temperature 38, 35 rpm; finally monomer conversion MU, 90 at the outlet of the reactor, after the end of the polymerization, the copolymer obtained by the fourth reactor The solution was subjected to a step of devolatilization, extrusion, granulation, and the like to obtain an ethylene-based copolymer (A-3); the production of the styrene-based copolymer (A-3) and its physical property analysis are shown in Table 1. 〇Synthesis Example d Synthesis of Stupid Vinyl Copolymer (A-4) In three series reactors, the first and second reactors are CSTR, the third reactor is PFR, and the SM 6·5 parts by weight , AN 355 parts, BMI 0. 0 28 parts by weight, PX-12 〇 · 〇〇 6 parts by weight, TDM 〇 · 2 weight: a mixture of parts 'and EB 25 parts by weight, at a flow rate of 36 kg / hour, Continuously feeding to the first reactor for polymerization; introducing the first reaction polymer solution into the second reactor, and mixing the SM 1 〇〇 parts by weight, - 2 9 A 0 · 0 3 3 parts by weight The solution was continuously supplied to the reactor at a flow rate of 2 kg / hour. κ combining reaction; introducing the polymer solution obtained in the second reactor into the third reactor, and adding the solution of SM 1 by weight

1247021 V. Inventive Note (27), continuously supplied to the third reactor at a flow rate of 2 kg/hour for polymerization; wherein the volumes of the first, second and third reactors are respectively 4 〇, 4 〇, 7 5 liters, the temperature of the reaction tank was 9 5, 1 0 5, and 1 35 ° C, respectively, the mixing rate was 120, 90, 35 rpm; finally, the monomer conversion rate at the outlet of the reactor was 71% by weight. After the end of the polymerization, the synthesis solution a is subjected to a step of devolatilization, extrusion, granulation, etc. of the copolymer solution obtained by the third reactor reaction, thereby obtaining a styrene ruthenium copolymer (A - 4 ). The formulation of the copolymer (A-4) and its physical property analysis are shown in Table 1. Synthesis Example e Synthesis of the ruthenium-based copolymer (A-5) in three series reactors, the first and second reactors are CSTR, the third anti-reactor is PFR, and the SM 64·5 parts by weight a mixed solution of AN 35.5 parts by weight, BMI 0.022 parts by weight, BPO 〇. 〇 2 parts by weight, TDM 0.2 parts by weight, and EB .25 parts by weight, continuously supplied to the first reactor at a flow rate of 36 kg/hour. Polymerization reaction; the t-reagent/gluten solution obtained in the first reactor is taken into the reactor-- and g Μ 1 〇〇 by weight, b Μ I 0·2 parts by weight, ΤΧ-29 Α 0·08 parts by weight The mixed solution is continuously supplied to the second reactor at a flow rate of 2 kg/hour to carry out a polymerization reaction; the polymer solution obtained in the second reactor is further introduced into the third reactor, and the SM 1 is added in parts by weight. The solution is continuously supplied to the third reactor at a flow rate of 2 kg/hour for polymerization; wherein the volumes of the first, second, and third reactors are respectively 40, 40, and 7 5 liters, and the reaction tank The temperatures are 9.5, 1 0 5 and 135 °C respectively. The search rates are 120, 90, 35 rpm, respectively. Reactor

1247021 V. INSTRUCTIONS (28) The monomer conversion rate of the outlet is 72% by weight. After the end of the polymerization, the copolymer solution obtained by the third reactor is subjected to steps of devolatilization, extrusion, granulation, etc., to obtain a styrene copolymer (A-5); the styrene copolymer ( The manufacturing formula of A-5) and its physical property analysis are listed in Table 1. Synthesis · Example f The synthesis of the stupid vinyl copolymer (A-6) is the same as that of the synthesis example b, except that the amount of the monomer used in the feed mixture solution of the first reactor is adjusted, respectively It is 60 parts by weight of SM, 34 parts by weight of AN, and 6 parts by weight of methyl methacrylate (hereinafter abbreviated as MMA), and the monomer conversion rate at the outlet of the final reactor is 74% by weight; the styrene copolymer (A-6) The manufacturing formulation and its physical property analysis are listed in the table - 〇 Synthesis Example g The synthesis of the styrenic copolymer (A-7) is the same as that of the synthesis example b, except that the first reactor feed mixture solution is used. The amount of the monomer used in the adjustment was adjusted to be 61 parts by weight of SM, 39 parts by weight of AN, and the monomer conversion rate at the outlet of the reactor was 72% by weight: the formulation of the styrene copolymer (A-7) And its physical property analysis is listed in Table 1. Synthesis Example h Synthesis of Stupid Vinyl Copolymer (A-8)

Same as the operation mode of the synthesis example b, except that the amount of the monomer used in the feed mixture solution of the first reactor is adjusted as SM

Page 32 1247021 V. Description of the invention (29) 7 3 weight injury, AN 2 7 parts by weight, and the amount of BM I used in the feed mixture solution of the first and second reactors is adjusted, first, first The amount of the two reactors is adjusted to 66 parts by weight of 〇·〇, 45 parts by weight of 〇·, and the monomer conversion rate at the outlet of the reactor is 73% by weight. • The formulation of the styrene copolymer (A-8) and Its physical property analysis is listed in Table 1. Comparison of synthetic Ϊ i i ^ 乙 系 common.. 茎 - 9) synthesis In two 3 series reactor, the first and second reactor are CSTR,

A mixed solution of SM 68 parts by weight, an 32 parts by weight, BPO 0.02 parts by weight, TDM 重置·2 reset portion 'and ΕΒ 25 parts by weight, was supplied to the first one at 4 〇 kg/hour. The reactor is subjected to a polymerization reaction; the first reaction agent=serving polymer solution is introduced into the second reactor for polymerization; wherein the volumes of the first and second reactors are respectively 4 〇, 4 〇 liter, and the reaction tank is The temperature fraction f is 100, 12 (TC, the stirring rate is 12 〇, 9 〇 r (10) respectively. The final reaction is the monomer conversion of the outlet is 52% by weight. After the χ κ end, the same synthesis example a will be from the second reactor. The copolymer solution obtained by the reaction is subjected to steps of devolatilization, extrusion, granulation, etc., to obtain benzene S = I 2 di(A to 9); the formulation of the styrene copolymer (A-9) and its physical properties The analysis is listed in Table 1.

Comparing the operation mode of the synthesizer of the synthesis example I cap-heart system-) ===, the difference is that the first reaction-reaction outlet 2;:;5 in 3 Ca == Fuhuafeng 53% by weight, the styrene Copolymer (A-1〇)

1247021 V. INSTRUCTIONS (30) The manufacturing formula and its physical property analysis are listed in the table to compare the operation mode of the synthetic quinone k styrene copolymer (A - 1 1 and 4 with the comparative synthesis example i, the difference is that the first In the reaction mixture bath, 0.035 parts by weight of divinylbenzene monomer (hereinafter abbreviated) was added, and the amount of TDM was adjusted to 重量·3 parts by weight, and finally the monomer conversion rate at the outlet of the reactor was 54% by weight; The formulation of the styrene-based copolymer (An) and its physical property analysis are shown in Table 1. Comparative Synthesis Example 1 The reaction of the ethyl ruthenium copolymer (A - 12) 4 in the two series, the SM 65.5 parts by weight, AN 34.5 weight TDM 0·2 parts by weight, and EB 25 weight flow rate, continuously supplied to the first reactor, the polymer solution, the weight fraction 'BMI 0 · 15 parts by weight mixed' continuous The second reactor is fed to the second reactor, and the volume of the reactor is 4%, 14,000, and 150. (:, the stirring rate is 5, the monomer conversion rate at the outlet of the reactor is after the end of the polymerization. 'It is usually to introduce the polymer solution into the devolatilization tank and volatize it; The preparation formula of the stupid ethylene copolymer (A-12) and the first and second reactors thereof are all CSTR, the parts, the BMI 0. 02 2 parts by weight, and the mixed solution of the parts, and the reaction solution of 3 7 kg / small reaction state The polymerization reaction is carried out; the second reactor is introduced into the second reactor, and the S Μ 1 0 0 solution is mixed, and the polymerization is carried out at a flow rate of 3 kg/hour; wherein, the first, 40 liters, and the temperature of the reaction tank are respectively 1 2 0, 9 0, 3 5 rpm; final amount 〇 / 〇. The unreacted monomer and its copolymer (A-12) were removed from the second reactor reaction; the stupid vinyl structural analysis is listed in Table I.

Page 34 1247021 V. INSTRUCTIONS (31) Synthesis of J is different from Synthetic Example m Difference copolymer (A - 13) The operation mode of Comparative Synthesis Example 1 is different from the first and second reactors. In the feed mixed solution, no BM I was added, and the reaction temperatures of the first and second reactors were respectively adjusted to 130, 140 ° C, and the monomer conversion rate at the outlet of the reactor was 49% by weight. The formulation of the copolymer (A-13) and its physical property analysis are shown in Table 1. , the synthesis of the η-based copolymer (A-14) is compared with the operation mode of the comparative synthesis example i. The same is that the first mash should be added to the mixed solution of the feed, adding MI 丨. 5 parts by weight; During the reaction, the reaction system = viscosity increases sharply, and the hue of the reaction product deteriorates, and the foreign matter and the stain of the molecular weight of the S, the molecular weight of the bridge are generated, and the flow coefficient of the reaction product is taken out; For 32. 5 . [Synthesis example of rubber graft copolymer (Β' -1 );] (4) In four reactors of series type, the first to fourth reactors are all CSTR, and 68 parts by weight of SM, 32 parts by weight of AN, and one秘换^ 十j olefin rubber (hereinafter referred to as BD) 7. 〇 weight I, BPO 0. 03 parts by weight, TDM 〇. 3 parts by weight, and eb 35 parts by weight of the mixed solution, at 40 kg / hour, ώ b , the flow rate of r — j ^ is continuously supplied to the reactor for polymerization; wherein the volumes of the first, second, third, and #: reactors are each 40 liters, and the temperature of the reaction tank is respectively For 1〇〇, brother ' 115 ' 130 ° , the stirring rate is 30 0, 200, 150, 90 rpm; the final monomer conversion rate of the reactor outlet is 65 wt%

Page 35! 247〇21 ^__ I, - V, invention description (32) After the end of the polymerization, the same as the synthesis example a, the reaction of the feather copolymer obtained by the fourth reactor reaction is carried out, such as devolatilization, extrusion, granulation, etc. The gum graft copolymer (B, 丨) can be obtained, and the rubber component content is 1% by weight. Synthesis example of rubber graft copolymer (B, -2)] L Table 2] Component parts by weight 1,3· Butadiene 150.00 Potassium persulfate solution (1%) 15.00 Potassium oleate 2.00 Distilled water 190.00 Ethylene glycol The mercapto acrylate 0.13 was reacted at the reaction temperature of 65 ° C for 14 hours according to the above formula 2, and the conversion was 94%, the solid content was about 36%, and the weight average particle diameter was about 〇10 to “m. Rubber emulsion. · 1 [Table 3] Ingredient parts by weight of butyl acetonate 90.00 methacrylic acid 10.00 potassium persulfate solution (1%) 0.50 sodium lauryl sulfate solution (10%) 0.50 η-dodecyl sulfur Alcohol 1.0 Distilled water 200.00 'According to the above formula 3, the reaction was carried out at a reaction temperature of 75 ° C for 5 hours to obtain a polymer agglomerating agent containing a ferulic acid group having a conversion rate of about 9 5 % and a p Η value of 0.6 · 0;

Page 36 1247021 V. Description of Invention (33): After that, 3 parts by weight (dry weight) of a carboxylic acid group-containing polymer aggregating agent is used to ferment 100 parts by weight of a synthetic rubber latex, and the obtained rubber is obtained. The pH of the emulsion is 8.5, and the average weight of the rubber is about 0.31 // m. Finally, the above-mentioned enlarged rubber emulsion is graft-polymerized with a styrene-acrylonitrile copolymer according to the formulation of the following Table 4 to produce a rubber graft copolymer (B' - 2 ). [Table 4] Ingredient weight part of hypertrophic rubber emulsion (dry weight) 100.0 ~ styrene monomer 75.0 C) Shi Teng Shan Zhao 25.0 Thirteen-dodecyl mercaptan 2.0 Argon-dissolved cumene 3.0 ' Ferrous sulfate Solution (0.2%) 3.0 ~~ Formaldehyde sodium sulfoxylate solution (10%) 0_9 Ethylenediaminetetraacetic acid solution (〇·25%) 3.0 —~ Rubber graft copolymer emulsion prepared according to the formula IV After the chlorination word is coagulated, and then dehydrated and dried to less than 2%, the rubber grafted 浐L (B '-2) (the rubber content of 5 〇% by weight and the rubber weight average particle size 〇3 j) can be obtained. Preparation Example of Styrene Resin Modified by Rubber] 〆m Simultaneous Grafting Preparation Example a' Preparation of Rubber Modified Resin (I -1 ) in Four Tandem Reactors, First and Second Reaction crying

Page 37 1247021 V. Description of invention (34)

CSTR, the third and fourth reactors are PFR, and will be SM 65·5 parts by weight, AN

34.5 parts by weight, BD 8.0 parts by weight, BMI 0.022 parts by weight, TX-29A 0. 04 parts by weight, TDM 0.3 parts by weight, and EB 35 parts by weight of the mixed solution, continuously at a flow rate of 37 kg / hour The ground is supplied to the first reactor for polymerization; the polymer solution obtained in the first reactor is introduced into the second reactor, and a mixed solution of SM 1 00 parts by weight and BMI 0.15 parts by weight is used at 3 kg/hour. The flow rate is continuously supplied to the second reactor for polymerization; the polymer solution obtained in the second reactor is introduced into the third reactor for polymerization; and the polymer solution obtained in the third reactor is further introduced into the fourth reaction. The polymerization reaction is carried out; wherein the volumes of the first, second, third, and fourth reactors are 40, 40, 75, and 75 liters, respectively, and the temperature of the reaction tank is divided;; is i〇0, 105, 115, 13 (TC, sandalwood rate is coffee, 2 〇〇 _, 1 50, 90 rpm; finally, the monomer shovel at the outlet of the device *. The conversion rate of dry plate is 75% by weight 〇 after the end of the polymerization, the same synthesis example a will be desulfurized, extruded, granulated, etc. from the copolymer solution of M mc — as a reaction Known in the first step, a rubber-modified styrene resin (I -1 ) is obtained, and the rubber is made up of eight people/knife and the content is heavy; the rubber is modified with a styrene resin (I~n A ^ ” 4 In the tetrahydro D-propan solution, the continuous phase of the stupid ethylene copolymer (A) was obtained, and the order of 丨-# ^ X ^ &amp; / was determined to be 24.2; the rubber modified styrene The manufacturing formula of the resin (: [~ηΑΑ &amp; value is ± τ 丄) and its physical property analysis results are shown in Table 5. After preparation b, 33⁄4 modified 乙烯 乙烯 vinyl resin (I - 2 ) in four applications The combined reactors are QQ~, and the second reaction is CSTR, the third and fourth reactors are PFR, and the SM 68 parts by weight ", :n, 32

1247021 -- ---^___ - V. INSTRUCTIONS (35) 'Parts by weight, BD 8.0 parts by weight, BMI 〇·〇〇〇2 parts by weight, TX-29A 0·04 reset parts, TDM 0·3 weight And a mixed solution of 35 parts by weight, continuously supplied to the first reactor at a flow rate of 40 kg/hour, wherein the volumes of the first, second, third, and fourth reactors are respectively 4 0, 4 0. , 7 5, 7 5 liters, the temperature of the reaction tank are 丨〇◦, 丨〇, 115, 13" C, respectively, the stirring rate is 3 〇〇, 2 〇〇, 15 〇, 9 〇 rpm; The monomer conversion rate % for the outlet. After the end of the polymerization, in the same manner as in Synthesis Example a, the copolymerization solution obtained by the fourth reactor reaction is subjected to steps of devolatilization, extrusion, granulation, etc., thereby obtaining a rubber-modified styrene resin (j-2). The rubber component content is 1 〇·3 wt〇/〇, and the rubber-modified styrene resin (I-2) is dissolved in a tetrahydrofuran solution to obtain a continuous phase of the styrene-based copolymer (A), and the M is measured. The value of 丨R is 21·1; the formulation of the rubber-modified stupid vinyl resin (I-2) and its physical property analysis are shown in Table 5. Grafting and kneading method; Preparation c' i-modified styrene-based rouge (TD 唧 唧 橡胶 rubber graft copolymer (B, _ 丨) 2 〇 parts by weight, rubber graft copolymer (B' -2 36 parts by weight, 44 parts by weight of the styrene-based copolymer (am), and 3 parts by weight of ethylene bisstamine (hereinafter referred to as EBS) 干·3 parts by weight, after dry mixing with a Hanschel mixer, The rubber modified benzene with particle size (pe l 1 et) can be obtained by melt-kneading the two-axis extruder with the temperature of the raw material tank at 20 0~22 0 °C and the die temperature of 220 °C. a vinyl resin (I-3) having a rubber component content of 20% by weight; the resin (I-3)

Page 39 1247021 V. INSTRUCTIONS (36) The results of the manufacturing formulations and their physical properties are listed in Table 6. Preparation Example d' Preparation of rubber-modified stupid vinyl resin (I-4). Rubber graft copolymer (B'-2) 36 parts by weight, rubber modified styrene resin (I-1) 20 parts by weight, 44 parts by weight of the styrene-based copolymer (A-1), and 0.3 parts by weight of EBS, and the extrusion conditions of the preparation example c' can be used to obtain a pel let-like rubber modification. The styrene resin (I-4) had a rubber component content of 20% by weight; the production formula of the resin (I-4) and the physical property analysis results thereof are shown in Table 6. Preparation Example e' Preparation of a rubber-modified stupid vinyl resin (I - 5 ) 40 parts by weight of a rubber graft copolymer (B' -2), 60 parts by weight of a styrene-based copolymer (A-1), and EBS 0. 3 parts by weight, with the extrusion conditions of the preparation example c', a rubber modified styrene resin (I-5) having a particle shape (pe 1 1 ) can be obtained, and the rubber component content is 20% by weight; The production formula of the resin (1-5) and the physical property analysis results are shown in Table 6. Preparation Example Γ~Γ The rubber-modified stupid vinyl resin (I-6)~(I - 1 2 ) was prepared in the same manner as in Preparation e' except that the styrene copolymer (A) was used. The type and amount of the styrene resin (I-6)~(I - 1 2 ) were determined by the modification and the physical property analysis results are shown in Table 6. Preparation of a preparation of a m-rubber modified stupid vinyl resin (I - 13 )

1247021 V. Description of the invention (37) The operation mode of the same as the preparation example c', except that the type of the styrene copolymer (A) is changed; the rubber modified styrene resin (I - 13) The manufacturing formulations and their physical property analysis results are listed in Table 6. The preparation method of the preparation example η' rubber-modified stupid vinyl resin (I - 14 ) was prepared in the same manner as in the preparation example d' except that the styrene resin modified by the simultaneous grafting method was used (I). And the type of the styrene-based copolymer (A) was changed; the production formula of the rubber-modified styrene-based resin (I - 14 ) and the physical property analysis results thereof are shown in Table 6. Comparing the preparation 〇'~s' rubber modified stupid vinyl resin (I - 15) ~ (I - 19) was prepared in the same manner as in the preparation example e' except that the styrene copolymer was used. The type of (A) was changed; the production formula of the rubber-modified styrene resin (I -1 5 ) to (I - 19 ) and the physical property analysis results thereof are shown in Table 6. [Examples and Comparative Examples of Flame Retardant Styrene Resin Composition] Example 1 A styrene resin (I - 3 ) modified with rubber, 100 parts by weight, a flame retardant (Π-1) [four Tetrabromo bisphenol A, manufactured by Grate Lakes, trade name BA - 5 9 P ] 18 parts by weight, flame retardant auxiliary antimony trioxide (hereinafter referred to as Sb203) 8 parts by weight, and EBS 0. 3 The parts by weight are dry-mixed by the Hanschel mixer, and then melted and kneaded by a two-axis extruder with a temperature of 180 to 200 watts at a die temperature of 200 ° C. A flammable styrene resin composition in the form of particles (pe 1 1 et s); the formulation of the resin composition and its physical property analysis are shown in Table 7.

1247021 V. INSTRUCTIONS (38) 宜2 Example 2 styrene-based resin modified with rubber (I - 4) 1 〇〇 by weight, flame retardant (Π - 2 ) (tetrabromobisphenol A diglycidyl 18 parts by weight of ether and tribromophenol addenda, 'DIC name EC-20 by DIC', sb203 8 parts by weight, and ebs 〇·3 parts by weight, with the extrusion conditions of Example 1, can be obtained with granules (pe 1 A flame retardant styrenic resin composition in the form of a film; the formulation of the resin composition and its physical property analysis are shown in Table 7. Examples 3 to 4 are the same as the operation mode of the second embodiment except that the type of the rubber-modified styrene resin (I) is adjusted; the flame retardant styrene system = the composition of the composition and the composition thereof The physical property analysis is listed in Table 7. /' 'Known fjfe Example 5 A styrene-based resin (j-7) which has been modified with rubber, 丨〇〇 by weight, and a yam ester (made by Taiwan Chimei Co., Ltd., trade name? (&gt;11〇) 3〇〇 weight Parts, also smoldering agent (Π - 3) [bisphenol A bis (diphenyl phosphate), big eight male knife and difficult name CR-741] 20 parts by weight, after dry blending with Hanschel mixer, ' The product tank temperature is 23 0~250 t: The die temperature is 2 50 °C with the exhaust port, and the raw material is melted and kneaded. The peUet-like D-bonded double-brake resin can be obtained. The preparation formula of the resin composition and the glycerol-like ethylene are shown in Table 7. The physical property analysis shows the operation mode of the same as the embodiment 5 except that the type of the vinyl resin (I) is one. Adjustment; the flame retardancy> The manufacturing formula of the modified stupid composition and its physical property analysis are listed in Table 7.

Page 42 1247021 V. INSTRUCTION DESCRIPTION (39) Examples 7 to 1 1 The operation mode of the same as in Example 1, except that the type of the styrene resin (I) modified with rubber and the flame retardant (Π) And the amount of the flame retardant auxiliary is adjusted; the manufacturing formula of the flame retardant styrene resin composition and the physical property analysis thereof are shown in Table 7. Comparative Example 1. The operation mode of the first embodiment is different from the modification of the rubber-modified styrene resin (I); the formulation of the flame-retardant styrene resin composition and its physical properties. The analysis is listed in Table VII. Compared with the vehicle, {column 2 to 3, the operation mode of the same embodiment 2, except that the type of the rubber-modified styrene resin (I) is adjusted; the flame retardant styrene resin composition Manufacturing formulations and their physical property analysis are listed in Table 7. 4:5 is the same as the operation mode of the embodiment 5 except that the type of the rubber modified styrene resin (I) is adjusted; the flame retardant styrene resin composition The manufacturing formulations and their physical property analysis are listed in Table 7. The operation mode of the first embodiment is the same as that of the first embodiment, except that the type of the rubber-modified styrene resin (I) is adjusted; the manufacture of the flame-retardant styrene resin composition The formulation and its physical property analysis are listed in Table 7. Comparative Example 10 to 1 1 The same operation mode as in Example 3 except that the amount of the flame retardant (Π) and the flame retardant auxiliary was adjusted; the flame retardant styrene resin composition

1247021 . V. The manufacturing formula and physical property analysis of the invention description (40) are listed in Table 7. [Evaluation method]

1. MIR The above styrene copolymer (A) has a MFR of MI (g/10 min) measured at a temperature of 2000 ° C and a load of ikg, a temperature of 2 ° C, and a load of 1 〇 1 ^ The measured MFR is HMI (g/1 0 points), then MIR = HMI/MI ratio. Wherein MFR refers to the melt flow index: the index is determined by the ASTM D-1 238 method. 2. Rubber content The Fourier Transform Infrared Spectrometer was tested by N i c ο 1 e t, model N e X u s 4 7 0. unit weight% . 3. The total content of the dimer or triad derived from the styrene monomer and the nitrile ethylene monomer. The rubber modified polyester (I) is dissolved in acetone and has a flame ion. Gas detector (GC) for the detector (FID)

Manufactured by Hewlett Packard; Model 5890A) for analysis and measurement. The unit is % by weight. 4. Time impact The test piece was measured by the A S T M D - 2 5 6 method, and the test piece was 1/4 inch in size with a defect. Unit·· kg - cm/ cm. 5 · Drip-burning phenomenon U L - 9 4 V 0 was used as the test method. The test piece with a thickness of 1 / 16 6 inches was used for evaluation, and 10 times of burning test was repeated to observe the number of times of drenching.

Page 44 1247021 V. INSTRUCTIONS (41) 〇: All are not drenched. △ : 1 to 2 times of drenching. X : 3 or more (including 3 times) drenching. 6. Stress crack resistance The test piece of 100mm X 1 2 · 7 hidden x 3—is placed on a fixture with a radius of curvature of 165 mm and then immersed in a 30% alcohol solution to measure the test piece. The time after the crack occurred. The longer the time, the better the cracking resistance. 〇: 48 hours or more △ ·· 24~48 hours X : 2 within 4 hours 7. Staining 10 g of the above-mentioned flame retardant styrene resin composition was pressed into a diameter of 200 mm and a thickness of 0 by a hot press. After a 3 mm round sheet, observe the number of stains. 〇: 0 to 1 point △ ·· 2 to 4 points X: 5 points or more (including 5 points) [Notes on the attached table] Table 1: Synthesis examples of styrene-based copolymer (A) Table 5: Simultaneous grafting method Preparation example of rubber modified styrene-based grease (I) Table 6: Preparation of rubber modified styrene resin (I) by grafting and kneading method Table 7: Modulation of flame retardant styrene resin composition

1247021 Simple description of the schema

Page 46 1247021 R1, R2: CSTR R3, R4: plug flow SM ., AN MMA-3⁄43⁄43⁄43⁄4骒鹞BMI N,N* -4, 4* -l·舛^飧驷诗讳讳萌驷鵾 DVBBpo TX 丨29A 1, 1—Λ—View WT&amp;^^^-3, 3, 5—wf 卩荈px—12 · 2,2-Beach (4,4-Bu-雒41-_菡衅^)锞(^荈^4^^^^4^3⁄4EB p舛 physical property analysis conditional reaction|styrene copolymer (A) 1 synthesis example and comparative synthesis example sc s 1 (R4) reactor · | fourth inverse (R3) should Third reverse (R2) reactor I second reverse I (Rl) reactor 1 feed flow rate (kg / hr) 1 stirring speed (rpm) 丨 temperature (°c) composition feed 1 feed flow (kg /hr) | Stirring speed (rpm) 1 o° Composition feed | Feed flow rate (kg/hr) | | Feed speed (rpm) 1 nc Composition feed flow rate (kg/hr) | Stirring speed (rpm 1 〇r initiator 1 polymerization from g starter life g cn CO chain transfer initiator 1 polymerization Ο CO S &gt; (parts by weight) 1 type 1 (parts by weight) 1 (parts by weight) 1 (parts by weight) 1 Type | 1 (parts by weight) I 1 (parts by weight) I rn llfflU W Ι φ . Mai 1 (parts by weight) 1 Type 1 (parts by weight) 1 type 1 (parts by weight) 1 (parts by weight) | (parts by weight) | (parts by weight) | (parts by weight) I oo o \ 0.04 (~1 〇DO CO en (-1 CO cn | 0.22 〇CD IND g CD cn IND an CD [&gt;0 1 TDM | ο ◦ ro 1 ΒΡ0 1 | 0.025 \ CO CJ1 cn 64.5 1 CO σ&gt; IND CD CO on &gt; 1 03 DO GO J_L CO Ol OO CJ1 \ 〇 5—\ CO CO ◦ ►~*· CD cn OO cn CD ro σ ◦ ο 1 ΤΧ-29Α 1 0. 022 1 34.5 1 65. 5 1 CO --a tND 〇CO cn DO cr DO r° an OO Cn OO cn 0.013 | TX-29A ί—^ g IND OJ OO OO ◦ 0.054 | TX-29A | | 0.066 1 〇◦ i&gt;o § ΓΟ cn 〇) ro 0.005 1 ΡΧ-12 1 0.007 1 CO ΟΊ ΟΙ 64.5 1 GO CD 1 cn OO η 23.2 ◦ ◦ ro GO cn CO an 0.033 | TX-29A 〇cr&gt; CsD g »&gt;· o cn t\D CJl 〇IND 1 0.006 1 1 ΡΧ-12 1 0.028 \ 35. 5 1 64.5 1 GO CD OO 〇&gt; CO cn &gt;- a- 23.0 ◦ c CsD OO cn H-1 OO cn 0. 08 | TX-29A | !Νΰ q rsD g CD cn ΓΟ 0*1 CD CO o \ 0.02 \ 3 \ 0.022 \ CO cn ΟΊ 64.5 1 CO CD IND o CO cn &gt; 1 cn CD ΓΟ CO cn OO ΟΊ CO 〇1 | 0.15 \ CD Q CO CJ3 oi OO cn o I&gt;0 | TDM 1 I ο. οι 1 1 ΤΧ-29Α 1 | 0. 022 1 S OJ OO o 1 cn &gt; CD |^ ro r ° CO cn CO cn 1 0^5 1 t-» 〇CO CO CD t-1 CD Cn DO cn o ro 1 ο.οι 1 1 ΤΧ-29Α 1 1 0.022\ CO CO σ〇OO CD CJl Ten CfQ DO CD Cn CO cn CO cn | 0.45 \ 〇CD CO S 〇cn CO ΟΊ CD IND 〇〇』ι 1 ΤΧ-29Α 1 \ 0.066 \ OO CO DO CD CJD CJl &gt; 1 OO 21.0 g OO an 〇DO s: ο CO OO OO OO OO g DO Ό § &gt; '~' rr 21.4 g S ro O'* CD IND s ◦ ο DO CO 3 1 1 OO ro CD GO 岂Q &gt; ◦ ·-· DO CO CD S ro cn C3 CO (1) s CD CD DO \ 0.035 1 OJ CND OO CO CD CD &gt; oo r° OO | 0.15 1 o CD CO g an ◦ OO CJl o DO gs; | 0.022 | OO • Private cn I 65.5 | CO ro o CD A-12 a iro Ο 〇o OO g 1~1 OO CJl o ro g CD | 34.5 1 I 65.5 I CO -J ro ,o OO o A-13 彐[!&gt;-]6 6 1&1; Effect bud (/\)-^岭^皇1247021 [表五]同Preparation Example of Preparation of Styrene Resin (I) Modified by Grafting Method and Comparative Preparation Example Comparison Example Preparation Example ab, Rubber Modified Styrene Resin (I) 1-1 1-2 Reaction Conditions One reactor (R1) Temperature (°C) 100 100 Stirring speed (rpm) 300 300 Into 3 bucket flow (kg/hr) 37 40 Feed composition SM (parts by weight) 65.5 68 AN (parts by weight) 34.5 32 BD ( Parts by weight 8 8 BMI (parts by weight) 0. 022 0.0002 Polymerization initiator type TX-29A TX-29A (parts by weight) 0.04 0.04 Chain transfer agent type TDM TDM (parts by weight) 0.3 0.3 EB · (parts by weight) 35 35 Second reactor (R2) Temperature (°C) 105 105 Stirring speed (rpn) 200 200 • Inlet flow rate (kg/hr) 3 Feed composition SM (parts by weight) 100 BMI (parts by weight) 0.15 Third Reactor (R3) Temperature (°C) 115 115 Stirring speed (rpni) 150 150 Fourth reactor (R4) Temperature (°C) 130 130 Stirring speed (rpm) 90 90 Physical analysis of rubber content (weight °/« 10 10.3 MIR (styrene-based copolymer (A) continuous phase.) 24.2 21. 1 From styrene monomer and The total content (% by weight) of the dimer or triad derived from the nitrileated vinyl monomer 0.93 0.90 R1, R2: CSTR R3, R4: plug flow SM styrene monomer AN acrylonitrile monomer BD butadiene Rubber BMI · Ν, Ν' -4,4'-diphenylnonane bismaleimide monomer TX-29A 1,1-bis-tert-butylperoxy-3, 3, 5-trimethyl Cyclohexane TDM T-dodecyl mercaptan EB Ethylbenzene 1247021 Wear AW -s ABC K* Nai composition (parts by weight) I Rubber modified stupid vinyl resin (I) j Preparation and comparison preparation W ^ ^ _ K Fan * Γ : $卜+3⁄4 & *鹞鹞知^ S I11 CT rtm (^ 鵾 3 3: inflammation Llj'v \m〇Γγ ]*Βο Rubber content (% by weight) Extruder die temperature (°c) Extruder material bath temperature (°c) Styrene copolymer (A) 舛:E Π 4H-naphthoquinone rubber graft copolymer (B') | A-13 A -12 A-ll A-10 &gt;&gt; oo &gt;&gt;&gt;&gt;&gt;&gt; K) &gt; 1~1 ώ 1~( 1 Η—^ B'-2 1 »——l 0.62 ΓΟ To IND CD . 200-220 . CO &lt;ΖΓ&gt; IND HH 1 GO 〇β Preparation Example 0.65 gg oo cr &gt; HH 1 Cl 0.60 g )—( 1 ΟΊ Ο)-&lt;3&gt; cn 〇〇gg 1~1 ^-b 0.63 IND s 1&quot;&quot;1 1 CfQ. 0.68 CJ5 oo CO DO 1««1 do Zr ◦ CJl CO CO cn CD 1~t 丄一-· 0.60 DO g ►—i 1 h—^ CD U^. 0.62 gg hH 1 1—* )_k ?»r 1 j 0.59 sg hH 1 - 0.62 DO CO CD s HH 1 l—l GO 3· Comparative Preparation CD C7D g IND CO CJD HH 1 Z3_ 0.54 g CD HH 1 (_k cn 〇_ 0.56 gg 1~1 1 CX) T5^ 0.57 g S HH 1 -J 1 —^ ΟΊ CD gg hH 1 oo 1.40 sg 1—H 1 H—^ CO C/^ 4Π-2 Θ»Jiyu Al·Consultation ^4^«靼小»舛缪泽都穿,;010鸿,褂和;§〇20 CNn—3 飧缪ΑΛ(卜舛i&骒器),&gt;,v,vc3i,^SQa;gcR-741, ISS03 ^^pc丨一10 杂杂^|Tengshenghoo (polycarbonate ), 卟; minus net»|&gt;&gt;|3 scale J^nl s»^^A(tetrabromo bisphenol A), GI* Ate Laks minus, ^SQ^BA-59P | physical 1 part) composition (weight 1 m &quot;W* pollution point financial stress cracking drip phenomenon and impact (kg-cm/.cm) Flammable agent (Π) Other resin resin vinyl based benzene 1 rubber change | mrr practice 1 graft mixed i branch method | simultaneous connection | Sb203 w 丄n ώ Π-1 PC-110 11 1 Ξ )—( 1 oo hH 1 *_L HH 1 HH 1 k—* cn HH 1 h—^ 1~1 1 CO HH 1 HH 1 HH 1 t_x CZ) HH HH ώ 1«&quot;1 Λ HH 1~l A HH 丄KH Do 1~1 ώ IH 1 〇〇〇1 OO oo --1 CD CD 1--- Example 〇〇〇oo OO Ο CD 〇〇〇〇〇oo oo CD CD CO 〇〇〇oo oo h—^ CD CD 〇〇〇CO 〇〇CD t&quot;«t CD CD ΟΊ 〇〇〇 IND cn g CO CD CD ◦ CD CD 〇〇〇Η—^ cn cn »—i CD CD 〇〇〇s CD CO H-1 CD CD oo 〇〇〇► —A OO oo *—4 oo CO 〇〇〇h—^ —o CO oo CD CD --ί 〇〇〇 oo oo CZ) CD 〇 XXA CD oo .〇〇o CD ►_k Comparative Example 〇 gt ;-k IND oo oo &lt;35 IND 〇XX IND oo oo o CD CO 〇XX DO DO When CD &gt;-1 CD CD 〇XX tND g Daddy CD j_k ο C3 cn 〇X 0 s oo oo o CD CTD • X D&gt; 0 t—^ oo oo st—io CD —J 〇〇X i~L oo 5S o cz&gt; CO 〇XX h— oo oo s CD CD CD 〇 ΓΟX ΓΟ CD cn H—i CD CD 〇• X 〇ΟΊ oo A cn b—^ 〇CD h_i

Claims (1)

1247021 VI. Patent application scope 1. A flame retardant styrene resin composition comprising a rubber modified styrene resin (I) 100 parts by weight and a flame retardant (Π) 1 to 40 parts by weight; Wherein the rubber-modified styrene resin (I) is (i - 1 ) 5 0 to 90 parts by weight of a styrene monomer, (i - 2 ) 10 to 50 parts by weight of a nitrile a vinyl monomer, (i-3) 0 to 40 parts by weight of another copolymerizable vinyl monomer-, and a total of 100 weights of the above (i-1), (i-2), and (i-3) And a styrene-based copolymer (A) obtained by copolymerizing a polyfunctional maleimide-based monomer as a continuous phase and a rubber particle (B) as a dispersion, and 0.00 0 5 to 1. The rubber composition of the rubber-modified styrene resin (I) is 40% by weight, and the two or three amounts derived from the styrene monomer and the nitrile vinyl monomer The total content of the body is 1.25% by weight or less of the rubber modified (I); and the MFR measured by the styrene copolymer (A) at a temperature of 200 ° C and a load of lkg is MI (g/ 10 points) The temperature of 2 0 0 °C, the load of 10 1 ^ measured 1 ^ 1? is 〇 1 (2/10 points), its ^ 111? (= leg 1 / ^ 11) in 21.5 ~ ' 3 0 . 0 · between. , Page 47