CN1594414A - Flame-retardant styrene resin compositions - Google Patents

Abstract

The invention discloses polystyrene compositions which comprise rubber modified polystyrene and flame resisting agent, wherein the rubber modified polystyrene is composed of phenethylene copolymer as continuous phase and rubber particles as discontinuous phase, the phenylethene copolymer is copolymerized from phenylethene monomer, nitrile ethylene monomer, other copolymerization ethylene monomer, and polyfunctional maleimide monomer, wherein the content of rubber in the rubber modified styrene resin is 1-40 wt%, and the content of dimers and trimers derivatized by the phenylethene monomers and nitrile ethane monomers in the rubber modified styrene resin is below 1.25 wt%, the molten flow index value the ratio of phenethylene copolymer MIR=HMI/MI is between 21.5-30.0.

Description

Flame-retarded phenylethylene series resin composition

Technical field

The present invention particularly provides a kind of stress cracking resistance, shock-resistance and flame retardancy excellence about a kind of flame-retarded phenylethylene series resin composition, and stain is few, and when burning is difficult for producing a flame-retarded phenylethylene series resin composition that drips the combustion phenomenon.

Background technology

Portion's product such as general electricmaterial, office equipment, trolley part, household supplies, it is in the machine-shaping process, and widely used phenylethylene resin series material all has incendive shortcoming.For example with flame during near these moulding product, then its moulding product promptly take fire, even remove burning things which may cause a fire disaster this moment, flame can not extinguish immediately yet.In recent years, security at fire, the requirement of the difficult burning of phenylethylene resin series is strict day by day, particularly portion such as electricmaterial, office equipment product all requirement must meet U.S. UL (Underwriters Laboratories, the safety of America laboratory) UL-94VO specification, and in the UL-94VO specification test event, promptly require the phenomenon (Dripping) of dripping of not burn.In the past, the method of the difficult burning of phenylethylene resin series, opening as described in the 2000-129071 communique as Japanese kokai publication hei 10-120863 and spy, is the incombustible agent with organic bromine based compound, phosphorus series compound or the like, and perhaps the difficulty combustion auxiliary agent of ANTIMONY TRIOXIDE SB 203 99.8 PCT etc. makes an addition to mix in the styrene resin and uses.But aforesaid method is because of can't effectively preventing the phenomenon of dripping of burning, so the phenylethylene resin series that makes can't pass through the test of UL-94VO specification, and because the mixing of the incombustible agent of volume makes the shock-resistance of phenylethylene resin series obviously descend on the contrary.

And the drug-resistant stress crack properties of nonflammable resin in the past is not good yet, need be improved.For the ABS resin of flame retardancy, its modification method is generally the content that improves the vinyl cyanide base in the ABS resin, but this method is also insufficient to the drug-resistant stress crack properties that improves resin.

Therefore, how to obtain good shock strength, processing formings such as flame retardancy, and have the flame retardancy thermoplastically styrene resin fat composition of good drug-resistant stress crack again, for being familiar with this technical field person, wish the problem that breaks through for a long time always.

Summary of the invention

The object of the present invention is to provide a kind of flame-retarded phenylethylene series resin composition, a kind of stress cracking resistance, shock-resistance and flame retardancy excellence particularly are provided, stain is few, and when burning is difficult for producing a flame-retarded phenylethylene series resin composition that drips the combustion phenomenon.

Flame-retarded phenylethylene series resin composition of the present invention is made up of rubber modified phenylethylene resin series (I) 100 weight parts and incombustible agent (II) 1～40 weight part; Wherein, this rubber modified phenylethylene resin series (I) is by the nitrilation vinyl monomer of the styrenic monomers of (i-1) 50～90 weight parts, (i-2) 10～50 weight parts, other copolymerizable vinyl monomer of (i-3) 0～40 weight part, more than total 100 weight parts of (i-1), (i-2), (i-3), and the multi-functional maleimide of 0.0005～1.0 weight part be monomer institute's copolymerization and styrene based copolymer (A) constitute as disperse phase as external phase and rubber particles (B); Wherein, the rubber amount of rubber modified phenylethylene resin series (I) is 1～40 weight %, and whole content of being measured bodies or three amount bodies by styrenic monomers and nitrilation vinyl monomer institute deutero-two account for below the 1.25 weight % of rubber modified phenylethylene resin series (I); And styrene based copolymer (A) is MI (a g/10 branch) in 200 ℃ of temperature, the measured MFR of loading 1kg, and 200 ℃ of temperature, the measured MFR of loading 10kg are HMI (g/10 branch), its MIR (=HMI/MI) between 21.5～30.0.

The object lesson of (i-1) used in the present invention styrenic monomers as: vinylbenzene, alpha-methyl styrene, right-t-butyl styrene, p-methylstyrene, neighbour-vinyl toluene ,-vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, Alpha-Methyl-p-methylstyrene and bromstyrol etc., wherein, preferable with vinylbenzene or alpha-methyl styrene.Above-mentioned each compound can be used alone or as a mixture.Based on total 100 weight parts of above-mentioned (i-1), (i-2), (i-3), the consumption of (i-1) of the present invention styrenic monomers is 50～90 weight parts, is preferably 55～85 weight parts, is more preferred from 58～80 weight parts.

The object lesson of (i-2) used in the present invention nitrilation vinyl monomer is as vinyl cyanide, Alpha-Methyl vinyl cyanide etc., and is wherein preferable with vinyl cyanide.Based on total 100 weight parts of above-mentioned (i-1), (i-2), (i-3), (i-2) of the present invention nitrilation vinyl monomer is 10～50 weight parts, is preferably 15～45 weight parts, is more preferred from 20～42 weight parts.

(i-3) used in the present invention other copolymerizable vinyl monomer is meant to have vinyl, and can with the monomer of (i-1) of the present invention styrenic monomers, the copolymerization of (i-2) nitrilation vinyl monomer, object lesson as: acrylic ester monomer, methacrylate ester monomer and simple function maleimide are monomer etc.

Wherein, acrylic ester monomeric concrete example is as methyl acrylate, ethyl propenoate, isopropyl acrylate, butyl acrylate, polyethyleneglycol diacrylate etc., and is wherein, preferable with butyl acrylate.

And methacrylate ester monomeric object lesson is as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, the methacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, methacrylic acid dodecane ester, methacrylic acid 2-hydroxyl ethyl ester, glytidyl methacrylate, dimethylaminoethyl methacrylate, EDMA ethylene dimethacrylate (ethylene dimethacrylate), dimethacrylate peopentyl esters (neopentyldimethacrylate) etc. are wherein with methyl methacrylate, butyl methacrylate is preferable.

Be meant and only contain single maleimide functional group in the monomer and the simple function maleimide is a monomer, its object lesson is as maleimide, N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, N-hexyl maleimide, N-octyl group maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-2-methyl maleimide, N-2,3-3,5-dimethylphenyl maleimide, N-2,4-3,5-dimethylphenyl maleimide, N-2,3-diethyl phenyl maleimide, N-2,4-diethyl phenyl maleimide, N-2,3-dibutyl phenyl maleimide, N-2,4-dibutyl phenyl maleimide, N-2,6 3,5-dimethylphenyl maleimides, N-2,3-dichlorophenyl maleimide, N-2,4-dichlorophenyl maleimide, N-2,3-dibromo phenyl maleimide or N-2,4-dibromo phenyl maleimide etc., wherein preferable with N-phenylmaleimide.

In addition, the vinyl monomer that other copolymerization is possible, acrylic monomer (as: vinylformic acid for example, methacrylic acid), Maleic Acid, Anhydrous, anhydrous methyl-maleic acid, anhydrous methylfumaric acid, fumaric acid (fumaric acid), methylene-succinic acid unsaturated carboxylic acid based compounds such as (itaconic acid) with and esterification be monomer (dimethyl fumarate for example, dibutyl itaconate), ethene, propylene, 1-butylene, the 1-amylene, 4-methyl-1-pentene, ethylene chloride, 1,1 Ethylene Dichloride, tetrafluoroethylene, one chlorine three is fluoridized ethene, the hexafluoro propylene, divinyl, propenyl amine, isobutenyl amine, vinyl acetate between to for plastic, ethyl vinyl ether, methyl vinyl ketone, triallyl isocyanate (triallyl isocyanate) etc.

Based on total 100 weight parts of above-mentioned (i-1), (i-2), (i-3), (i-3) of the present invention other copolymerizable vinyl monomer consumption is 0～40 weight part, is preferably 1～34 weight part, is more preferred from 3～30 weight parts.

Multi-functional maleimide used in the present invention is a monomer, is meant the minimum compound that contains 2 maleimide functional groups, for example 2 or 3 or 3 above maleimide functional groups' compound.Wherein, be that monomer is good with bismaleimides again, its structural formula can general expression (1) expression General expression (1)

[in the formula, X is the alkylidene group (alkylene) of carbon number 1～10, arylidene (arylene), carbonyl (carbonyl group) ,-SO ₂-,-SO-,-O-, (R can be alkylidene group to-O-R-O-, arylidene)], concrete example is: N, N '-4,4 '-(3,3 '-dimethyl diphenylmethane) bismaleimides [N, N '-4,4 '-(3,3 '-dimethyl diphenyl methane) bismaleimide], N, N '-4,4 '-(3,3 '-diethyl ditan) bismaleimides [N, N '-4,4 '-(3,3 '-diethyl diphenylmethane) bismaleimide], N, N '-4,4 '-ditan bismaleimides (N, N '-4,4 '-diphenyl methane bismaleimide), N, N '-4,4 '-2,2-diphenyl propane bismaleimides (N, N '-4,4 '-2,2-diphenyl propane bismaleimide), N, N '-4,4 '-diphenyl ether bismaleimides (N, N '-4,4 '-diphenyl etherbismaleimide), N, N '-3,3 '-sulfobenzide bismaleimides (N, N '-3,3 '-diphenylsulfone bismaleimide), N, N '-4,4 '-sulfobenzide bismaleimides (N, N '-4,4 '-diphenyl sulfone bismaleimide), N, N '-4,4 '-diphenyl sulfoxide bismaleimides (N, N '-4,4 '-diphenyl sulfoxide bismaleimide), N, N '-4,4 '-benzophenone bismaleimides (N, N '-4,4 '-benzophenone bismaleimide), N, N '-1,3-phenylene bismaleimides (N, N '-1,3-phenylene bismaleimide), wherein with N, N '-4,4 '-ditan bismaleimides, N, N '-1,3-phenylene bismaleimides is preferable.Based on total 100 weight parts of above-mentioned (i-1), (i-2), (i-3), multi-functional maleimide of the present invention is that monomeric consumption is 0.0005～1.0 weight part, is preferably 0.001～0.3 weight part, is more preferred from 0.003～0.15 weight part.If multi-functional maleimide is a monomeric consumption when being higher than 1.0 weight parts, then in the polymerization process of styrol copolymer (A), the viscosity of polymkeric substance is rapid rising, and easily produces polymer bridge formation foreign matter and stain.

The manufacture method of styrene based copolymer of the present invention (A) can be finished by the general bulk of using or solution polymerization, emulsion polymerization reaction, outstanding turbid polyreaction; Wherein preferable with bulk or solution polymerization.The previous reaction device can comprise: column flow reactor (PFR), complete mixing reactor (CSTR) or contain the reactor etc. of silent oscillation mixing tank.Reactor quantity can be one, also can and use two or more, is preferably more than three or three.When using plural reactor, first reactor is preferable with complete mixing reactor (CSTR), and final reactor is to use columnar flow formula reactor (PFR) preferable.When making styrene based copolymer of the present invention (A), its manufacture is the material solution of reaction usefulness to be sent in the reactor continuously react, and the polymerization initiator can be added in the reaction.

Styrene based copolymer of the present invention (A) in the mill, and is common, addible polymerization initiator.Based on above-mentioned (i-1), (i-2), (i-3) total 100 weight parts, the usage quantity of polymerization initiator is 0～1 weight part, be preferably 0.001～0.5 weight part, spendable polymerization initiator can be simple function polymerization initiator or multi-functional polymerization initiator, wherein, concrete simple function polymerization initiator is for example: dibenzoyl peroxide (benzoyl peroxide), dicumyl peroxide (dicumylperoxide), tert-butyl peroxide (t-butyl peroxide), tert-butyl hydroperoxide (t-butylhydroperoxide), Cumene Hydroperoxide 80 (cumene hydroperoxide), tert butyl peroxy benzoate (t-butyl-peroxy benzoate), two-2-ethylhexyl peroxy dicarbonate (bis-2-ethylhexyl peroxy dicarbonate), tert-butyl hydroperoxide sec.-propyl carbonic ether (tert-butyl peroxy isopropyl carbonate, be called for short BPIC), cyclohexanone peroxide (cyclohexanone peroxide), 2,2 '-azo-two-isopropyl cyanide (2,2 '-azo-bis-isobutyronitrile), 1,1 '-azo bis cyclohexane-1-carbonyl nitrile (1,1 '-azo-bis cyclohexane-1-carbonitrile), 2,2 '-azo-two-2-methylbutyronitrile (2,2 '-azo-bis-2-methyl butyronitrile) etc.Wherein preferable with dibenzoyl peroxide, dicumyl peroxide.

The object lesson of multi-functional polymerization initiator has: 1,1-pair-tert-butyl hydroperoxide hexanaphthene (1,1-bis-t-butyl peroxy cyclohexane), 1,1-pair-tert-butyl hydroperoxide-3,3,5-trimethyl-cyclohexane (1,1-bis-t-butylperoxy-3,3,5-trimethyl cyclohexane, be called for short TX-29A), 2,5-dimethyl-2,5-pair-(2-ethyl peroxidation hexanoyl) hexane [2,5-dimethyl-2,5-bis-(2-ethylhexanoxy peroxy) hexane], 4-(tert-butyl hydroperoxide carbonyl)-3-hexyl-6-[7-(tert-butyl hydroperoxide carbonyl) heptyl] hexanaphthene 4-(t-butylperoxy carbonyl)-3-hexyl-6-[7-(t-butyl peroxy carbonyl) heptyl] cyclohexane}, two-tertiary butyl diperoxy azelate (di-t-butyl-diperoxyazelate), 2,5-dimethyl-2, two (benzoyl the peroxidation)-hexanes [2 of 5-, 5-dimethyl-2,5-bis-(benzoyl peroxy) hexane], two-tert-butyl hydroperoxide-six hydrogen-terephthalate (di-t-butyl peroxy-hexahydro-terephthalate), 2,2-two (4,4-two-tert-butyl hydroperoxide) cyclohexyl propane [2,2-bis-(4,4-di-t-butyl peroxy) cyclohexyl propane, be called for short PX-12], multi-functional single peroxycarbonates (multifunctional monoperoxycarbonate) (for example U.S. ATOFINA corporate system, trade(brand)name Luperox JWE) etc.; Wherein preferable with TX-29A, PX-12.

The temperature of reaction of above-mentioned reactor is to be controlled at 20～300 ℃, is preferably 60～250 ℃, is more preferred from 80～240 ℃, and the pressure of reactor is to be controlled at l～10kg/cm ²Between; And, can use chain-transfer agent among the present invention for the molecular weight of controlling polymers, based on total 100 weight parts of above-mentioned (i-1), (i-2), (i-3), the usage quantity of chain-transfer agent is 0～2 weight part, is preferably 0.001～1 weight part; Employed chain-transfer agent can be simple function chain-transfer agent or multi-functional chain-transfer agent, and concrete simple function chain-transfer agent has:

1) mercaptan (mercaptan) class: methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, just-lauryl mercaptan, stearyl-mercaptan (stearyl mercaptan), uncle-lauryl mercaptan (t-dodecyl mercaptan is called for short TDM), just-propyl group mercaptan, n-octyl mercaptan, uncle-octyl mercaptan, uncle-nonyl mercaptan etc.

2) alkanamine (alkyl amines) class: single ethylamine, diethylamide, triethylamine, single isopropylamine, diisopropylamine, monobutyl amine, di-n-butyl amine, three-n-butylamine etc.

3) other is for example: pentaphenylethane (pentaphenylethane), α-Jia Jibenyixierjuwu (α-methyl styrene dimer), terpinolene (terpinolene), wherein with in the thio-alcohol just-lauryl mercaptan, uncle-lauryl mercaptan are preferable.

Multi-functional chain-transfer agent is for example: isoamyl tetrol four (3-mercaptopropionic acid ester) [pentaerythritoltetrakis (3-mercapto propionate)], isoamyl tetrol four (2-mercaptoacetate) [pentaerythritol tetrakis (2-mercapto acetate)], three-(2-Thiovanic acid) trishydroxymethyl propyl ester [trimethylolpropane tris (2-mercapto acetate)], three-(3-thiohydracrylic acid) trishydroxymethyl propyl ester [trimethylolpropane tris (3-mercapto propionate)], three-(6-mercaptohexanoic acid) trishydroxymethyl propyl ester [trimethylol-propane tris (6-mercaptohexanate)] etc.; Above-mentioned cited person, preferable with three-(3-thiohydracrylic acid) trishydroxymethyl propyl ester.

The method for making of above-mentioned styrene based copolymer (A), be material solution to be imported reaction unit continuously react, when the whole monomers in the material solution reach behind the fixed turnover ratio, again polymer solution is taken out continuously by reaction unit, importing the devolatilization device removes unreacted monomer and volatilization composition, afterwards, give granulation again.The final monomer turnover ratio of general polymerization reaction is more than the 50 weight %, is preferably more than the 60 weight %, is more preferred from more than the 70 weight %.General devolatilization device can use decompression degassing vessel device, or the extrusion de-gassing vessel.Reclaim unreacted monomer or volatilization composition with condenser more afterwards, after the moisture in the recovery liquid can being removed in case of necessity, use as material solution again.

Styrene based copolymer of the present invention (A) optionally can add solvent in the mill.Based on total 100 weight parts of above-mentioned (i-1), (i-2), (i-3), the usage quantity of solvent is 0～100 weight part, is preferably 0～60 weight part, is more preferred from 1～50 weight part; Spendable solvent can be benzene, toluene, ethylbenzene, p-Xylol, o-Xylol, m-xylene, reaches pentane, octane, hexanaphthene, reaches methylethylketone, acetone, methyl butyl ketone etc.

Styrene based copolymer of the present invention (A) is MI (a g/10 branch) in 200 ℃ of temperature, the measured MFR of loading 1kg, 200 ℃ of temperature, the measured MFR of loading 10kg are HMI (g/10 branch), its MIR (=HMI/MI) usually between 21.5～30.0, preferable between 21.8～29.0, be more preferably under 22.0～28.0 between; Wherein MFR means melt flow index, and this index is to measure and get with ASTM D-1238 method.The MIR numerical value regulate and control method of multipolymer (A) can and be used for reaching by a kind of of following method or several.When being the copolymerization of multipolymer (A), multi-functional maleimide is monomeric addition and interpolation opportunity, the selection of multi-functional polymerization initiator and consumption, the selection of reactor, monomeric final transformation efficiency is that the part consumption of monomer or multi-functional polymerization initiator moves to second or second later mode such as polymerization reactor adding and reaches for example or with the styrenic monomers of above-mentioned (i-1), multi-functional maleimide.

Stress cracking resistance of the present invention is good, stain is few in order to reach, be difficult for producing the flame-retarded phenylethylene series resin composition that drips the combustion phenomenon and keep the shock-resistance excellence when burning, in the time of need satisfying the polyreaction of (1) of the present invention styrene based copolymer (A) simultaneously, multi-functional maleimide be monomeric consumption between 0.0005～1.0 weight part, and the MIR of (2) styrene based copolymer (A) is between 21.5～30.0.

Rubber modified phenylethylene resin series of the present invention (I), be as external phase with styrene based copolymer (A), rubber particles (B) makes as disperse phase, and wherein, the amount of rubber part is generally 1～40 weight %, is preferably 3～35 weight %, is more preferred from 5～30 weight %.The amount of rubber part of the present invention is if between 1～40 weight %, and then the balance of the flame retardancy of flame-retarded phenylethylene series resin composition and shock-resistance is preferable.

The manufacture method of rubber modified phenylethylene resin series (I) of the present invention can make an addition to the rubber composition in the polyreaction processing procedure of styrene based copolymer (A) and participate in reaction (following with while grafting method abbreviation).Perhaps rubber composition (as ordinary rubber or rubber graft copolymer, being good with rubber graft copolymer especially) is directly mixed extrusion with styrene based copolymer of the present invention (A) and make (following with grafting mix method abbreviation).Aforesaid while grafting method generally can adopt block polymerization, solution polymerization process, emulsion polymerization method or outstanding turbid polymerization to be finished.The manufacture method of aforesaid rubber graft copolymer generally can emulsion polymerization method, the block polymerization of emulsification finished, and is wherein preferable with emulsion polymerization method.

The manufacture method of rubber modified phenylethylene resin series (I) of the present invention, below enumerate two kinds of methods and be illustrated:

＜method one: the method for grafting simultaneously 〉

Method one can utilize bulk or solution polymerization to make rubber modified phenylethylene resin series of the present invention (I).Method one employed reactor can comprise: column flow reactor (PFR), complete mixing reactor (CSTR) or contain the reactor etc. of silent oscillation mixing tank.Reactor quantity can be one, also can and use two or more, is preferably more than three or three.When using plural reactor, first reactor is preferable with complete mixing reactor (CSTR), and final reactor is to use columnar flow formula reactor (PFR) preferable.Manufacture is sent into continuously for the material solution (containing the rubber composition) that will be satisfied with rubber modified phenylethylene resin series (I) of the present invention earlier and is reacted in the reactor, temperature of reaction is controlled at 30～300 ℃, be preferably 60～250 ℃, be more preferred from 80～240 ℃, and the pressure of reactor normally is controlled at 1～10kg/cm ²Between; And be the molecular weight of controlling polymers, in the manufacturing of rubber modified phenylethylene resin series (I) of the present invention, can optionally use polymerization initiator or chain-transfer agent.

The method for making of above-mentioned rubber modified phenylethylene resin series (I), be material solution to be imported reaction unit continuously react, when the whole monomers in the material solution reach behind the fixed turnover ratio, again polymer solution is taken out continuously by reaction unit, import the devolatilization device unreacted monomer and volatilization composition are removed, afterwards, give granulation again, and obtaining comprising styrene based copolymer (A) as external phase, rubber particles (B) is as the rubber modified phenylethylene resin series (I) of disperse phase.The final monomer turnover ratio of general polymerization reaction is more than the 50 weight %, is preferably more than the 60 weight %, is more preferred from more than the 70 weight %.General devolatilization device can use decompression degassing vessel device, or the extrusion de-gassing vessel.Reclaim unreacted monomer or volatilization composition with condenser more afterwards, after the moisture in the recovery liquid can being removed in case of necessity, use as material solution again.

In the preceding method one, the bulk of rubber modified phenylethylene resin series (I) or the employed material solution of solution polymerization process include: (i-1) 50～90 parts by weight of styrene are monomer, (i-2) 10～50 weight part nitrilation vinyl monomers, other copolymerizable vinyl monomer of (i-3) 0～40 weight part (above total 100 weight parts), and be monomer, 0～100 weight part solvent, and the rubber of 0.5～25 weight part with respect to the multi-functional maleimide of 0.0005～1.0 weight part of total 100 weight parts of (i-1), (i-2), (i-3); Wherein, styrenic monomers, nitrilation vinyl monomer, other copolymerizable vinyl monomer, multi-functional maleimide are that monomer, solvent reach optionally and the polymerization initiator of interpolation, specifying of the kind of chain-transfer agent and usage quantity is same as the material solution of making styrene based copolymer (A), do not give unnecessary details at this.

Aforesaid method-in, also available emulsion polymerization reacts and makes rubber modified phenylethylene resin series (I).The method for making of the method for making of emulsion polymerization reaction and following rubber like graft copolymer (B ') is identical, but described in the consumption employing method one of monomer and rubber.

In the bulk or solution polymerization of rubber modified phenylethylene resin series (I) of the present invention, rubber and styrenic monomers, monomeric mixing solutionss such as nitrilation vinyl monomer are in the polymeric initial stage, rubber phase is that the state with external phase exists, but graft polymerization reaction along with rubber, styrenic monomers, monomeric transformation efficiencys such as nitrilation vinyl monomer increase gradually, and be accompanied by the stirring of reactor, the rubber composition is gradually by styrenic monomers, monomers such as nitrilation vinyl monomer and polymkeric substance thereof surround, and change dispersed particle state (disperse phase) into, on the other hand, styrenic monomers, monomers such as nitrilation vinyl monomer and polymer transition thereof are external phase.Last rubber particles forms mutually.Weight average particle diameter 0.05～10 μ m of rubber particles is preferably 0.1～5 μ m, is more preferred from 0.1～2 μ m.

The concrete example of the rubber composition in the method one has: diene series rubber, polyolerin elastomer (routine ethylene-propylene rubber), polyacrylic ester are rubber, polysiloxane series rubber etc.Aforementioned diene series rubber is: at the polymer below 0 ℃, the concrete example of diene series rubber is the diene monomer composition through glass tansition temperature after the polymerization: divinyl rubber, synthetic polyisoprene, neoprene, EPDM rubber, vinylbenzene-diene series rubber, vinyl cyanide-diene series rubber etc.; Wherein, divinyl rubber has two kinds of high-cis (Hi-Cis) content and low cis (Low-Cis) content; In the high-cis rubber, the typical weight of its cis (Cis)/vinyl (Vinyl) consists of (94～99%)/(0～5%), and all the other compositions then are trans (Trans) structure; Its Mooney (Mooney) viscosity is at 20～120, and molecular weight ranges is with 100,000～800, and 000 is good; In the low cis rubber, the typical weight compositing range of cis/vinyl is in (20～40%)/(6～20%), and all the other are transconfiguration, and its Mooney (Mooney) viscosity is at 20～120, and molecular weight ranges is with 100,000～800, and 000 is good; The concrete example of vinylbenzene-diene series rubber such as styrene butadiene rubbers, styrene isoprene rubber etc., that it can be block copolymerization zoarium, random copolymers or constituent is cumulative/multipolymer of (taper) decrescence.Wherein cinnamic part by weight scope is with preferable below the 50 weight % in the styrene/butadiene rubbers, and molecular weight ranges is preferably 50,000～600, and 000 is preferable; Above-mentioned rubber is good with divinyl rubber and styrene/butadiene rubbers.

＜method two: the grafting method of mixing 〉

Method two can be mixed by styrene based copolymer (A) and rubber graft copolymer (B '), and extrusion makes rubber modified phenylethylene resin series of the present invention (I).

In the method two, usually with styrene based copolymer (A) and rubber graft copolymer (B '), with the Han Xieer mixing machine of general use do mix after, again with after the mixing machine melting mixing such as extrusion mixing machine, kneader or Banbury (Banbury) internal mixer etc., extrusion granulation again.

The method for making of rubber graft copolymer (B '), general spendable bulk or solution polymerization, emulsion polymerization reaction or outstanding turbid polyreaction are finished.Wherein rubber graft copolymer (B ') with the manufacture method of bulk or solution polymerization, is that material solution is carried out graft polymerization reaction.Material solution is: (i-1) other copolymerizable vinyl monomer of the nitrilation vinyl monomer of the styrenic monomers of 50～90 weight parts, (i-2) 10～50 weight parts, (i-3) 0～40 weight part, more than add up to 100 weight parts, the solvent of 0～100 weight part and 0.5～25 parts by weight of rubber reach optionally and polymerization initiator, the chain-transfer agent of interpolation; It is monomer that material solution does not comprise multi-functional maleimide usually, is monomer if use multi-functional maleimide, and its used in amounts is below usage quantity lower limit of the present invention.Wherein, styrenic monomers, nitrilation vinyl monomer, other copolymerizable vinyl monomer, solvent reach optionally and the polymerization initiator of interpolation, specifying of the kind of chain-transfer agent and usage quantity is same as the material solution of making styrene based copolymer (A), and the explanation of the composition concrete example of rubber composition is with the explanation of method one.

In the bulk or solution polymerization of rubber graft copolymer of the present invention (B '), rubber and styrenic monomers, monomeric mixing solutionss such as nitrilation vinyl monomer are in the polymeric initial stage, rubber phase is that the state with external phase exists, but graft polymerization reaction along with rubber, styrenic monomers, monomeric transformation efficiencys such as nitrilation vinyl monomer increase gradually, and be accompanied by the stirring of reactor, the rubber composition is gradually by styrenic monomers, monomers such as nitrilation vinyl monomer and polymkeric substance thereof surround, and change dispersed particle state (disperse phase) into, on the other hand, styrenic monomers, monomers such as nitrilation vinyl monomer and polymer transition thereof are external phase.Last rubber particles forms mutually.Weight average particle diameter 0.05～10 μ m of rubber particles is preferably 0.1～5 μ m, is more preferred from 0.1～2 μ m.

In addition rubber graft copolymer (B ') also can be finished by emulsion polymerization, its manufacture method is with rubber latex 40～90 weight parts (solid) and monomer or monomer mixture 60～10 weight parts such as styrenic monomers 15～95 weight %, nitrilation vinyl monomer 5～50 weight %, other copolymerizable monomer 0～35 weight %, and the emulsifying agent, initiator and the chain-transfer agent that optionally add carry out graft polymerization reaction, and obtain the rubber graft copolymer emulsion; Again with aforementioned graft copolymer emulsion via condense, dehydration, drying and other steps, to obtain rubber graft copolymer required for the present invention (B ').

Rubber composition concrete example explanation in the aforementioned rubber latex is good with diene series rubber again wherein with the explanation of the rubber composition in the method one.The manufacture method of diene series rubber emulsion, can diene monomer (for example divinyl) or diene monomer 100～50 weight % and other copolymerizable monomer 0～50 weight %, for example: copolymerizable monomer such as vinylbenzene, vinyl cyanide and (methyl) acrylate aggregate into the diene series rubber emulsion of weight average particle diameter 0.05～0.6 μ m with emulsion polymerization method; After also aforementioned monomer can being made the small particle size diene series rubber emulsion of weight average particle diameter 0.05～0.20 μ m with emulsion polymerization method, again with the loose method of freezing loose method, mechanical loose method or additive, with the big particle diameter diene series rubber emulsion of the loose one-tenth of aforementioned small particle size diene series rubber emulsion weight average particle diameter 0.22～0.6 μ m, in order to further carrying out graft copolymerization; Wherein, employed additive can be in the loose method of additive: acidic substance such as acetic anhydride, hydrogenchloride, sulfuric acid, or be salt-base substances such as sodium-chlor, Repone K, calcium chloride, and (methyl) vinylformic acid-(methyl) acrylate copolymer (as methacrylic acid-butyl acrylate copolymer, EUDRAGIT L100-55) etc. contains carboxylic acid group's polymer coagulant.

In the rubber modified phenylethylene resin series of the present invention (I), whole content by styrenic monomers and nitrilation vinyl monomer institute deutero-two amount bodies or three amount bodies account for below the 1.25 weight % of rubber modified phenylethylene resin series (I), be preferably below the 1.10 weight %, be more preferred from below the 0.95 weight %.

Be difficult for producing a flame-retarded phenylethylene series resin composition that drips the combustion phenomenon for reaching when burning of the present invention, in the time of need satisfying the polyreaction of (1) of the present invention styrene based copolymer (A) simultaneously, multi-functional maleimide is that monomeric consumption is between 0.0005～1.0 weight part, and the MIR of (2) styrene based copolymer (A) reaches whole content of (3) measuring bodies or three amount bodies by styrenic monomers and nitrilation vinyl monomer institute deutero-two and accounts for below the 1.25 weight % of rubber modified phenylethylene resin series (I) between 21.5～30.0.And the regulate and control method by whole content of styrenic monomers and nitrilation vinyl monomer institute deutero-two amount bodies or three amount bodies of rubber modified phenylethylene resin series (I) can and be used for reaching by a kind of of following method or several.When being the copolymerization of styrene based copolymer (A), the selection of polymerization initiator and consumption, polymerization temperature, the modes such as selection of polymerization time or devolatilization device and method are reached, for example low temperature polymerization cooperates the use of polymerization initiator, and reinforcement devolatilization processing (extruder adds the devolatilization of devolatilization auxiliary agent) etc. is reached.

Flame-retarded phenylethylene series resin composition of the present invention is made up of rubber modified phenylethylene resin series (I) and incombustible agent (II).

Flame-retarded phenylethylene series resin composition of the present invention, usually system is with rubber modified phenylethylene resin series (I) and incombustible agent (II), after dried the mixing of Han Xieer mixing machine with general use, again with after the mixing machine melting mixing such as extrusion mixing machine, kneader or Banbury (Banbury) internal mixer etc., extrusion granulation again.

In the flame-retarded phenylethylene series resin composition of the present invention, based on above-mentioned rubber modified phenylethylene resin series (I) 100 weight parts, the usage quantity of its incombustible agent (II) is 1～40 weight part, is preferably 2～38 weight parts, is more preferred from 3～35 weight parts.When the usage quantity of incombustible agent (II) is lower than 1 weight part, then the flame retardancy of flame-retarded phenylethylene series resin composition is not good, when the usage quantity of incombustible agent (II) is higher than 40 weight parts, and the shock-resistance deficiency of flame-retarded phenylethylene series resin composition then.It is incombustible agent or phosphorus series flame-resisting agent that above-mentioned spendable incombustible agent (II) can be halogen, wherein, concrete halogen incombustible agent is for example: tetrabromo-bisphenol, the carbonic ether oligomer of tetrabromo-bisphenol, tetrabromo-bisphenol two (2,3-dibromo propyl ether), tetrabromo-bisphenol two (2-bromine ether), the accrete epoxy oligomer of tetrabromo-bisphenol diglycidylether and bromination biphenol, the tetrabromo-bisphenol derivative of tetrabromo-bisphenol diglycidylether and tribromophenol annexation etc., decabromodiphynly oxide, octabromodiphenyl ether, the two tetrabromo phthalimides of ethyl, hexabromocyclododecane, 1, two (pentabromobenzene) ethane of 2-, 2,3-dibromopropyl pentabromo-phenylate, two (2,4, the 6-tribromophenoxy) ethane, or the like bromize aromatic compound; Clorafin, chlorinated naphthalene, perchloro-cyclopentadecane, chlorination aromatics, chlorination alicyclic compound, or the like.Wherein preferable with the accrete epoxy oligomer of tetrabromo-bisphenol, tetrabromo-bisphenol diglycidylether and bromination biphenol, tetrabromo-bisphenol diglycidylether and tribromophenol annexation.Decided the above compound of purpose and can be used separately or two or more using with by reaching.

In the flame-retarded phenylethylene series resin composition of the present invention, can add difficult combustion auxiliary agent in case of necessity to increase its flame retardancy.Employed difficult combustion auxiliary agent is as the oxide compound of classes such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony tetroxide, antimony peroxide, and the stibnate of class such as sodium antimonate etc.Be preferable wherein with ANTIMONY TRIOXIDE SB 203 99.8 PCT.This difficulty combustion auxiliary agent, based on above-mentioned rubber modified phenylethylene resin series (I) 100 weight parts, its usage quantity is 0～20 weight part, is preferably 1～18 weight part, is more preferred from 3～15 weight parts.

The object lesson of phosphorus series flame-resisting agent has: tricresyl phosphate (toluene ester), tricresyl phosphate (diformazan phenyl ester), phosphoric acid (tolyl diphenyl), triphenylphosphate, tricresyl phosphate (isopropyl biphenyl ester), trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate (butoxy ethyl ester), phosphoric acid (octyl group diphenyl), orthoxenol be phosphoric acid ester, tetramethylolmethane be phosphoric acid ester, neopentyl glycol be phosphoric acid ester, displacement neopentyl glycol be phosphoric acid ester, nitrogenous be phosphoric acid ester, and the aromatic phosphoric ester shown in following (2) formula or the like.Particularly use to good with the aromatic phosphoric ester shown in (2) formula.

(in the following formula, Ar ¹, Ar ², Ar ³, Ar ⁴Be identical or different not halogen-containing aromatic base, and X is a selected structure from the formula of following (3)～(5).(3)～(5) in the formula, R ¹～R ⁸Be the alkyl of identical or different hydrogen atom or carbonatoms 1～5, Y is direct bonded O, S, SO ₂, C (CH ₃) ₂, CH ₂, CHPh; Ph is a phenyl.And (2) n in the formula is the integer more than 0, and k, the m in (2) formula respectively is the integer below 2 more than 0, and (k+m) is the integer below 2 more than 0.) in addition relevant this aromatic phosphoric ester, also can and use with other heteroid aromatic phosphoric ester.

N in the following formula (2) is the integer more than 0, and by the viewpoint of flame retardancy, the upper limit of its n value is being good below 40; Be preferably below 10, the best is below 5.

In addition, k, m respectively are the integer below 2 more than 0, and k+m is the integer below 2 more than 0.Being preferably k, m respectively is the integer below 1 more than 0, and best is that k, m respectively are 1.

In following formula (3)～(5), R ¹～R ⁸Alkyl for identical or different hydrogen atom or carbonatoms 1～5.The object lesson of the alkyl of this carbonatoms 1～5 is as follows: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, neo-pentyl, tert-pentyl etc.Being good with hydrogen atom, methyl, ethyl wherein, is best especially with the hydrogen atom.

In addition, Ar ¹, Ar ², Ar ³, Ar ⁴Be identical or different not halogen-containing aromatic series base.Wherein the aromatic series base can be the aromatic series base that contains benzene skeleton, naphthalene skeleton, indenes skeleton, anthracene skeleton.Be good wherein with the aromatic series base that contains benzene skeleton or naphthalene skeleton.These aromatic series bases can be replaced by organic residue of halogen atom not (with organic residue of carbonatoms 1～8 by good), and substituent number does not have specific limited, and are good with 1～3.Object lesson is: phenyl, tolyl, xylyl, cumyl, 1,3, the aromatic series base of 5-trimethylphenyl, naphthyl, indenyl, anthryl or the like.Being good with phenyl, tolyl, xylyl, cumyl, naphthyl wherein, is the best with phenyl, tolyl, xylyl especially.

The phosphoric acid ester that sell in market has: PX-200, PX-201, PX-130, CR-733S, TPP, CR-741, CR747, TCP, TXP, CDP that big eight chemical companies make, can use from wherein selecting more than a kind or 2 kinds; Use more than a kind or 2 kinds to preferable and from PX-200, TPP, CR-733S, CR-741, CR747, select; Especially be the best to use PX-200, CR-733S, CR-741.

In the flame-retarded phenylethylene series resin composition of the present invention, can add the difficult combustion of aggretion type auxiliary agent in case of necessity to increase its flame retardancy.The difficult combustion of employed aggretion type auxiliary agent is as tetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/perfluoro alkyl vinyl ether multipolymer, tetrafluoroethylene/ethylene multipolymer, R 1216/propylene copolymer, poly-1,1-difluoroethylene, vinylidene fluoride/ethylene copolymer or the like.Be good wherein with tetrafluoroethylene, tetrafluoroethylene/perfluoro alkyl vinyl ether multipolymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene multipolymer, poly-vinylidene fluoride; Especially be the best with tetrafluoroethylene, tetrafluoroethylene/ethylene multipolymer.This difficulty combustion auxiliary agent, based on above-mentioned rubber modified phenylethylene resin series (I) 100 weight parts, its usage quantity is 0～20 weight part, is preferably 0.02～10 weight part, is more preferred from 0.1～5 weight part.

In the flame-retarded phenylethylene series resin composition of the present invention, can add various additives in case of necessity, as antioxidant, lubricant, UV light absorber, ultra-violet stabilizer, charged preventor, tinting material etc., the interpolation time can or mix the extrusion stage in the polymerization stage of styrene based copolymer (A) or rubber modified phenylethylene resin series (I) or flame-retarded phenylethylene series resin composition.Based on the flame-retarded phenylethylene series resin composition of 100 weight parts, the consumption of additive is generally below 6 weight parts.Other additive also can optionally add as impacting modification agent etc., and based on the flame-retarded phenylethylene series resin composition of 100 weight parts, the consumption that impacts the additive of modification agent etc. is generally below 30 weight parts.

In the flame-retarded phenylethylene series resin composition of the present invention, but benzene mixed vinyl copolymer (A) resin in addition in case of necessity.Be in the flame-retarded phenylethylene series resin composition, can contain external phase is styrene based copolymer (A) various polymkeric substance in addition.This polymkeric substance can be acrylonitrile-butadiene-styrene resin, acrylonitrile styrene resin (AS), acrylonitrile-butadiene-αJia Jibenyixi resin, acrylonitrile-styrene-methyl-methacrylate resin, acrylonitrile-styrene-N phenyl maleimide resin, vinylbenzene-Maleic Acid, Anhydrous resin, vinylbenzene-N-phenylmaleimide resin, polymethylmethacrylate, polycarbonate resin, vinylbenzene-methacrylic resin, methacrylic acid-butadiene styrene resin, acrylonitrile-butadiene-N phenyl maleimide-styrene resin, polyamide resin, vibrin, polyphenylene oxide resin, vinyl cyanide-acrylic elastomer-styrene resin, vinyl cyanide-(ethylene-propylene diene series rubber)-styrene resin, vinyl cyanide-silica gel-styrene resin and other resin, this resin can separately or merge use.Based on the rubber modified phenylethylene resin series (I) of 100 weight parts, the consumption of this polymkeric substance is generally below 500 weight parts.

[embodiment and comparative example]

Aforementioned and other technology contents, characteristics and effect of the present invention in the explanation of following cooperation embodiment and comparative example, can clearly be understood.

[synthesis example of styrene based copolymer (A)]

Synthesis example a

Synthesizing of styrene based copolymer (A-1)

At three in-line reactors, be respectively first, two reactors are complete mixing reactor (hereinafter to be referred as CSTR), the 3rd reactor is column flow reactor (hereinafter to be referred as PFR), with styrene monomer (hereinafter to be referred as SM) 64.5 weight parts, acrylonitrile monemer (hereinafter to be referred as AN) 35.5 weight parts, N, N '-4,4 '-ditan bismaleimide amine monomers (hereinafter to be referred as BMI), 0.025 weight part, polymerization initiator dibenzoyl peroxide (hereinafter to be referred as BPO) 0.02 weight part, chain-transfer agent uncle-lauryl mercaptan (hereinafter to be referred as TDM) 0.2 weight part, and the mixing solutions of solvent ethylbenzene (hereinafter to be referred as EB) 25 weight parts, with 36kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor gained is imported second reactor, and,, be supplied to second reactor continuously and carry out polyreaction with 2kg/ hour flow with the mixing solutions of SM 100 weight parts, BMI 0.22 weight part; Polymers soln with the second reactor gained imports the 3rd reactor again, and with the mixing solutions of SM 100 weight parts, BMI 0.04 weight part, with 2kg/ hour flow, is supplied to the 3rd reactor continuously and carries out polyreaction; Wherein, the volume of first, second, third reactor is respectively 40,40,75 liters, and the temperature of reactive tank is respectively 95,105,135 ℃, and stir speed (S.S.) is respectively 120,90,35rpm; The monomer conversion 72 weight % of final reactor outlet.

After polymerization ends, normally will import the devolatilization groove by the copolymer solution of the 3rd reactor reaction gained, again through extrusion devolatilization device and import devolatilization auxiliary agent (water) devolatilization, remove unreacted monomer and other fugitive constituent with this device; And through the polymerization melts of devolatilization, its extrusion granulated can obtain styrene based copolymer (A-1); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-1) are listed in table one.

Synthesis example b

Synthesizing of styrene based copolymer (A-2)

At three in-line reactors, being respectively first and second reactor is CSTR, the 3rd reactor is PFR, with SM 65.5 weight parts, AN 34.5 weight parts, BMI 0.022 weight part, polymerization initiator 1,1-pair-tert-butyl hydroperoxide-3,3,5-trimethyl-cyclohexane (hereinafter to be referred as TX-29A) 0.01 weight part, TDM 0.2 weight part, and the mixing solutions of EB 25 weight parts, with 37kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor gained is imported second reactor, and with SM 100 weight parts, the mixing solutions of BMI 0.15 weight part with 3kg/ hour flow, is supplied to second reactor continuously and carries out polyreaction; Again the polymers soln of the second reactor gained is imported the 3rd reactor and carry out polyreaction; Wherein, the volume of first, second, third reactor is respectively 40,40,75 liters, and the temperature of reactive tank is respectively 95,105,135 ℃, and stir speed (S.S.) is respectively 120,90,35rpm; The monomer conversion 74 weight % of final reactor outlet.

After polymerization ends, will carry out steps such as devolatilization, extrusion, granulation by the copolymer solution of the 3rd reactor reaction gained with synthesis example a, can obtain styrene based copolymer (A-2); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-2) are listed in table one.

Synthesis example c

Synthesizing of styrene based copolymer (A-3)

At four in-line reactors, being respectively first and second reactor is CSTR, three, the 4th reactor is PFR, with SM 64.5 weight parts, AN 35.5 weight parts, BMI 0.007 weight part, polymerization initiator 2, two (4, the 4-di-tert-butyl peroxide) cyclohexyl propane (hereinafter to be referred as PX-12) 0.005 weight parts of 2-, TDM 0.2 weight part, and the mixing solutions of EB 25 weight parts, with 36kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor gained is imported second reactor, and with the mixing solutions of SM 100 weight parts, BMI 0.066 weight part, TX-29A 0.054 weight part, with 2kg/ hour flow, be supplied to second reactor continuously and carry out polyreaction; Polymers soln with the second reactor gained imports the 3rd reactor again, and with the mixing solutions of SM 100 weight parts and TX-29A 0.013 weight part, with 2kg/ hour flow, is supplied to the 3rd reactor continuously and carries out polyreaction; Again the polymers soln of the 3rd reactor gained is imported the 4th reactor and carry out polyreaction; Wherein, the volume of first, second, third, fourth reactor is respectively 40,40,75,75 liters, and the temperature of reactive tank is respectively 95,105,130,135 ℃, and stir speed (S.S.) is respectively 120,90,38,35rpm; The monomer conversion 76 weight % of final reactor outlet.

After polymerization ends, will carry out steps such as devolatilization, extrusion, granulation by the copolymer solution of the 4th reactor reaction gained with synthesis example a, can obtain styrene based copolymer (A-3); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-3) are listed in table one.

Synthesis example d

Synthesizing of styrene based copolymer (A-4)

At three in-line reactors, being respectively first and second reactor is CSTR, the 3rd reactor is PFR, with SM 64.5 weight parts, AN 35.5 weight parts, BMI 0.028 weight part, PX-12 0.006 weight part, TDM 0.2 weight part, and the mixing solutions of EB 25 weight parts, with 36kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reaction gained is imported second reactor, and,, be supplied to second reactor continuously and carry out polyreaction with 2kg/ hour flow with the mixing solutions of SM 100 weight parts, TX-29A 0.033 weight part; Polymers soln with the second reactor gained imports the 3rd reactor again, and with the solution of SM 100 weight parts, with 2kg/ hour flow, is supplied to the 3rd reactor continuously and carries out polyreaction; Wherein, the volume of first, second, third reactor is respectively 40,40,75 liters, and the temperature of reactive tank is respectively 95,105,135 ℃, and stir speed (S.S.) is respectively 120,90,35rpm; The monomer conversion 71 weight % of final reactor outlet.

After polymerization ends, will carry out steps such as devolatilization, extrusion, granulation by the copolymer solution of the 3rd reactor reaction gained with synthesis example a, can obtain styrene based copolymer (A-4); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-4) are listed in table one.

Synthesis example e

Synthesizing of styrene based copolymer (A-5)

At three in-line reactors, being respectively first and second reactor is CSTR, the 3rd reactor is PFR, with SM 64.5 weight parts, AN 35.5 weight parts, BMI 0.022 weight part, BPO 0.02 weight part, TDM 0.2 weight part, and the mixing solutions of EB 25 weight parts, with 36kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor gained is imported second reactor, and,, be supplied to second reactor continuously and carry out polyreaction with 2kg/ hour flow with the mixing solutions of SM 100 weight parts, BMI 0.2 weight part, TX-29A 0.08 weight part; Polymers soln with the second reactor gained imports the 3rd reactor again, and with the solution of SM 100 weight parts, with 2kg/ hour flow, is supplied to the 3rd reactor continuously and carries out polyreaction; Wherein, the volume of first, second, third reactor is respectively 40,40,75 liters, and the temperature of reactive tank is respectively 95,105,135 ℃, and stir speed (S.S.) is respectively 120,90,35rpm; The monomer conversion 72 weight % of final reactor outlet.

After polymerization ends, will carry out steps such as devolatilization, extrusion, granulation by the copolymer solution of the 3rd reactor reaction gained with synthesis example a, can obtain styrene based copolymer (A-5); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-5) are listed in table one.

Synthesis example f

Synthesizing of styrene based copolymer (A-6)

Operating method with synthesis example b, difference is that employed monomer consumption is done an adjustment in the charging mixing solutions with first reactor, be respectively SM 60 weight parts, AN 34 weight parts, and methyl methacrylate (hereinafter to be referred as MMA) 6 weight parts, the monomer conversion 74 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-6) are listed in table one.

Synthesis example g

Synthesizing of styrene based copolymer (A-7)

With the operating method of synthesis example b, difference is that employed monomer consumption is done an adjustment in the charging mixing solutions with first reactor, is respectively SM 61 weight parts, AN 39 weight parts, the monomer conversion 72 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-7) are listed in table one.

Synthesis example h

Synthesizing of styrene based copolymer (A-8)

Operating method with synthesis example b, difference is that employed monomer consumption is done an adjustment in the charging mixing solutions with first reactor, be respectively SM 73 weight parts, AN 27 weight parts, and employed BMI consumption is done an adjustment in the charging mixing solutions of first, second reactor, the consumption of first, second reactor is adjusted into 0.066 weight part, 0.45 weight part respectively, the monomer conversion 73 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-8) are listed in table one.

Compare synthesis example I

Synthesizing of styrene based copolymer (A-9)

At two in-line reactors, first and second reactor is all CSTR, with SM 68 weight parts, AN 32 weight parts, BPO 0.02 weight part, TDM 0.2 weight part, and the mixing solutions of EB 25 weight parts, with 40kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; Again the polymers soln of the first reactor gained is imported second reactor and carry out polyreaction; Wherein, the volume of first, second reactor is respectively 40,40 liters, and the temperature of reactive tank is respectively 100,120 ℃, and stir speed (S.S.) is respectively 120,90rpm; The monomer conversion 52 weight % of final reactor outlet.

After polymerization ends, will carry out steps such as devolatilization, extrusion, granulation by the copolymer solution of the second reactor reaction gained with synthesis example a, can obtain styrene based copolymer (A-9); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-9) are listed in table one.

Compare synthesis example j

Synthesizing of styrene based copolymer (A-10)

With the operating method of synthesis example i relatively, difference is in the charging mixing solutions with first reactor, to add BMI 0.01 weight part, the monomer conversion 53 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-10) are listed in table one.

Compare synthesis example k

Synthesizing of styrene based copolymer (A-11)

With the operating method that compares synthesis example i, difference is in the charging mixing solutions with first reactor, add divinyl benzene monomer (hereinafter to be referred as DVB) 0.035 weight part, and 0.3 weight part of the consumption of TDM adjustment, the monomer conversion 54 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-11) are listed in table one.

Compare synthesis example 1

Synthesizing of styrene based copolymer (A-12)

At two in-line reactors, first and second reactor is all CSTR, with SM 65.5 weight parts, AN 34.5 weight parts, BMI 0.022 weight part, TDM 0.2 weight part, and the mixing solutions of EB 25 weight parts, with 37kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor gained is imported second reactor, and with SM 100 weight parts, the mixing solutions of BMI 0.15 weight part with 3kg/ hour flow, is supplied to second reactor continuously and carries out polyreaction; Wherein, the volume of first, second reactor is respectively 40,40 liters, and the temperature of reactive tank is respectively 140,150 ℃, and stir speed (S.S.) is respectively 120,90,35rpm; The monomer conversion 50 weight % of final reactor outlet.

After polymerization ends, normally will import the devolatilization of devolatilization groove by the copolymer solution of the second reactor reaction gained, remove unreacted monomer and other fugitive constituent with this device; Can obtain styrene based copolymer (A-12); The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-12) are listed in table one.

Compare synthesis example m

Synthesizing of styrene based copolymer (A-13)

With the operating method that compares synthesis example 1, difference is in the charging mixing solutions with first and second reactor, do not add BMI, and the temperature of reaction of first and second reactor is adjusted to 130,140 ℃ respectively, the monomer conversion 49 weight % of final reactor outlet; The manufacturing prescription and the Physical Property Analysis thereof of this styrene based copolymer (A-13) are listed in table one.

Compare synthesis example n

Synthesizing of styrene based copolymer (A-14)

With the operating method of synthesis example i relatively, difference is in the charging mixing solutions with first reactor, to add BMI 1.5 weight parts; In the reaction process, the viscosity that is because of reaction sharply rises, follow form and aspect variation, the many high-molecular weight bridge formation foreign matters of generation and the stain of resultant of reaction, cause polyreaction to proceed, and the resultant of reaction that takes out is 32.5 through the MIR of mobility-thickness product determinator analysis.

[synthesis example of rubber graft copolymer (B '-1)]

At four in-line reactors, the first～four reactor is all CSTR, with SM 68 weight parts, AN 32 weight parts, divinyl rubber (hereinafter to be referred as BD) 7.0 weight parts, BPO 0.03 weight part, TDM0.3 weight part, and the mixing solutions of EB 35 weight parts, with 40kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; Wherein, the volume of first, second, third, fourth reactor is all 40 liters, and the temperature of reactive tank is respectively 100,105,115,130 ℃, and stir speed (S.S.) is respectively 300,200,150,90rpm; The monomer conversion 65 weight % of final reactor outlet.

After polymerization ends, will carry out steps such as devolatilization, extrusion, granulation by the copolymer solution of the 4th reactor reaction gained with synthesis example a, can obtain rubber graft copolymer (B '-1), rubber constituent amount 10 weight %.

[synthesis example of rubber graft copolymer (B '-2)]

[table two]

Composition	Weight part
		1,3-butadiene	????150.00
Potassium persulfate solution (1%)	????15.00
		Potassium oleate	????2.00
Distilled water	????190.00
		Ethylene glycol dimethacrylate	????0.13

According to the reaction 14 hours under 65 ℃ of temperature of reaction of above table two prescription, the synthetic rubber latex that obtain transformation efficiency and be 94%, solids content is about 36%, weight average particle diameter is about 0.1 μ m.

[table three]

Composition	Weight part
		Butyl acrylate	????90.00
Methacrylic acid	????10.00
		Potassium persulfate solution (1%)	????0.50
Sodium dodecyl sulfate solution (10%)	????0.50
		The n-lauryl mercaptan	????1.0
Distilled water	????200.00

According to the reaction 5 hours under 75 ℃ of temperature of reaction of above table three prescription, obtain that transformation efficiency is about 95%, the polymer coagulant emulsion that contains the carboxylic acid group of pH value 6.0.

Afterwards, utilize the synthetic rubber latex of next loose 100 weight parts of the polymer coagulant that contains the carboxylic acid group of 3 weight parts (dry weight), the pH value of resulting rubber latex is 8.5, and its rubber weight average particle diameter is about 0.31 μ m.

At last, with the prescription of aforementioned enlarged rubber emulsion, the rubber latex of aforementioned hypertrophyization is carried out graft polymerization reaction with styrene-acrylonitrile copolymer again, to make rubber graft copolymer (B '-2) according to following table four.

[table four]

Composition	Weight part
		Enlarged rubber emulsion (dry weight)	????100.0
Styrene monomer	????75.0
		Acrylonitrile monemer	????25.0
Uncle's lauryl mercaptan	????2.0
		Cumene Hydroperoxide 80	????3.0
Copperas solution (0.2%)	????3.0
		Formaldehyde sodium sulfoxylate solution (10%)	????0.9
Ethylene dinitrilotetra-acetic acid solution (0.25%)	????3.0

Condense with calcium chloride according to the prepared rubber graft copolymer emulsion of table four prescription, through dewatering, being dried to below 2%, can make rubber graft copolymer (B '-2) (rubber content 50 weight %, rubber weight average particle diameter 0.31 μ m) again.

[making the preparation example of rubber modified phenylethylene resin series]

The method of grafting simultaneously

Preparation example a '

The preparation of rubber modified phenylethylene resin series (I-1)

At four in-line reactors, being respectively first and second reactor is CSTR, three, the 4th reactor is PFR, with SM 65.5 weight parts, AN 34.5 weight parts, BD 8.0 weight parts, BMI 0.022 weight part, TX-29A 0.04 weight part, TDM 0.3 weight part, and the mixing solutions of EB 35 weight parts, with 37kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; The polymers soln of the first reactor gained is imported second reactor, and,, be supplied to second reactor continuously and carry out polyreaction with 3kg/ hour flow with the mixing solutions of SM 100 weight parts, BMI 0.15 weight part; Again the polymers soln of the second reactor gained is imported the 3rd reactor and carry out polyreaction; And importing the 4th reactor again, the polymers soln of the 3rd reactor gained carries out polyreaction; Wherein, the volume of first, second, third, fourth reactor is respectively 40,40,75,75 liters, and the temperature of reactive tank is respectively 100,105,115,130 ℃, and stir speed (S.S.) is respectively 300,200,150,90rpm; The monomer conversion 75 weight % of final reactor outlet.

After polymerization ends, will carry out steps such as devolatilization, extrusion, granulation by the copolymer solution of the 4th reactor reaction gained with synthesis example a, can obtain rubber modified phenylethylene resin series (I-1), rubber constituent amount 10 weight %; The phenylethylene resin series that this is rubber modified (I-1) is dissolved in the tetrahydrofuran solution, obtains styrene based copolymer (A) external phase, and the value of measuring its MIR is 24.2; The manufacturing prescription and the Physical Property Analysis thereof of this rubber modified phenylethylene resin series (I-1) the results are shown in table five.

Preparation example b '

The preparation of rubber modified phenylethylene resin series (I-2)

At four in-line reactors, being respectively first and second reactor is CSTR, three, the 4th reactor is PFR, with SM 68 weight parts, AN 32 weight parts, BD 8.0 weight parts, BMI 0.0002 weight part, TX-29A 0.04 weight part, TDM 0.3 weight part, and the mixing solutions of EB 35 weight parts, with 40kg/ hour flow, be supplied to first reactor continuously and carry out polyreaction; Wherein, the volume of first, second, third, fourth reactor is respectively 40,40,75,75 liters, and the temperature of reactive tank is respectively 100,105,115,130 ℃, and stir speed (S.S.) is respectively 300,200,150,90rpm; The monomer conversion 74 weight % of final reactor outlet.

After polymerization ends, will carry out steps such as devolatilization, extrusion, granulation by the copolymer solution of the 4th reactor reaction gained with synthesis example a, can obtain rubber modified phenylethylene resin series (I-2), rubber constituent amount 10.3 weight %; The phenylethylene resin series that this is rubber modified (I-2) is dissolved in the tetrahydrofuran solution, obtains styrene based copolymer (A) external phase, and the value of measuring its MIR is 21.1; The manufacturing prescription and the Physical Property Analysis thereof of this rubber modified phenylethylene resin series (I-2) are listed in table five.

The grafting method of mixing

Preparation example c '

The preparation of rubber modified phenylethylene resin series (I-3)

With rubber graft copolymer (B '-1) 20 weight parts, rubber graft copolymer (B '-2) 36 weight parts, styrene based copolymer (A-1) 44 weight parts, and ethylenebisstearamide (ethylenebisstearamide, hereinafter to be referred as EBS) 0.3 weight part, after do mixing with the Han Xieer mixing machine, again with 200～220 ℃ of raw material tank temperature, the twin shaft extruder fusion with venting port that die head temperature is 220 ℃ is mixed, can make the rubber modified phenylethylene resin series (I-3) of tool particle (pellet) shape, rubber constituent amount 20 weight %; The manufacturing prescription and the Physical Property Analysis thereof of this resin (I-3) the results are shown in table six.

Preparation example d '

The preparation of rubber modified phenylethylene resin series (I-4)

With rubber graft copolymer (B '-2) 36 weight parts, rubber modified phenylethylene resin series (I-1) 20 weight parts, styrene based copolymer (A-1) 44 weight parts, and EBS 0.3 weight part, extrusion condition with preparation example c ', can make the rubber modified phenylethylene resin series (I-4) of tool particle (pellet) shape, rubber constituent amount 20 weight %; The manufacturing prescription and the Physical Property Analysis thereof of this resin (I-4) the results are shown in table six.

Preparation example e '

The preparation of rubber modified phenylethylene resin series (I-5)

With rubber graft copolymer (B '-2) 40 weight parts, styrene based copolymer (A-1) 60 weight parts and EBS 0.3 weight part, extrusion condition with preparation example c ', can make the rubber modified phenylethylene resin series (I～5) of tool particle (pellet) shape, rubber constituent amount 20 weight %; The manufacturing prescription and the Physical Property Analysis thereof of this resin (I-5) the results are shown in table six.

Preparation example f '～l '

The preparation of rubber modified phenylethylene resin series (I-6)～(I-12)

With the operating method of preparation example e ', difference is that the kind of styrene based copolymer (A) and consumption are done an adjustment; The manufacturing prescription and the Physical Property Analysis thereof of this rubber modified phenylethylene resin series (I-6)～(I-12) the results are shown in table six.

Comparative preparation example m '

The preparation of rubber modified phenylethylene resin series (I-13)

With the operating method of preparation example c ', difference is the kind of styrene based copolymer (A) to be done one change; The manufacturing prescription and the Physical Property Analysis thereof of this rubber modified phenylethylene resin series (I-13) the results are shown in table six.

Comparative preparation example n '

The preparation of rubber modified phenylethylene resin series (I-14)

With the operating method of preparation example d ', difference is that the kind of phenylethylene resin series (I) that while grafting legal system is rubber modified and styrene based copolymer (A) is done one and changed; The manufacturing prescription and the Physical Property Analysis thereof of this rubber modified phenylethylene resin series (I-14) the results are shown in table six.

Comparative preparation example o '～s '

The preparation of rubber modified phenylethylene resin series (I-15)～(I-19)

With the operating method of preparation example e ', different locating is the kind of styrene based copolymer (A) to be done one change; The manufacturing prescription and the Physical Property Analysis thereof of this rubber modified phenylethylene resin series (I-15)～(I-19) the results are shown in table six.

[embodiment of flame-retarded phenylethylene series resin composition and comparative example]

Embodiment 1

Rubber modified phenylethylene resin series (I-3) 100 weight parts, incombustible agent (II-1) [tetrabromo-bisphenol (tetrabromo bisphenol A), Grate Lakes system, trade(brand)name BA-59P] 18 weight parts, difficulty are fired the auxiliary agent antimonous oxide (hereinafter to be referred as Sb ₂O ₃) 8 weight parts, reach EBS 0.3 weight part, after mixing so that the Han Xieer mixing machine is dried, again with 180～200 ℃ of raw material tank temperature, the twin shaft extruder fusion with venting port that die head temperature is 200 ℃ is mixed, and can make the flame-retarded phenylethylene series resin composition of tool particle (pellet) shape; The manufacturing prescription and the Physical Property Analysis thereof of this resin combination are listed in table seven.

Embodiment 2

With rubber modified phenylethylene resin series (I-4) 100 weight parts, incombustible agent (II-2) (tetrabromo-bisphenol diglycidylether and tribromophenol annexation, DIC system, trade(brand)name EC-20) 18 weight parts, Sb ₂O ₃8 weight parts, and EBS 0.3 weight part with the extrusion condition of embodiment 1, can make the flame-retarded phenylethylene series resin composition of tool particle (pellet) shape; The manufacturing prescription and the Physical Property Analysis thereof of this resin combination are listed in table seven.

Embodiment 3～4

With the operating method of embodiment 2, difference is the kind of rubber modified phenylethylene resin series (I) to be done one adjust; The manufacturing prescription and the Physical Property Analysis thereof of this flame-retarded phenylethylene series resin composition are listed in table seven.

Embodiment 5

With rubber modified phenylethylene resin series (I-7) 100 weight parts, polycarbonate (the strange U.S. corporate system in Taiwan, trade(brand)name PC-110) 300 weight parts, and incombustible agent (II-3) [dihydroxyphenyl propane two (diphenyl phosphoester), big eight corporate systems, trade(brand)name CR-741] 20 weight parts, after do mixing with the Han Xieer mixing machine, again with 230～250 ℃ of raw material tank temperature, the twin shaft extruder fusion with venting port that die head temperature is 250 ℃ is mixed, and can make the flame-retarded phenylethylene series resin composition of tool particle (pellet) shape; The manufacturing prescription and the Physical Property Analysis thereof of this resin combination are listed in table seven.

Embodiment 6

With the operating method of embodiment 5, difference is the kind of rubber modified phenylethylene resin series (I) to be done one adjust; The manufacturing prescription and the Physical Property Analysis thereof of this flame-retarded phenylethylene series resin composition are listed in table seven.

Embodiment 7～11

With the operating method of embodiment 1, difference is the consumption of the kind of rubber modified phenylethylene resin series (I), incombustible agent (II) and difficult combustion auxiliary agent to be done one adjust; The manufacturing prescription and the Physical Property Analysis thereof of this flame-retarded phenylethylene series resin composition are listed in table seven.

Comparative example 1

With the operating method of embodiment 1, difference is the kind of rubber modified phenylethylene resin series (I) to be done one adjust; The manufacturing prescription and the Physical Property Analysis thereof of this flame-retarded phenylethylene series resin composition are listed in table seven.

Comparative example 2～3

With the operating method of embodiment 2, difference is the kind of rubber modified phenylethylene resin series (I) to be done one adjust; The manufacturing prescription and the Physical Property Analysis thereof of this flame-retarded phenylethylene series resin composition are listed in table seven.

Comparative example 4～5

With the operating method of embodiment 5, difference is the kind of rubber modified phenylethylene resin series (I) to be done one adjust; The manufacturing prescription and the Physical Property Analysis thereof of this flame-retarded phenylethylene series resin composition are listed in table seven.

Comparative example 6～9

With the operating method of embodiment 1, difference is the kind of rubber modified phenylethylene resin series (I) to be done one adjust; The manufacturing prescription and the Physical Property Analysis thereof of this flame-retarded phenylethylene series resin composition are listed in table seven.

Comparative example 10～11

With the operating method of embodiment 3, difference is the consumption of incombustible agent (II) and difficult combustion auxiliary agent to be done one adjust; The manufacturing prescription and the Physical Property Analysis thereof of this flame-retarded phenylethylene series resin composition are listed in table seven.

[evaluation method]

1.MIR

Above-mentioned styrene based copolymer (A) is MI (a g/10 branch) in 200 ℃ of temperature, the measured MFR of loading 1kg, and 200 ℃ of temperature, the measured MFR of loading 10kg are HMI (g/10 branch), the then ratio of MIR=HMI/MI.Wherein, MFR means melt flow index, and this index system measures and gets with ASTM D-1238 method.

2. rubber amount

Fourier transform infrared line spectrometer (FourierTransform Infrared Spectrometer) test with Nicolet corporate system, model Nexus 470.Unit: weight %.

3. measure whole content of bodies by styrenic monomers and nitrilation vinyl monomer institute deutero-two amount bodies or three

After rubber modified phenylethylene resin series (I) was dissolved in acetone, (Hewlett Packard company made by the gas chromatographic detector (GC) with flame ionization detector (FID); Model 5890A) analyzes and measure.Unit is weight %.

4. shock-resistance

Measure according to ASTM D-256 method, test film is of a size of 1/4 inch, attached breach.Unit: kg-cm/cm.

5. drip the combustion phenomenon

With the benchmark of UL-94 VO as test method(s), the test film of used thickness 1/16 inch judges, and repeats 10 times and makes combustion testing, observes the number of times that drips combustion.

Zero: all do not drip combustion.

△: 1～2 time combustion.

*: (contain 3 times) more than 3 times and drip combustion.

6. stress cracking resistance

The test film of 100mm * 12.7mm * 3mm is positioned over impregnated in 30% the spirituous solution time that be full of cracks takes place in determination test sheet dipping back on the tool that radius-of-curvature is 165mm again.Time, long more then stress cracking resistance was good more.

More than zero: 48 hour

△: 24～48 hours

*: in 24 hours

7. stain

After getting 10 grams above-mentioned flame-retarded phenylethylene series resin composition being pressed into the thin rounded flakes of diameter 200mm, thickness 0.3mm with thermocompressor, observe the stain number.

Zero: 0～1 point

△: 2～4 points

*: (contain 5 points) more than 5

[subordinate list explanation]

Table one: the synthesis example of styrene based copolymer (A)

Table five: the preparation example of the phenylethylene resin series (I) that the legal system of grafting simultaneously is rubber modified

Table six: the mix preparation example of the rubber modified phenylethylene resin series of legal system (I) of grafting

Table seven: the modulation of flame-retarded phenylethylene series resin composition

The synthesis example of [table one] styrene based copolymer (A)

Synthesis example and comparison synthesis example					Synthesis example								Compare synthesis example
																		????a	????b	????c	????d	????e	????f	????g	????h	????i	????j	????k	????l	????m
					Styrene based copolymer (A)					????A-1	????A-2	????A-3	????A-4	????A-5	????A-6	????A-7	????A-8														????A-9	????A-10	????A-11	????A-12	????A-13
Reaction conditions	First reactor (R1)	Temperature (℃)																????95	????95	????95	????95	????95	????95	????95	????95	????100	????100	????100	????140	????130
					Stirring velocity (rpm)			????120	????120	????120	????120	????120	????120	????120	????120	????120	????120														????120	????120	????120
		Feed rate (kg/hr)																????36	????37	????36	????36	????36	????37	????37	????37	????40	????40	????40	????37	????37
					Feed composition	????SM	(weight part)	????64.5	????65.5	????64.5	????64.5	????64.5	????60	????61	????73	????68	????68														????68	????65.5	????65.5
		????AN	(weight part)	????35.5														????34.5	????35.5	????35.5	????35.5	????34	????39	????27	????32	????32	????32	????34.5	????34.5
						????MMA	(weight part)						????6
		????BMI	(weight part)	????025														????0.022	????0.007	????0.028	????0.022	????0.022	????0.022	????0.066	????0	????0.01		????0.022	????0
						????DVB	(weight part)																							????035
		The polymerization initiator	Kind	????BPO														????TX-29A	????PX-12	????PX-12	????BPO	????TX-29A	????TX-29A	????TX-29A	????BPO	????BPO	????BPO
						(weight part)	????0.02	????0.01	????0.005	????0.006	????0.02	????0.01	????0.01	????0.01	????0.02	????0.02	????0.02
			Chain-transfer agent	Kind														????TDM	????TDM	????TDM	????TDM	????TDM	????TDM	????TDM	????TDM	????TDM	????TDM	????TDM	????TDM			????TDM
		(weight part)				????0.2	????0.2	????0.2	????0.2	????0.2	????0.2	????0.2	????0.2	????0.2	????0.2	????0.3	????0.2													????0.2
				????EB														(weight part)	????25	????25	????25	????25	????25	????25	????25	????25	????25	????25	????25		????25	????25
		Second reactor (R2)	Temperature (℃)			????105	????105	????105	????105	????105	????105	????105	????105	????120	????120	????120	????150													????140
	Stirring velocity (rpm)																	????90	????90	????90	????90	????90	????90	????90	????90	????90	????90	????90	????90		????90
				Feed rate (kg/hr)			????2	????3	????2	????2	????2	????3	????3	????3																????3		????3
	Feed composition	????SM	(weight part)															????100	????100	????100	????100	????100	????100	????100	????100				????100		????100
				????BMI	(weight part)	????0.22	????0.15	????0.066		????0.2	????0.15	????0.15	????0.45				????0.15													????0
		The polymerization initiator	Kind																	????TX-29A	????TX-29A	????TX-29A
				(weight part)			????0.054	????033	????0.08
			The 3rd reactor (R3)															Temperature (℃)			????135	????135	????130	????135	????135	????135	????135	????135
	Stirring velocity (rpm)			????35	????35	????38	????35	????35	????35	????35	????35
																	Feed rate (kg/hr)			????2		????2	????2	????2
	Feed composition	????SM	(weight part)	????100		????100	????100	????100
																	????BMI	(weight part)	????0.04
		The polymerization initiator	Kind			????TX-29A
																	(weight part)			????0.013
			The 4th reactor (R4)	Temperature (℃)					????135
	Stirring velocity (rpm)																		????35
				Feed rate (kg/hr)
	Physical Property Analysis	MIR															????24	????23.1	????22.5	????23.2	????23	????23.5	????22.7	????26.5	????21	????21.4	????24.1	????22.8	????21.1

R1，R2：CSTR???????????????????R3，R4：plug?flow

The SM styrene monomer

The AN acrylonitrile monemer

The MMA methyl methacrylate monomer

BMI N, N '-4,1 '-ditan bismaleimide amine monomers

The DVB Vinylstyrene

The BPO dibenzoyl peroxide

TX-29A 1, and 1-pair-tert-butyl hydroperoxide-3,3, the 5-trimethyl-cyclohexane

PX-12 2, two (4,4-two-tert-butyl hydroperoxide) the cyclohexyl propane of 2-

Uncle TDM-lauryl mercaptan

EB ethylbenzene

The preparation example of the phenylethylene resin series (I) that [table five] grafting simultaneously legal system is rubber modified

Preparation example and comparative preparation example					Preparation example	The comparative preparation example
							????a’	????b’
					Rubber modified phenylethylene resin series (I)					????I-1	????I-2
Reaction conditions	First reactor (R1)	Temperature (℃)										????100	????100
					Stirring velocity (rpm)			????300	????300
		Feed rate (kg/hr)								????37	????40
					Feed composition	????SM	(weight part)	????65.5	????68
		????AN	(weight part)	????34.5						????32
						????BD	(weight part)	????8	????8
		????BMI	(weight part)	????0.022						????0.0002
						The polymerization initiator	Kind	????TX-29A	????TX-29A
		(weight part)	????0.04	????0.04
							Chain-transfer agent	Kind	????TDM	????TDM
		(weight part)	????0.3	????0.3
						????EB		(weight part)	????35	????35
		Second reactor (R2)	Temperature (℃)				????105				????105
	Stirring velocity (rpm)					????200		????200
				Feed rate (kg/hr)			????3
	Feed composition	????SM	(weight part)					????100
				????BMI	(weight part)	????0.15
		The 3rd reactor (R3)	Temperature (℃)					????115	????115
	Stirring velocity (rpm)					????150	????150
				The 4th reactor (R4)	Temperature (℃)			????130	????130
	Stirring velocity (rpm)									????90	????90
					Physical Property Analysis	Rubber amount (weight %)						????10	????10.3
MIR (styrene based copolymer (A) external phase)				????24.2						????21.1
						By styrenic monomers and nitrilation vinyl monomer derived two the amount bodies or three the amount bodies whole content (weight %)					????0.93	????0.9

R1，R2：CSTR?R3，R4：plug?flow

The SM styrene monomer

The AN acrylonitrile monemer

The BD divinyl rubber

BMI N, N '-4,4 '-ditan bismaleimide amine monomers

TX-29A 1, and 1-pair-tert-butyl hydroperoxide-3,3, the 5-trimethyl-cyclohexane

Uncle TDM-lauryl mercaptan

EB ethylbenzene

The mix preparation example of the rubber modified phenylethylene resin series of legal system (I) of [table six] grafting

Preparation example and comparative preparation example			Preparation example										The comparative preparation example
																				????c’	????d’	????e’	????f’	????g’	????h’	????i’	????j’	????k’	????l’	????m’	????n’	????o’	????p’	????q’	????r’	????s’
			Rubber modified phenylethylene resin series (I)			????I-3	????I-4	????I-5	????I-6	????I-7	????I-8	????I-9	????I-10	????I-11	????I-12	????I-13	????I-14	????I-15	????I-16																		????I-17	????I-18	????I-19
Form (weight part)	Rubber graft copolymer (B ')	????B’-1																		????20										????20
			????B’-2	????36	????36	????40	????40	????40	????32	????46	????40	????40	????40	????36	????36	????40	????40	????40	????40																		????40
		The rubber modified phenylethylene resin series (I) of while grafting legal system																		????I-1		????20
	????I-2													????20
																				Styrene based copolymer (A)	????A-1	????44	????44	????60
	????A-2				????60
																			????A-3						????60
	????A-4						????68
																			????A-5								????54
	????A-6								????60
																			????A-7										????60
	????A-8										????60
																			????A-9												????44	????44	????60
	????A-10														????60
																			????A-11																????60
	????A-12																????60
																			????A-13																		????60
	The extrusion condition	Extruder raw material tank temperature (℃)		?????????????????????????????????????????????????????????????????????????????????????????????????200-220
The extruder die head temperature (℃)																					???????????????????????????????????????????????????????????????????????????????????????????????????220
		Physical Property Analysis	Rubber amount (weight %)		????20	????20	????20	????20	????20	????16	????23	????20	????20	????20	????20	????20	????20	????20	????20	????20																		????20
By styrenic monomers and nitrilation vinyl monomer derived two the amount bodies or three the amount bodies whole content (weight %)																					????0.62	????0.65	????0.6	????0.58	????0.63	????0.68	????0.54	????0.6	????0.62	????0.59	????0.62	????0?61	????0.54	????0.56	????0.57	????1.56	????1.4

The modulation of [table seven] flame-retarded phenylethylene series resin composition

Flame-retarded phenylethylene series resin composition				Embodiment
														????1	????2	????3	????4	????5	????6	????7	????8	????9	????10
				Form (weight part)	Rubber modified phenylethylene resin series (I)	The method of grafting simultaneously	????I-1						????100
????I-2
							The grafting method of mixing	????I-3	????100
????I-4		????100
								????I-5			????100
????I-6						????100
								????I-7					????100
????I-8																????100
								????I-9														????100
????I-10																		????100
								????I-11																????100
????I-12
								????I-13
????I-14
								????I-15
????I-16
								????I-17
????I-18
								????I-19
Other resin		????PC-110														????300	????300
					Incombustible agent (II)		????II-1	????18												????15	????21	????18	????18
????II-2		????18	????18											????18
							????II-3					????20	????20
Difficult combustion auxiliary agent		????Sb2O3	????8											????8	????8	????8			????6					????9	????8	????8
					Physical properties	Shock-resistance (kg-cm/cm)			????16	????12	????11	????12	????28							????25	????17	????18	????17				????17
Drip the combustion phenomenon			????○	????○										????○	????○	????○	????○	????○	????○					????○	????○
						Stress cracking resistance			????○	????○	????○	????○	????○							????○	????○	????○	????○			????○
Stain			????○	????○										????○	????○	????○	????○	????○	????○					????○	????○

PC-110 polycarbonate resin (polycarbonate), the strange U.S. corporate system in Taiwan

II-1 tetrabromo-bisphenol (tetrabromo bisphenol A), Grate Lakes system, trade(brand)name BA-59P

II-2 tetrabromo-bisphenol diglycidylether and tribromophenol annexation, DIC system, trade(brand)name EC-20

II-3 dihydroxyphenyl propane two (diphenyl phosphoester), big eight corporate systems, trade(brand)name CR-741

The Sb2O3 antimonous oxide

Claims (1)

1. a flame-retarded phenylethylene series resin composition is characterized in that this constituent comprises rubber modified phenylethylene resin series (I) 100 weight parts and incombustible agent (II) 1～40 weight part;

Wherein, this rubber modified phenylethylene resin series (I) is by the nitrilation vinyl monomer of the styrenic monomers of (i-1) 50～90 weight parts, (i-2) 10～50 weight parts, other copolymerizable vinyl monomer of (i-3) 0～40 weight part, more than total 100 weight parts of (i-1), (i-2), (i-3), and the multi-functional maleimide of 0.0005～1.0 weight part be monomer institute's copolymerization and styrene based copolymer (A) constitute as disperse phase as external phase and rubber particles (B); Wherein, the rubber amount of rubber modified phenylethylene resin series (I) is 1～40 weight %, and whole content of being measured bodies or three amount bodies by styrenic monomers and nitrilation vinyl monomer institute deutero-two account for below the 1.25 weight % of rubber modified (I); And styrene based copolymer (A) is the MIg/10 branch in 200 ℃ of temperature, the measured melt flow index mfr of loading 1kg, 200 ℃ of temperature, the measured melt flow index mfr of loading 10kg are the HMIg/10 branch, and its melt flow index ratio MIR=HMI/MI is between 21.5～30.0.