TW567191B - Method for preparing thermoplastic styrenic copolymer and thermoplastic resin formed from the copolymer - Google Patents

Abstract

The present invention provides a method for preparing a thermoplastic styrenic copolymer (A) and products and derivatives therefrom. The invented method comprises polymerizing 30 to 100 parts by weight of a styrenic monomer, 0 to 45 parts by weight of nitrilized ethylenic monomer, 0 to 40 parts by weight of copolymerizable ethylenic monomer (100 parts by weight in total), and 0.0005 to 1.0 parts by weight of a polyfunctional maleimide monomer. A thermoplastic resin consisted of the copolymer (A) has excellent processing properties including fluidity and branching properties, etc. A thermoplastic styrenic resin composition consisting of a styrenic copolymer according to the invention and a rubber component also has excellent mechanical properties including fluidity, etc., as well as free of defects, such as thinning, non-uniform gloss on the surface of coating, etc. The styrenic copolymers according to the present invention, besides being applicable on ordinary electronic and electrical products, are particularly applicable on the formation of sheet material for refrigerator.

Description

567191 V. Description of the Invention (1) [Field of the Invention] The present invention provides a method for producing a thermoplastic styrene copolymer (A) and a resin or resin composition thereof, which is based on the thermoplastic styrene copolymer (A ) During the polymerization manufacturing step, a polyfunctional maleimide monomer is added for copolymerization to obtain a thermoplastic resin or a resin composition thereof having the advantages of high fluidity, good divergence, and good molding processability. [Background of the Invention] Powerful and mechanical, and gloss and electrical appliances can be injected into products with specific requirements. In order to achieve the shortcomings of molecular weight uniformity and flowability, improvements such as divinyl compounds are required in the range of 2,-1 827 1 1; low and processability are better than automobile molding and processing, this requirement is required. Can be stable and stable, said Ben Gong, kaikai 'general base (di v, but in the thermoforming thermoplastic styrene resin, have a good evaluation, is a major feature of all parts. Generally speaking During molding and stretch molding, if some of the above resins need to be pre-formed, the resin must have thermoforming or vacuum forming properties. However, generally, the processability of the tree is deteriorated and the productivity is increased. Patent publication such as JP-A-8-269137 It is revealed that the added divergent agent is an inyl) compound or if such single-layer defects are used in multiple passes, it is easy to cause its processing moldability, physics, especially the good shape of the molded product, and it is widely used in electronics, thermoplastic, and stupid vinyl. Resin type and other molding methods. The thermoforming and vacuum forming methods require sheeting and then molding. High melt strength, that is, high tree shape, when the molecular weight of a good thickness and homogeneous grease is maintained, the disadvantages such as reduction will be caused. In order to improve this 5-9-1 4 9 9 1 2 and kaiping, multi-functional reactive monomers, such as acrylate, can be added in the manner of adding divergent agents, although it can avoid the reduction of fluidity Causes resin to adhere

567191 V. Description of the invention (2) Carbide is formed on the surface of the pipeline, and 诰 = the resin has a poor hue. Because of 1 :: =: =; molecular weight, and avoiding the problem of flowable Si which has been waiting for a long time. ',,,'-those skilled in the art, [inventive purpose] That is, the main purpose of the present invention is to provide a ^ copolymer U) made ^ *, which is at the time of (A) polymerization manufacturing steps ， Add multi-functional It, f this ethylene fluorene copolymer copolymerization ... Manufactured according to this; ";;; = = amine monomer k-movability and high degree of divergence, and good molding processability and other advantages. ^ ^ This description Another object is to provide a 敎 ^ ^ ^ ^ product (Ch which is a thermoplastic styrene system, copolymerized ;: B: =; thermal stability and impact resistance of the composition = ί J 2 2 good physical properties, And there is no thin meat phenomenon and uneven gloss of the coating surface. [Detailed description of the invention] And Chengming Department provides a thermoplastic resin with high fluidity, high degree of divergence, and good hue === good workability. The thermoplastic resin consists of 30 It is suspected to be i part of styrene monomer derivative, 0 to 45 parts by weight of nitrile ethylene T = early body derivative, 0 to 40 parts by weight of copolymerizable vinyl monomer derivative, the above total 100 Part by weight, and 0. 0 0 0 5 to 1.0 part by weight of a multifunctional maleimide imide-based monomer derivative Thermoplastic Styrene Page 5 567191 V. Description of the invention (3) Copolymer (A). Specific examples of the styrene monomer are: styrene, α-methylstyrene, p-third Butylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2, 4-dimethylstyrene, ethylstyrene, α-methyl-p-methyl Among them, styrene and bromostyrene are preferred. Among them, styrene or α-methylstyrene is preferred. Each of the above compounds can be used alone or in combination. The styrene-based monomer derivative of the present invention is 30 to 100. Parts by weight, preferably 3 2 to 9 5 parts by weight, more preferably 3 5 to 90 parts by weight. The nitrile vinyl monomer used in the present invention may be acrylonitrile, α-methacrylonitrile, etc. Among them, acrylonitrile is preferred. The nitrile vinyl monomer derivative constituting the present invention is 0 to 45 parts by weight, preferably 2 to 40 parts by weight, and more preferably 3 to 40 parts by weight. Used in the present invention The copolymerizable ethylene-based monomers may be: acrylate-based monomers, fluorenyl acrylate-based monomers, and monofunctional maleimide-based imide-based monomers, and more Functional vinyl monomers, etc. Among them, specific examples of the acrylate monomers include methyl acrylate, ethyl acrylate, isopropyl acrylate, and butyl acrylate, among which butyl acrylate is preferred. Methacrylic acid Specific examples of the ester-based monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl acrylate, and methacrylic acid. Cyclohexyl ester, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, among which methyl methacrylate and butyl methacrylate An ester is preferred. A monofunctional maleimide-based monosystem means that the monomer contains only a single monomer.

Page 6 567191 V. Description of the invention (4) Maleimide functional groups, specific examples of which are: maleimide, N-fluorenylmaleimide, N-isopropylmaleimide Amine, n-butylmaleimide imine N-hexylmaleimide imide, N-octylmaleimide imine, n-h dihexylmaleimide imide, N-cyclohexylmaleimide Imine, N-phenylmaleimide, n-2 '3 or 2,4-monomethylbenzyl imine, N-2,3-or 2,4-diethylbenzyl horse Lyme imine, N-2, 3- or 2, 4-dibutylphenylmaleimide, N-2, 6 diamidophenylmaleimide, N-2, 3- or 2,4-dichlorophenylmaleimide, N-2, 3- or 2,4-dibromophenylmaleimide, etc. Among them, N-benzylmaleimide is preferred. The aforementioned polyfunctional vinyl monosystem does not contain a polyfunctional maleimide-based monomer, and the addition amount thereof is preferably 0 to 4 parts by weight, more preferably 0 to 2 parts by weight, and specific examples are: 1) Divinyl benzene, 1,2,4-trivinylbenzene, 1,3,5-trivinylbenzene benzene) and so on. 2) ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate Ethylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate , 1,6-hexanediol monomethylpropionate (1,6-

Page 7 567191 V. Description of the invention (5) hexylene glycol dimethacrylate), neoopentyl glycol dimethacrylate (PGDMA for short), dipropylene glycol dipropylene glycol di me t ha cr y 1 ate), polypropylene glycol dimethacrylate, 2,2-bis- (4-methacrylateoxydiethoxyphenyl) propane [2, 2-1 ^ 3- (4-11161118〇11〇 and 7 (116 1: 11〇 and 7 phenyl) propane] and other dimethyl acrylates. 3) Trimethylol trimethylol propane trimethacrylate), trimethacrylate and triethylol ethane trimethacrylate. 4) ethylene glycol diacrylate, diethylene glycol diacrylete, tri ethylene glycol diacrylate, polyethylene glycol diacrylate ), 1,3-di-propylene glycol diacrylate, 1,4-di-butylene diacrylate, 1,4-di-butylene diacrylate, 1,6-hexylene glycol diacrylate, neopentyl glycol diacrylate 'PGDA', dipropylene glycol diacrylate ), Polypropylene glycol diacrylate

Page 8 567191 V. Description of the invention (6) di aery 1 ate), 2, 2-bis (4-acryloxypropoxyphenyl) propane [2, 2-bis (4-acry loxy propoxy pheny 1) propane ], 2, 2-bis (4-acryloxy diethoxyphenyl) propane [2, 2-bis (4-acryloxy di ethoxy phenyl) propane] and other diacrylates. 5) Triacrylates such as trimethylol propane triacrylate, triethylol ethane triacrylate, and the like.

6) Tetramethyl methacrylate (tetra trame thy 1 ο 1 me thane tetraacrylate) and other tetraacrylates. 7) Polyfunctional vinyl monomers that do not belong to the above, such as: tetramethylene bis (ethyl fumarate), hexamethylene bis (ethyl fumarate), hexamethylene bis (acrylamide) )], Triallyl cyanate, triallyl cyanate, etc.

In addition, unsaturated monomers such as acrylic monomers (eg, acrylic acid, methacrylic acid), anhydrous maleic acid, anhydrous maleic maleic acid, fumaric acid, and esters and ethylene , Acrylic, 1-butane, 1-pentane, 4-methyl-1-pentene, ethylene chloride, ethylene chloride fork, ethylene tetrafluoride, monogas ethylene trifluoride, hexafluoropropylene, Butadiene, allylamine, isobutyleneamine, vinyl acetate, ethyl vinyl ether, methyl vinyl fluorene, etc. may also be copolymerizable vinyl monomers. The copolymerizable ethylene-based monomer derivative of the invention of the stomach is 0 to 40 parts by weight ', preferably 2 to 40 parts by weight, and more preferably 3 to 38 parts by weight.

Page 9 567191

V. Description of the invention (7) Specific examples of the monomers of the polymerized vinyl-based monomer derivative are as described above, preferably, at least one selected from an acrylate monomer and a methacrylate-based monomer (mono-functional malay) Imine-based monomer. The polyfunctional maleimide imide monomer used in the present invention refers to a compound having two maleimide imine groups, for example, two or three or four maleimide Functional compounds. Among them, bismaleimide-based monomer is preferred, and its structural formula can be expressed by general formula (1)

General formula (1) [wherein X is alkylene, arylene, carbonyl group, -S02-, -SO-, ~ 〇-, -〇-— may be Alkyl'arylene)] Specific examples are: Ν, Ν'-4, 4 '-(3, 3'-difluorenyldiphenylmethane) bismaleimide [N, N'-4, 4 '-(3,3'-dimethyl diphenyl methane) bismaleiraide], N, N'-4,4'-(3,3'-diethyldiphenylmethane) bismaleimide [N, N '_4,4'-(3,3 '-diethyl diphenyl methane) bi sma1e imi de], N, N' -4, 4 '-diphenylmethane bismaleimide (N, N'-4, 4'-diphenyl methane bismaleimide),

Page 10 Support 91

V. Description of the invention (8) N, N, -4, 4 '-(N, N, -4, 4' N, N, -4, 4 '-(N, N' 4 'Ν, N, -3 , 3 '-(Ν, Ν' -3, 3 'Ν, Ν' 4 '-(Ν, Ν, -4, 4' Ν, Ν, -4, 4 '-(Ν, Ν, -4, 4 0parts by weight of the present invention ~ 1.0 parts by weight. The plastic resin of the present invention 0. 0 0 0 5 weight molding The imine-based monomers used in the materials are particularly deteriorating. 2,2-diphenylpropane bismaleimide-2, 2-diphenyl propane bisma1eimide), diphenyl ether bismaleimide-diphenyl ether bismaleimide), diphenyl alum bismaleimide-diphenyl su1fone bismaleimide), diphenyl alum bismaleimide-diphenyl sulfide bismaleimide), diphenyl alum bismaleimide-diphenyl sulfide bismaleimide), benzophenone bismaleimide), and 4,4'-diphenylpyridine bismaleimide are preferred. The polyfunctional maleimide-based monomer derivative is preferably 0.000 ′, preferably 0. 0 (Π ~ 0. 8 parts by weight, and more preferably, 0.03 ~ 0.6. When the thermal polyfunctional maleimide imide-based monomer derivative of the thermoplastic styrene copolymer (A) is less than parts, the thermoplastic resin, especially when used as a polymer, has a large elongation. Poor flowability when used as a multifunctional malaysian thermoplastic molding material. Thermoplasticity formed by the thermoplastic stupid ethylene copolymer (A) of the present invention.

567191

The residual polyfunctional maleimide-based monomer in the resin is not more than 1000 ppm, preferably not more than 60 Ppm, and more preferably not more than 30 ppm. The remaining monomers were measured by dissolving the thermoplastic resin in tetrahydrofuran, and the resin solution X w, Hewlett Packard Company, No. 6890Δ gas chromatograph with a flame extractor ( Gas chromatography). The unit of measurement value is ppm, which is based on i00wt% thermoplastic resin. When the residual polyfunctional maleimide-based monomer is less than 100ppm, the hue of the thermoplastic resin is better. In the thermoplastic resin composed of the thermoplastic styrene copolymer (A) of the present invention, MZ (Z average molecular weight) / MW (weight average molecular weight) ranges from 2 to 8, preferably 2.5 to 7 and more preferably 3 ~ 6. The measurement method uses a gel dialysis chromatograph (manufactured by GPC 'Waters Company) with two functions of differential refractive index detection and light scattering detection as a detector. When the MZ / MW of the thermoplastic resin is between 2 and 8, the fluidity, maximum elongation viscosity, and hue of the thermoplastic resin are better.

It is stated that the divergence ratio (gM) of the thermoplastic resin is between 0.45 and 0.95 [when the molar mass (molar_S) = 1X 106 g / mole (g / m〇1)], the divergent ratio Index of the degree of divergence of polymers

Multi-angle laser light scattering system (Multi-angle laser Ught scatteHng MALLS) manufactured by Technology Corporation, model Minidawn. In this measurement method, the sample obtained by column chromatography is used for each polymer, and the smaller the value, the greater the degree of divergence. The measurement method is a water dialysis gel chromatography (Gpc) series Wyatt

Page 12

567191 V. Description of the invention (ίο) The light scattering measured at different angles is then used to measure the molecular weight of each slice layer. The definition of the divergence ratio is: \ rh (r2) b: the radius of rotation of the divergent molecule (r2) !: the radius of rotation of the linear molecule. , When m〇iar mass = 1 χ 106 (g / m〇1), gM is between

0.45 to 0.95, preferably 0.5 to 0.9, and more preferably 0.6 to 0.8. When the bifurcation ratio gM is between 0.45 and 0.95, the flowability, maximum elongation viscosity, and hue of the thermoplastic resin are better.

— The manufacturing method of the thermoplastic styrenic copolymer (A) of the present invention can be completed by a continuous block or solution polymerization reaction, an emulsion polymerization reaction, and a suspension polymerization reaction, which are generally used; Reverse or solution polymerization is preferred. When the thermoplastic styrenic copolymer (A) of the present invention is completed by a continuous block or solution polymerization reactor, the reaction can include 1: a column flow reactor, a fully mixed (CSTR) ) Reactors, or reactors including static mixers, etc., in which a fully mixed reaction is preferred / I and the number of reactors can be one, or two or two can be used in combination to produce the heat of the present invention. In the case of the plastic styrenic copolymer (A), the preparation method is to continuously feed the raw material solution (丨) for the reaction into the reactor for the reaction, and a polymerization initiator can be added to the reaction. The thermoplastic stupid ethylene copolymer (A) of the present invention can be added during manufacture

Page 13 567191

V. Description of the invention (11) The polymerization initiator is used in an amount of 0 to 1 part by weight, and preferably 10,000 parts by weight. The usable polymerization initiator may be: Initiators or polyfunctional initiators, among which the specific monofunctional initiators are, for example, benzoyl peroxide, dicumyl peroxide, peroxidized tertiary Butyl (t — butyl earth peroxide), t — butyl hydroperoxide, cumene hydroperoxide, (3 — butyl hydroperoxide) buty (peroxy benzoate), di-2-ethylhexyl peroxy dicarbonate, tert-butyl peroxy isopropyl carbonate (BPIC) Cyclohexanone peroxide, 2, 2'-azo-bis-isobutyronitrile, 1,1'-azobis -1,2-, 1-azo-cyclohexane carbonitrile, 2,2'-azo-bis-2-methylbutane Nitrile (2,2'-32〇-1) 13-2-11161; 11711311171'〇1111;]: 116) and the like. Among them, dibenzophenoxide and diphenylisopropyl peroxide are preferred. Specific examples of the polyfunctional starter that can be used in the present invention are: 1,1-bis-t-butyl peroxy cyclohexane (TX-22), 1, 1-bis-third butyl peroxy-3,3,5-trimethylcyclohexane (1,1-bis -1-butylperoxy- 3,3,5-trimethyl cyclohexane, TX-29A for short), 2 , 5-dimethyl-2, 5-bis- (2-ethylhexanoxy) hexane [2, 5-dime thy 2, 2, 5-bis- (2-ethylhexanoxy peroxy) hexane], 4- (Third butyl peroxide

Page 14 567191 V. Description of the invention (12) Tetyl) -3-hexyl-6- [7- (Third-butylperoxy) heptyl] cyclohexyl {4- (t-butyl peroxy carbonyl) -3-hexyl-6- [7- (t-butyl peroxy car bony 1) hep ty 1] cyclohexane}, di-t-butyl-diperoxyazelate, 2 , 5-dimethyl-2,5-bis (benzyl peroxide) -hexane [2,5-dimethyl-2,5-bis- (benzoyl peroxy) hexane], di-third butyl peroxide -Hexahydro-terephthalic acid (di-t-butyl peroxy-hexahydro-terephthalate, referred to as ΒΡΤΤΗ), 2,2-bis (4,4-di-tert-butylperoxy) cyclohexylpropane [ 2,2-bis- (4,4-di-1-butyl peroxy) cyclohexyl propane], etc .; among them, 1,1-bis-third butyl peroxy-3, 3, 5-trimethylcyclohexane Di-tertiary butyl peroxide-hexahydro-terephthalate is preferred. The reaction temperature of the above-mentioned reactor is controlled at 20 ~ 300 ° C, preferably 60 ~ 250 ° C, more preferably 80 ~ 200 ° C. 5 The pressure of the reactor is controlled at 1 Between ~ 10 kg / cm2, the time that the raw material solution stays in the reactor is generally from 0.5 to 15 hours, preferably 10 hours; and in order to control the molecular weight of the polymer, the thermoplastic benzene of the present invention In the production of the ethylene-based copolymer (A), a chain transfer agent may be used, and the amount thereof is 0 to 2 parts by weight, preferably 0.001 to 1 part by weight; the chain transfer agent used in the present invention may be Monofunctional chain transfer agent or φ multifunctional chain transfer agent, and specific monofunctional chain transfer agents are: 1) Mercaptans: methyl mercaptan, n-butyl mercaptan, cyclohexylsulfide Alcohol, n-dithiol mercaptan, steary 1 mercaptan, tertiary dodecyl mercaptan (TDM), n-propyl mercaptan, n- -Octyl mercaptan

Page 15 567191 V. Description of the invention (13), third-octyl mercaptan, third-nonyl mercaptan, etc. 2) Alkylamines: monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, di-n-butylamine, triamine -N-butylamine and the like. 3) Other examples: pentapheny lethane, a-methyl styrene dimer, terpinolene, among which the normal thiols are- Dodecyl mercaptan and tertiary dodecyl mercaptan are preferred. Polyfunctional chain transfer agents are, for example, isopentaerythritol tetrakis (3-mercaptopropionate) [pentaerythritol tetrakis (3-mercapto propionate)], isopentatriol tetrakis (2-mercaptoacetate) [pentaerythritol tetrakis (2 -mercapto ethanate)], isopentaerythritol tetrakis (4-mercapto butanate) [pentaerythritol tetrakis (4-mercapto butanate)], isopentatriol tetra (5-mercapto butanate) [pentaerythritol tetrakis (5-mercapto pentanate)], pentaerythritol tetrakis (6-inercapto hexanate)], trimethylolpropane tris (2- mercapto ethanate)], trimethylolpropane tris (3-mercapto propionate) (TMPT), tri- (6-mercaptohexanoic acid) [trimethylol-propane tris (6-mercapto hexanate)] and the like; among the above, tris- (3-weiylpropionic acid) trishydroxypropylpropyl ester is preferred. After the polymerization of the polymer is completed, the obtained copolymer (A) is usually dissolved.

Page 16 567191 V. Description of the invention (14) f Use a preheater to heat, and then remove the unreacted monomer and other volatiles in a devolatization step. Generally, a decompression device can be used in the devolatization step. f Extrude the degassing device to remove the volatiles, and then use cold = liquid 'and remove the moisture in the recovery liquid, and then re-use as the original Su = devolatized polymer melt. Thermoplastic styrene copolymer (A). The raw material solution (I) for the thermoplastic styrene-based copolymers invented by the waiter includes right q η 1 η η Tongue A # 〇〇45 重 IP 沪 #t Reset parts of styrene-based monomer Body, ^ Li nitrile vinyl soap body, 〇 ~ 40 weight parts of copolymerizable ethylene ^ early —, the total of the above 100 parts by weight, 〇 0 005 ~ 1. 〇 parts by weight of multi-guan At sex Malay The imine-based monomer, 〇 ~ 60 weight = B month dagger-based monomer is preferably 32 ~ M, and the medium is preferably styrene, ^ 32, 95, and more preferably 35 ~ 90. Parts by weight. Xu Wai series monomer is preferably 2 to 40 parts by weight, more preferably ^ to ㈣ weight; Ug = vinyl series monomer is preferably 2 to 40 parts by weight, more preferably 3 to 38 weight ::, two = The functional maleimide imide-based monomer is preferably 0.003 to 0.6 parts by weight. In the case of Xia Li, the raw material solution used in the process is the same as that described above. Here, ": 糸 monomer 'is preferably selected from at least one kind of propionate." Acid i: Body weight: Monofunctional maleimide imide monomer η. The wound is preferably 2 to 40 parts by weight, more preferably 3 to 38 parts by weight. Toluene, o-xylene, m-xylene ethyl acetate, 7 ethylbenzene and pentane, octane, cyclohexane

567191 V. Description of the invention (15), and acetophenone, propionate, and butylene are equivalent. In the present invention, the thermoplastic stupid ethylene-based copolymer (A) can be further used as the continuous phase, and the rubber particles (B) can be used as the dispersed phase to obtain a thermoplastic styrene-based resin composition (C), in which the thermoplastic styrene The manufacturing method of the resin composition (C) is a method in which a rubber component can be added to a polymerization process of a thermoplastic styrene-based copolymer (A), and participates in the reaction to form a thermoplastic styrene containing rubber particles (B). Based resin composition (c), or rubber components such as general rubber or rubber graft copolymers, especially rubber graft copolymers, which are directly mixed and extruded with the thermoplastic styrene copolymer (A) of the present invention A thermoplastic styrene-based resin composition was obtained. The weight-average particle diameter of the rubber particles (β) is generally from 0.05 to 10 / zm, more preferably from 0 ·, and more preferably from 1 to 5 / zm ', to 0. Bu. The polymerization method can be formed by a block or solution polymerization reaction, an emulsion polymerization reaction or a suspension polymerization reaction generally used. The following two methods are used for illustration: Method 1: It is prepared by continuous block polymerization or solution polymerization.

The manufacturing method of the thermoplastic styrene resin composition (◦) of the present invention can be completed by a generally used continuous block or solution polymerization reaction; the reactor may include: a column flow reactor , Complete mixing (CSTR) reactors, or reactors with static mixers, etc., of which complete mixing reactors are preferred, and the number of reactors can be one, or two or more can be used in combination; The thermoplastic styrene resin composition (C) of the present invention is manufactured by continuously feeding the reacted raw material solution (π) into the reactor for the reaction, and the reaction temperature is controlled at 30 ~ 3 0 ° c , Preferably 60 ~ 25Gt, more preferably fine. c, and the pressure of the reactor is controlled at

Page 18 ^ 67191 V. Description of the invention (16) ^ J ^ t ^ ^ ^ ^ ^ ^ ^ < af f01 J: Amount, I # Μ θ # 1 乂 佺 is small 4; and is a molecule that controls the polymer The description of the Z1ί system in the manufacture of the styrene-based resin composition (c) is the same as that used in the above-mentioned thermoplastic styrene copolymer (A), and is not described here. Solution: = :; Γ: Closing 7 · 'is usually to dissolve the obtained resin composition with 0 ..., and then remove the unreacted monomer by the devolatilization step and formula: ^ 山 二 = 々General dehydration In the volatilization step, the device of the degassing degassing tank can be used to remove the volatiles, and then collected by a condenser into # 2 to remove the moisture in the recovered liquid, and then use it as a raw material solution again. The volatile polymer melt is extruded and granulated to obtain the thermoplastic stupid vinyl resin composition (c) of the present invention. πTake ^ ^ The shape or solution of the thermoplastic styrene resin composition (c), Λ: ΐ The raw material solution (11) used contains: 30 to 100 parts by weight of styrene monomer, 0 to 45 parts by weight of a nitrile vinyl-based monomer, 0 to 40 parts by weight of copolymerizable = vinyl-based monomer, the total of the above is 100 parts by weight, and 0.005 to $ 0 parts by weight of polyfunctional Malay醯 imine-based monomer, 0 ~ 60 weight parts of solvent and L 5 ~ 25 weight parts of rubber; among them, styrene-based monomer, nitrile ethylene, single, other copolymerizable ethylene-based monomers, etc. The functional amount and functional description of the functional Malayan monomers, monomers, and polymerization initiators and chain transfer agents are the same as those of the raw material solution (I), and will not be repeated here. 'In the block or solution polymerization of the thermoplastic stupid vinyl resin composition (C) of the present invention, as the graft polymerization proceeds, the monomers are grafted onto the rubber.

Page 19 567191 V. Description of the invention (17) On the rubber, the rubber component undergoes a reverse reaction and changes from the original continuous phase to the dispersed particle phase, and forms a weight in the final thermoplastic styrene resin composition (C). The average particle diameter is from 0.05 to 10, preferably from. To 5 // m, and more preferably from 0.1 to 1 #m of rubber particle phase. Specific examples of the rubber in the raw material solution (Π) include diene rubber, polyolefin rubber (example: ethylene-propylene rubber), polyacrylate rubber, polysiloxane rubber, and the like. The aforementioned diene rubber is a polymer whose glass transition temperature is below 0 ° C after the diene monomer component is polymerized. Specific examples of the diene rubber: butadiene rubber, isoprene rubber, chlorine Butadiene rubber, EPDM rubber, styrene-diene rubber, acrylonitrile-diene rubber, etc .; of which, butadiene rubber has high cis (Hi-Cis) content and low cis (L0w- Cis) content; in Nanshun rubber, its cis (Cis) / vinyl (

Vinyl) has a typical weight composition of (94 ~ 99%) / (〇 ~ 5%), and the rest of the composition is a trans structure; its Mooney viscosity is between 20 and 120, and its molecular weight ranges from 10, 000 ~ 800, 〇〇〇 is better; in low cis rubber, the typical weight composition range of cis / vinyl is (20 ~ 40%) / (6 ~ 20%), the rest is trans structure, its Mooney viscosity is between Between 20 and 120, the molecular weight range is preferably 100,000 to 80,000; specific examples of styrene-diene rubber are styrene-butadiene rubber, styrene-isoprene rubber Etc., which may be a block co-reformer, a random copolymer, or a copolymer whose composition gradually increases / decreases (taper). Among them, the weight ratio of stupid ethylene in styrene / butadiene rubber is preferably 50% by weight or less, and the molecular weight range is preferably 50,000-600,000; the above-mentioned rubber is preferably Butadiene rubber and styrene / butadiene rubber are preferred. Method Two: Graft copolymerization of a thermoplastic styrene copolymer (A) and rubber

Page 20 56il91 V. Description of the invention (18) Object (D) is mixed and extruded. The thermoplastic ethylenic resin composition (C) of the present invention can also be dry-blended by a thermoplastic styrene copolymer (A) and a rubber graft copolymer (D) using a general Henschel mixer. After that, use a mixer such as an extruder mixer, a kneader or a Banbury mixer to blend the mixture, and then extrude the granules. Among them, the 'rubber graft copolymer (D) can be reacted by a block or solution polymerization reaction, an emulsion polymerization reaction which is generally used. The rubber graft copolymer (D) method is based on a raw material solution (Π) as follows: 30 to 100 parts by weight of a styrene dilute monomer, 0 to 40 parts by weight of 100 parts by weight, 0 to 0 parts by weight 60 parts by weight of the aforementioned raw material solution (m) does not include a specific example of a multi-rubber component, which explains that in the original graft copolymerization of the present invention, the ingredients of the "adherent graft polymerization reaction" undergo reverse reaction from the original, and the final The average particle size control of thermoplastic styrene: 0.05 ~ 1 0 // m, compared with # πι rubber particle phase. It should be suspended polymerization reaction to complete the block or solution polymerization reaction. Grafting t-reaction reaction 'raw material solution (melon) -based monomer, 0 ~ 4 5 parts by weight of nitrile ethylene copolymerized ethylene-based monomer , The above combined solvent and 0.5 to 25 parts by weight of rubber; functional maleimide imide-based monomer, and the description of the feed solution (Π). Monomer or solution polymerization reaction of polymer (D) 'monomers are grafted on the rubber, and the continuous phase from rubber is transformed into particle dispersed phase. The olefinic resin composition (C) has a weight of 0.1 to 5 // m. It is more preferable that the o pj is grafted and co-polymerized at home, and the saccharification is completed. The method is to use 40 ~ 90 parts by weight of the rubber emulsion (solid content) and 100 ~ 30% by weight of the monomer, 60 to 10 parts by weight of monomers or monomer mixtures such as nitrile vinyl monomers 0 to 45% by weight, and other copolymerized monomers 0 to 40% by weight,

567l9i V. Description of the invention (19) = Grafting reaction with emulsifier, initiator and chain transfer agent added as needed to obtain rubber graft copolymer emulsion; and then grafting the aforementioned copolymer emulsion Through the steps of coagulation, dehydration, and drying, the rubber graft copolymer (D) of the present invention is obtained. The specific examples of the rubber composition of the rubber emulsion are the same as those of the raw material solution (π). The rubber composition is better. Diene-based rubber emulsions can be diene-based monomers (such as butadiene) or diene-based monomers 100 to 50% by weight and other copolymerizable monomers, such as styrene, Copolymerizable monomers such as acrylonitrile and (meth) acrylic acid esters are polymerized by emulsion polymerization to produce rubber emulsions with an average particle diameter of 0.05 to 0.003 m; the weight of the aforementioned & polymerized polymerization method can also be obtained After the small particle size rubber emulsion having an average particle size of 0.05 to 0.20, # to cold; the East Mast method, the mechanical mast method or the additive mast method, the aforementioned small particle size rubber emulsion is enlarged to a weight average particle size. 22 ~ 〇6: Two in preparation for further graft copolymerization reaction; in #, the additive is fertile; the additives of m can be: acid acetate, hydrogen chloride, sulfuric acid and the like, or sodium lice, potassium gas, For salt-based substances such as calcium vapor, ^ (fluorenyl) acrylic acid_ (meth) acrylic acid ester-based copolymers (such as butyl acrylate copolymer, methacrylic acid_acrylic acid) specifically contain carboxylic acid groups. Polymer agglutinating agent.有 In the present invention, the thermoplastic stupid vinyl resin composition (c) is 40% by weight, preferably 35% by weight, and more preferably 6, weight: 'When the rubber content is between 40% by weight , Then the thermoplastic resin composition (C) has better mechanical properties such as impact strength and fluidity? Rubber modified thermoplastic styrene resin composition of the present invention

Page 22 567191 V. Description of the invention (20) (c) The remaining polyfunctional maleimide-based imine monomer is 100 ppm or less, preferably 60 ppm or less, and more preferably 30 ppm or less. When the remaining polyfunctional horse is If the lymeimide-based monomer is less than 1000 ppm, the thermoplastic styrene resin composition (C) has better thermal stability and fewer stains. In the thermoplastic styrene resin composition (c) of the present invention, in the composition of the thermoplastic styrene copolymer (A), the polyfunctional maleimide-based monomer has a biological content of 0.0 005 to 1. Part by weight, preferably 0.000 0.8, part by weight, more preferably 0.03 to 0.6 parts by weight; when the content of the polyfunctional maleimide-based monomer derivative is less than 0. · When it is 005 parts by weight, the "plastic resin composition", especially when used as a thermoplastic molding material, has a thinning phenomenon during vacuum molding, and the coating table: 2 Two non-uniform '* polyfunctional maleimide imide-based monomer derivatives (3. m m ΐ 份 parts') thermoplastic thermoplastic styrenic resin composition is not good: Him: plastic molding material use, money Good stability, can be uneven and the gloss of the coating surface is not uniform. Ethylene styrene-ethyl fluorene copolymer ⑴ or thermoplastic benzene oxidation: π ^, if necessary, can add various additives such as antioxidants, colorants, etc., Adding time can be used in tinctures: electrification prevention (A) or thermoplastic stupid detection, ... Copolymers Ethylene Copolymers ⑴ or Thermoplastic Decabenzene 1 Ethylene 00 Heavy Summer: of _ parts by weight or less. Other additives such as 糸 resin composition ⑹ 6 need to be added, the amount of addition is generally equal to = 1, impact modifier It can also be seen in 100 parts by weight of thermoplastic benzene 567191 V. Description of the invention (21) 30 parts by weight or less of the ethylene-based copolymer (A) or the thermoplastic styrene resin composition (c). In the plastic styrene copolymer (A) or the thermoplastic stupid vinyl resin composition (C), other resins such as acrylonitrile-butadiene_stuple ethylene resin, acrylonitrile-stupil ethylene resin, and propylene Nitrile-butadiene-α-fluorenyl styrene resin, acrylonitrile-styrene-methacrylic acid methyl ester resin, acrylonitrile-benzyl ethylene-N phenylmaleimide resin, styrene-anhydrous maleic acid resin , Styrene-N phenylmaleimide resin,

Polymethyl methacrylate, polycarbonate resin, styrene-methacrylic resin, methacrylic acid-butadiene-styrene resin, acrylonitrile-butadiene-N-phenylmaleimide-styrene Resin, polyamide resin, polyester resin, polybenzyl resin, acrylonitrile-acrylic acid rubber_styrene resin, acrylonitrile_ (ethylene-propylene diene rubber) —styrene resin, acrylonitrile—silicone -Styrene resin and other resins, which can be used alone or in combination. It is generally used in an amount of 80 parts by weight or less based on 1,000 parts by weight of the thermoplastic styrene copolymer (A) or the thermoplastic styrene resin composition (c). [Example 1] Preparation of thermoplastic styrenic copolymer (A- 丨) 68 parts by weight of styrene monomer, 32 parts by weight of acrylonitrile monomer, N, N, ψ -4, 4'-diphenyl 0.02 parts by weight of methanebismaleimide monomer, 200 parts by weight of ethylbenzene, 0.02% by weight of benzyl peroxide peroxide as a polymerization initiator, and second-order dodecylmercaptan 〇 2 parts by weight of raw materials are mixed and continuously supplied to two series-type fully-mixed continuous reactors, the reactor volumes of which are 40 liters and 70 liters, respectively, and the internal temperatures of the two reactors are maintained at 1 〇 〇

Page 24 567191 V. Description of the invention (22) ° C and 120 ° C, the pressure of the reactor is maintained at 4 kg / cm2, and the total residence time in the reactor is 2 hours. The monomer conversion rates of the two reactors are maintained separately. 30% by weight and 50% by weight. After the polymerization is completed, the obtained copolymer solution is usually heated by a preheater, and then the unreacted monomers and other volatile components are removed by devolatilization in a decompression degassing tank. The thermoplastic styrenic copolymer (A-1) of the present invention can be obtained by extruding and granulating it; the manufacturing formula of the thermoplastic styrenic copolymer (A-1) and its physical properties are listed in Table 1. [Example 2] The thermoplastic styrene copolymer (a-2) was prepared in the same manner as in Example 1. The difference was that N, N'-4, 4, -diphenylphenylmethane bismaleate The amount of fluorene imine monomer is adjusted to 0.01 parts by weight; the manufacturing formula of the thermoplastic styrenic copolymer (A-2) and its physical properties are listed in Table 1. [Example 3] The thermoplastic styrene copolymer (A-3) was prepared in the same manner as in Example 1. The difference was that the amount of each monomer mixed was adjusted to 58 weight of styrene monomer. Parts, 22 parts by weight of acrylonitrile monomer, N, N'-4,4'-di-benzylmethane bismaleimide monomer, 0.00 parts by weight, and additional N-phenylmaleimide The monomer (N-phenyl maleimide, referred to as N-PMI) is 20 parts by weight; the manufacturing formula of the thermoplastic styrene-based ||| copolymer (A-3) and its physical properties are listed in Table 1. [Example 4] Thermoplastic stupid ethylene copolymer (A-4) was prepared in the same manner as in Example 1, except that the raw materials were mixed, and neopentyl glycol dipropionic acid g monomer was added. (Neopentyl glycol diacry late, referred to as PGDA) 0.01 parts by weight, and the polymerization initiator

Page 567191

V. Description of the invention (23) Change the type to 1, 1, 3, 3, 5-trimethylcyclohexane (1, 1-bis-t-butylperoxy-3, 3, 5-trimethyl cyclohexane (referred to as TX-29A) 0. 01 5 parts by weight, the internal temperature of the reactor is maintained at i 20 ° C and 140 ° C, respectively, the thermoplastic styrene-ethyl fluorene copolymer (A-4) The manufacturing formula and its physical properties are listed in Table 1. [Example 5] Preparation of thermoplastic styrene copolymer (a-5)

100 parts by weight of styrene monomer, 0,02 parts by weight of N, N, -4,4, _diphenylmethane bismaleimide monomer, 8 parts by weight of ethylbenzene, and a polymerization initiator peroxidized Dibenzidine 0.20 parts by weight and the chain transfer agent tertiary dodecyl mercaptan 0.20 parts by weight of raw materials were mixed and continuously supplied to three series-type complete mixing continuous reactors, and the reaction The volume of the reactor is 100 liters. The internal temperature of the reactor is maintained at 110 ° C, 130 ° C and 160 ° C, the pressure of the reactor is maintained at 3 kg / cm2, and the total residence time in the reactor is 7 hours. The monomer conversion rates of the three reactors were maintained at 30 weights, respectively. /. 60% by weight and 85% by weight.

After the polymerization is completed, the obtained copolymer solution is usually heated by a preheater, and then the unreacted monomer and other volatiles are removed by degassing in a reduced pressure degassing tank. The extruded granulation can obtain the thermoplastic stupid ethylene copolymer (A-5) of the present invention. The manufacturing formula of the thermoplastic stupid ethylene copolymer (A-5) and its physical properties are listed in Table 1. [Comparative Example 1] The thermoplastic styrene copolymer (A-6) was prepared in the same manner as in Example 1, except that N, N'-4, 4'-diphenylmethane bismaleate was not used.醯 imine monomer. The manufacturing formula of this thermoplastic styrene-based copolymer (A-6) and its physical properties are shown in Table 1.

Page 26 567191 V. Description of the invention (24) --- [Comparative Example 2] The thermoplastic styrene copolymer (a-7) is prepared in the same manner as in Example 1, except that N, n, ~ 4 4, The amount of mono-phenylmethane bismaleimide monomer is adjusted to a wide range. 7 The manufacturing formula of the thermoplastic styrene copolymer (A-7) and ^ are listed in Table 1. Wan and its physical properties analysis [Example 6] Preparation of thermoplastic styrene resin composition 组成 — 丨) 74 parts by weight of styrene monomer, 26 parts by weight of acrylonitrile monomer, 12 parts by weight of butadiene rubber, N , N, -4,4,4-diphenylmethane bismaleimide subbody 0.02 weight part, ethylbenzene 20 weight part, polymerization initiator diphenyl peroxide 0.05 weight part and The chain transfer agent tertiary dodecyl mercaptan 0.3 parts by weight of raw materials are mixed and continuously supplied to four series-type fully-mixed continuous reactors, each of which has a volume of 45 liters. Internal temperature: ^ 95, 10 (TC, 110 u12 (rc, the reactor pressure, respectively, 5 kg / cm2, 4 kg / cm2, 4 kg / cm2 and 4 kg / cm2, the reactor Inner tick :: time is 4 hours, the monomer conversion rate of the four reactors is maintained at 2; %%, 31% by weight, 45% by weight, and 52% by weight. ^ ^ After the copolymerization is completed, usually the obtained The copolymer solution is I, II, I, and then removed in a reduced pressure degassing tank to remove unreacted monomers and ^ ~ ^^; and the depolymerized polymer melt, Extruded and granulated, that is, the phase is: tt stupid vinyl monomer derivative, fluorinated vinyl monomer derivative (B) = can, stupid vinyl copolymer (A) as a continuous phase, rubber The particle / Γ_η is the weight average particle diameter of the plastic colloidal particles (β) of the thermoplastic stupid vinyl resin composition composed of the dispersed phase of the blade; 0.81 // m; the manufacturing formula of the thermal ethylene resin composition (cn and its physical properties) Minute

567191 V. Description of the invention (25) The analysis is shown in Table 2. [Example 7] Preparation of thermoplastic styrene resin composition (c-2)

The method of operation is the same as that of Example 6, except that the type and amount of the raw material mixture are adjusted, which are 66 parts by weight of styrene monomer, 23 parts by weight of acrylonitrile monomer, and N-phenylmaleic acid. Imide monomer 丨 丨 weight part, 20 parts by weight of ethylbenzene, 11 parts by weight of butadiene rubber, N, ν '~ 4,4, -diphenylmethanebismaleimide imide monomer 0.02 weight Parts, 0.55 parts by weight of neopentyl glycol dipropylene ^ ester body, 0.05 parts by weight of polymerization initiator dibenzylmethoxide and chain transfer agent tertiary dodecyl mercaptan 0.3 Parts by weight of raw materials are mixed; the rubber particles (B) of the thermoplastic styrene resin composition (c-2) have a weight average particle diameter of 0.8 · m; the thermoplastic styrene resin composition (C- 2) The manufacturing formula and its physical properties are listed in Table 2. [Comparison Example 3] The thermoplastic stupid vinyl resin composition ([_ 3) was prepared in the same manner as in Example 6, except that N, N, 4, 4, 2-dibenzyl sintered was not used. Bismaleimide imide monomer; rubber particles (B) of the thermoplastic stupid resin composition (C-3) weight average particle diameter 0.8 · m "δ xuan thermoplastic styrene resin composition (◦-3) The manufacturing formula and its physical properties are listed in Table 2.

[Comparative Example 4] The thermoplastic styrene resin composition (c-4) was prepared in the same manner as in Example 6, except that N, n, -4, 4, -diphenylmethane bismaleate was used. The amount of fluorene imine monomer is adjusted to 丨. 1 part by weight; the manufacturing formula of the thermoplastic vinyl fluorene resin composition (C-4) and its physical properties are listed in Table 2. [Reference Example 1] Preparation of rubber graft copolymer (D-1)

Page 28 567191 V. Description of the invention (26) 72 parts by weight of styrene monomer, 28 parts by weight of acrylonitrile monomer, 20 parts by weight of ethylene monomer, 6.5 parts by weight of butadiene rubber, polymerization initiator peroxide 0.05 parts by weight of benzamidine and 0.3 parts by weight of dodecyl mercaptan of the chain transfer agent tertiary dodecyl mercaptan are mixed and continuously supplied to four series-type fully-mixed reactors whose reactor volumes are all It is 4 5 liters. The internal temperature of the reactor is maintained at 90 ° c, 100 Ό, 110 ° C, and 120 ° c. The pressure in the reactor is maintained at 4 kg / cm2. The monomer conversion rate of the four reactors is maintained at 23 weights. %, 35% by weight, 42% by weight, and 51% by weight. After the copolymerization of the copolymer is finished, usually the copolymer solution obtained is heated by a heater and then removed in a reduced pressure degassing tank to remove unreacted monomers and volatiles. Weight average particle diameter of rubber particles ：: (Rubber content 10% by weight [Reference Example 2] Preparation of rubber graft copolymer (D-2) °

Parts I parts by weight | --1 --— — I 150.00 I ^ — — Ή I 1 5. 00 | —I — — Ή I 2.00 I to h I 1,3-butadiene 丨 丨-— one one — —— 丨 potassium persulfate solution (1%) l · — | " _ — | · _ 丨 1 — _ _ I potassium oleate

J

Page 567191

Page 30 567191 V. Description of the invention (28)

Distilled water 200.〇〇 According to the above formula for 5 hours at a reaction temperature of 75 ° C, 缸 缸 judging the conversion rate of about 95%, ρ 6 value 6 · 0 polymer coagulant containing carboxylic acid group.

After that, 3 parts by weight (dry weight) of a polymer containing a wei acid group was used to enlarge 100 parts by weight of a synthetic rubber latex. The pH of the obtained rubber emulsion was 8.5, and the average rubber particle diameter was About 0.31 # m ° Finally, the grafting was carried out, and then the above-mentioned hypertrophized rubber emulsion was polymerized according to the following formula to produce a rubber graft copolymer (D-2). I into I -----------

Parts I by weight I. --- Old_ '--' — | Feibu Dahua Rubber Emulsion (Dry Weight) | ΐοο · StyreneΗ 75. 0 l · Acrylonitrile l · l · Third grade twelve Alkyl mercaptan cumene hydroperoxide

25. 0 | I 2. 0 | I 3 · 0 I

Page 31

567191 V. Description of the invention (29) I 3. 0 I ———— j— — — — —j I Ferrous sulfate solution (0, 2%) I — * —-- I Formaldehyde sodium hyposulfite solution (丨0 〇 / 〇)

—I — * -—.. ......... —___ I — —-— Ethylene diamine tetraacetic acid solution (0.25%) The rubber graft copolymer solution prepared according to the formula above is used to Gasification about coagulation ', and then dehydration and drying to less than 2%, the rubber graft copolymer (D-2) required by the present invention (rubber content 50% by weight, rubber weight average particle diameter 0 · 31 # m) 〇 [Example 8] Preparation of thermoplastic styrene resin composition (c-5) 20 parts by weight of a rubber graft copolymer (D-1) and 30 parts by weight of a rubber graft copolymer (D-2) Parts, thermoplastic styrenic copolymer (A —) 50 weight injury--ethylene bisstearamide (EBS) 0.3 parts by weight, dry-mixed with a Hanschel mixer Then, the raw material tank temperature 2 0 0 ~ 2 2 0 C 'die head temperature 2 2 0 ° C with a twin-shaft extruder with an exhaust port and kneading' can produce pellet-like heat (pe 1 1 et) Plastic styrene-based resin composition (C-5) and its rubber particles (B) average particle size 0.36 / zm; the | formula for manufacturing thermoplastic plastic styrene-based resin composition (C-5) and its Physical properties They are listed in Table III. [Example 9] The thermoplastic styrene resin composition (C-6) was prepared in the same manner as in Example 8, except that the thermoplastic styrene copolymer (A-1) was made of thermoplastic styrene Copolymer (A__3)

Page 32 567191 V. Description of the invention (30), and the raw material tank temperature is 220 ~ 24 (TC 'die temperature 24 (rc; the thermoplastic styrene resin composition (C-6) manufacturing formula and its physical properties) The analysis is shown in Table 3. [Persistent Example 10] Preparation of thermoplastic styrene resin composition (c-7) 36 parts by weight of a rubber graft copolymer (D-2) and a thermoplastic styrene copolymer (A-1) 64 parts by weight and 0.3 parts by weight of bisethylstearylamine, dry-blended with a Hanschel mixer, and then at a raw material tank temperature of 2000 to 2200, the die head Mixing with a twin-shaft extruder with an exhaust port at a temperature of 220 t can produce pellet-shaped thermoplastic stupid vinyl resin composition (c_7) and the average weight of rubber particles (B). 3l // m; The thermoplastic formulation of ethylene-based resin composition (C-7) and its physical properties are listed in Table 3 ° [贯 例 11] Thermoplastic stupid ethylene-based resin composition (c-8 ) Preparation / Consistent operation method of Example 10, except that the thermoplastic styrene copolymer (A-1) is a thermoplastic styrene copolymer (A-3) replace 'and the raw material tank temperature is 220 ~ 240 ° C, the die temperature is 240 ° C; the manufacturing formula of the thermoplastic styrene resin composition (C-8) and its physical properties are listed in Table 3. [Comparative Example 5] Thermoplastic stupid vinyl resin composition (c-9) was prepared in the same manner as in Example 8. The difference was that the thermoplastic styrene copolymer (A-1) was made thermoplastic. The stupid ethylene-based copolymer (A-6) was substituted, and ② The manufacturing formula of thermoplastic ethylenic resin composition (C-9) and its physical properties are listed in Table 3. [Comparative Example 6] Thermoplastic styrene-based resin Preparation of composition (c_1〇)

Page 33 567191 V. Description of the invention (31) The operation mode is the same as that in Example 8, except that the thermoplastic styrene copolymer (A-1) is replaced by the thermoplastic styrene copolymer (A-7). ; The manufacturing formula of the thermoplastic styrene resin composition (C-1 0) and its physical properties are listed in Table 3. [Comparative Example 7] The thermoplastic styrene resin composition (c— 丨 丨) was prepared in the same manner as in Example 10 except that the thermoplastic styrene copolymer (A-1) was made thermoplastic The styrenic copolymer (A-6) is substituted; the manufacturing formula of the thermoplastic styrenic resin composition (C-11) and its physical properties are listed in Table III. [Comparative Example 8] The thermoplastic styrene resin composition (c-1 2) was prepared in the same manner as in Example 10 except that the thermoplastic styrene copolymer (A-1) was thermoplastic Styrenic copolymer (a-7) substitution: The manufacturing formula of the thermoplastic styrene resin composition (C_12) and its physical properties are listed in Table 3. The physical property measurement standards in the examples and comparative examples of the present invention are as follows: 1 · Composition of thermoplastic resin or thermoplastic styrene-based resin composition (C): Rich by model Nicolet company, model Nexus 470 Test of Fourier Transform Infrared S pectrometer. The composition unit of the thermoplastic resin is parts by weight, which is based on 100 parts by weight of a styrene monomer derivative and a nitrile vinyl monomer derivative and a copolymerizable vinyl monomer derivative. The thermoplastic styrene The unit of the rubber content of the resin composition (C) is% by weight. The content of BMI monomer derivatives is determined by the raw materials in the polymerization reaction.

567191

V. Description of the invention (32) Calculated by the input amount, the conversion rate of each monomer and the recovered volatile components. 2. Residual BMI monomer: It consists of thermoplastic resin or thermoplastic styrene, and rhenium is dissolved in tetrahydrofuran. 'The thermoplastic resin or the solution of the thermoplastic vinyl composition (C) was analyzed and measured using a gas chromatograph (GC) with a flame detector provided by Hewlett Packard Co., Ltd. No. 6890A. The unit of the residual BMI monomer is ppm, which is based on 100% by weight of a thermoplastic resin or 100% by weight of a thermoplastic styrene resin composition (C). Μ not detected (N · D): indicates that the residual BMI monomer is below 2pprn. 3. MZ and MW: An analytical measurement using a gel dialysis chromatography (GPC) with differential curvature and light scattering detection, manufactured by Waters, was performed on a column: KD-80 6M. Device: Water RI-2410 Mobile phase: THF (flow rate 1 · 0 cc / mi η) 4 · Bifurcation ratio (gM): a gel dialysis chromatograph manufactured by Waters Corporation in series and manufactured by Wyatt Technology, Minidawn Multi-angle laser light scattering (MALLS). The measurement method is to measure the molecular weight of each slice layer by using the light scattering measured at different angles from the sample obtained by column chromatography. The difference ratio is defined as:

Page 35 567191 V. Description of the invention (33) \ r% (r2) b: half-rotation of the divergent molecule (r2) i: half-rotation of the linear molecule 5 · Μ I (melt flow index) According to ASTM D- 1 238 method test, test temperature 22 (rc bit is grams / 10 minutes (g / lOmin). Dali i ug early in the present invention, the melting and dispersing of the divergent resin ^ The larger the value, the better the melt strength, and Please refer to the first figure for the device. It is the measurement of the maximum elongation and dryness. The device is heated by a heater (nitrogen heating) 10, the hot lice are discharged from the outlet 50, and a capillary rheometer 2 〇 (capiiiary rhe⑽eter) is connected with a pair of first rollers 30 on the outside of the discharge port to lead out the molten resin 90. In order to guide the molten resin 90 to the outlet 50, the first roller 30 and the A pair of second rollers 40 are arranged between the outlets 50, so that the first roller 40 is not drawn sideways to the other two rooms after being picked up by the first roller 30, and the second roller 40 is used to melt the molten metal. The resin 90 is guided to the outlet 50, wherein the first roller 30 is provided with 10ad "η to sense the pulling force (Pa), and the pulling force is It is defined as elongational viscosity. The measurement conditions are 140X: ~ 16 (TC under nitrogen at 0.5 · 1 0.5 / sec shear rate. 7. Hue · Made by Nippon Denshoku, Model NDj-3 〇〇a color difference meter test, directly determine the resin. The quartz colorimetric cell (ce 丨 j) used

Page 567 191, Description of Invention (34) The dimensions are 5.5cmx 4.0cmx 2.4cm. 8 · Thermal stability (△ γ 丨): The above thermoplastic styrenic resin composition (C) is injected into an injection machine with a capacity of 4.2 oz. (Injection temperature: 230 ° C). The diameter of the molded product is 5 A disc with a thickness of 1/8 inch in centimeters. The disc is then placed in an oven for 2 hours at a temperature of 200 ° C. During this period, the model and model of Datacolor International are used.

The Spectraf lash 5 00 color difference meter measures the yellow index (YI) of the disc before and after heating. △ YI = YI after heating — before heating ΥΙ

9 · Thin meat phenomenon: The above thermoplastic styrene resin composition (c) is extruded by a uniaxial extruder (diameter 90 °) manufactured by Yuli Shipbuilding Co., and extruded 500 mm X 500 mm X 2 mm thick at 235 ° c. The flat surface of the flat plate was then shaped with a female vacuum forming tool at 160 C to form the inner wall of the refrigerator freezer. After molding, 10 points were measured on the molded product to determine the thickness of the meat, and the difference between the maximum value and the minimum value was determined. 〇: No thin meat phenomenon, the difference is 0.5 mm or less. X: There is a thin meat phenomenon, and the difference is 0.5 mm or more. 11 1 0 Coating surface gloss: The thermoplastic styrene resin composition (C) described above was shot at a temperature of 23 ° with a 4 × 2oz injection machine with an injection temperature of 15cm in length, 7cm in width, and thickness. · 3 cm flat plate, spray with acrylic paint and observe the color change. 〇 ·· Uniform surface gloss. X: The gloss of the coating surface is not uniform and there is a phenomenon of paint absorption. 11 Stain: After taking 10 g of the above thermoplastic styrene resin composition (c) and pressing it into a circular sheet with a diameter of 20 mm and a thickness of 0.3 mm by a hot press,

567191 V. Description of the invention (35) Observe the number of stains. 1 2 Weight average particle diameter: The above thermoplastic styrene resin composition (C) is made into an ultra-thin slice or an emulsion coating film, and after dyeing, it is photographed with a transmission electron microscope at a magnification of 1,000, and the photograph is taken. Approximately 2,000 to 10,000 rubber-dispersed particles were obtained, the particle diameters were measured, and the weight-average particle diameter was determined by the following formula. Except for the obtained thermoplastic resin ', and its derived properties of heat settability, impact strength, appearance, and surface gloss that are not electrical, in particular, the present invention is indeed a novel and plastic embodiment of the present ethylene-based copolymer. Give examples of modifications or changes that you are familiar with. Weight average particle size = IniDi4 / IniDi3 ni-rubber particle diameter j) 丨 Refer to each embodiment of the present invention, the invention has excellent processing characteristics such as its mobility, divergence, etc. The vinyl fluorene resin composition (C) has good mechanical properties such as flowability, and has no shortcomings, such as thin meat. It can be used for general electronics and daggers for the molding of ice-phase plates. Therefore, the heat can be made into a method and the finished product and its derivatives with industrial use value. This top: it ^ The above is only the number of the present invention. The number can be equal to the number of people who support it. According to the spirit of the present invention, 2% L is included in the scope of the patent application for this invention. 567191

The figure briefly illustrates the first-figure plan view of the device for measuring the maximum elongation viscosity of the present invention. The figure number illustrates: heater 10 capillary rheometer 20 first roller: wheel 30 second roller 40 D50 melting Resin 9 0 Description of the attached table: Table-Manufacturing formula and physical property analysis between the Example 1 and Comparative Example of the thermoplastic styrene copolymer (A) of the present invention 0 Table 2 • _ · The thermoplastic styrene-based vinyl of the present invention Resin composition (C) Manufacturing formula and physical property analysis between each example and comparative example. Table Three References • The thermoplastic styrene resin composition (C) of the present invention and manufacturing formula and physical property between each example and comparative example Analysis 0 Page 39 567191 ST: Thanks zzs (styrene) AN: alsl (acrylonitrile) N-PMI: N-Xie glffl B. N.phenyl maleimide BMI: N, N--4,4--zl ^^. ai ^ «liH ^ i55® (N, N--4,4rdiphenylmethanebismaleimide) PGDA: §fawh®zl31s (n eopentyl glycol diacrylate) BPO: 贵贵 (CVH 谢 -ffl 尔 (benzoyl peroxide) TDM: ® (il ^ + h wiwi? ® (t-dodecyl mercaptan) Rl δR3: Chi III® Optochlorine® Le BMI 锢 Cocoon (ppnoss ^ so __% ^ 沣 4 获 ®ssg NP: m ^ (is! Lff (Non Detectable) MZ: Z Book 菡 φ ^ _ MW gM molar mass = 1M 0aQ " / mol B4H- / N : gwpi Analysis results of physical properties Reaction conditions Thermoplastic resin composed of thermoplastic styrene copolymer (A) Φ Hue 1 Maximum elongation viscosity (Pax 106) 1 2 HH [MZ / MW MW (million) MZ (million) 1 Residual BMI monomer (ppm) Resin composition (parts by weight) Retention time in the reactor (hr) i Reaction pressure (kg / cm2) Rl / R2 (Rl / R2 / R3) Reaction temperature (° C) R1 / R2 (or R1 / R2 / R3) a part w ® § w (d) BMI monomer derivative (c) N-PMI monomer derivative (b) AN monomer derivative ⑻ ST monomer derivative chain transfer agent (parts by weight) Polymerization initiator (parts by weight) (e) PGDA monomer (d) BMI monomer (c) N-PMI monomer (b) AN monomer (a) ST monomer KJ \ 12.3 I 0.61 31.8 130.5 ND 0.02 〇 to 〇〇to to 1 4.0 / 4.0 | 100/120 TDM (0.2) 1 ΒΡΟ (0 · 02) 1 ο 0.02 ο U) Κ) os 00 > Example 1 to 1 0.75 1 U) 78.3 ND 0.01 〇K) 〇〇ίο to 1 4.0 / 4.0 | 100/120 TDM (0.2) ΒΡΟ (0.02) ο 0.01 ο U) Κ) 〇 \ 00 > Example 2 as 00 00 to U) 1 0.72 | 2.63 21.6 56.8 ND 0.01 Μ Μ g to 4.0 / 4.0 100/120! j 1 TDM (0.2) | | ΒΡΟ (0.02) | ο 1 0.01] Content K) to U \ 00 Implementation Example 3 ΰ! 13.5 Uj 1 0.63 30.2 135.9 ND 0.02 〇to oo to to 4.0 / 4.0 120/140 TDM (0.2) TX-29A (0.015) 0.01 1 0.02 1 ο U) K) ON 00 Implementation i 〇〇g 1 0.68 U) to ND 0.02 〇ο o 3.0 / 3.0 / 3.0 110/130/16 〇 TDM (0.02) ΒΡΟ (0.02) | ο 1 0.02 1 ο o Cj \ Example 5 k) 1 0.98 ZJ.J 39.9 ND 〇〇K) 00: K) K) 4.0 / 4.0 100/120 | TDM (0.2) | ΒΡΟ (0.02) | ο ο ο U) K) Os 00 | Comparative Example 1 00 1 15.6 1 ο -JZ-jJ 1 994.5 1 1 1231 1 〇to 00 K) K) 1 4.0 / 4.0 1 100/120 TDM (0.2) 1 | ΒΡΟ (0.02) | ο ο u > K) 〇 \ 00 Comparative Example 2 ψι 567191 ST: Thank you ^ (styrene) AN: 31 ^ l (acrylonitrile) N-PMI: N-Tse glw ^ lsgs ^ -phenylmaleimide) BD: Hn ^ (butadiene) domi: N, N-.4,4--Il Tse wlai ^ lffl ^ HsCN, N--4,4 --diphenyl methane bismaleimide) PGDA: ff ^ wzlgpll3ls-step sl ((neopentyl glycol diacrylate) BPO: ® »(cvh 谢 -ffl 尔 (benzoyl peroxide) TDMMllll & -fzl ^ -wi & ^ rdodecyl mercaptan) R1 R2 R3:铖 lllfa 镝 n > River J® 骓 R4: Window Ml} Porphyry JS 骓 磡 BMI marriage sl (ppm): ygiH00 »_% Ν 涝 4 won 4 Thank ^ 溆 溆 © 牦 牦 妈Latent (c) Mb. ^ I ^ fSIMEECNOnDetectable) Physical properties Residual resin composition BMI monomer (ppm) M ma m Quotienta Reaction conditions Thermoplastic styrenic resin composition (c) Thin surface gloss phenomenon Thermal stability 2 Hi > irt Wj llinli ρ_ _ Residency in the reactor (hr) Reaction pressure (kg / cm2) R1 / R2 / R3 / R4 Reaction temperature (° C) R1 / R2 / R3 / R4 Composition of the monomer supplied (weight Parts) Chain transfer agent (parts by weight) Polymerization initiator (parts by weight) (f) PGDA monomer (e) BMI monomer (d) BD rubber ⑹ N-PMI monomer 丨 (b) AN monomer ⑻ ST monomer. 〇U) K) ND 4.5 / 4/4/4 95/100/110/120 TDM (0.3) BPO (0.05) ο 0.02 μ-k ro ο to 〇 \ η Example 6 〇〇Lh ND s: 4.5 / 4/4/4 95/100/110/120 TDM (0.3) BPO (0.05) 0.005 1 0.02 N— * h— * to U) Cs OS 1 Example 7 XX UJ L / > ND 4.5 / 4/4/4 95/100/110/120 TDM (0.3) BPO (0.05) ο ο ίο Ο to ON 〇 U) Comparative Example 3 X 〇g hJ 4 ^ 4.5 / 4/4/4 95/100/110/120 TDM (0.3) BPO (0.05) ο f3 〇 to Os Comparative Example 4

EB S: ^ [Ns »a ^ _r > (ethy lene b isstealide) 1sf 50 ow Physical properties Extrusion conditions Residual BMI monomer (ppm) in resin composition j Rubber content (% by weight) in resin composition wg ίϋ Heat Plastic styrene resin composition (C) Surface gloss, thin flesh phenomenon, stain point, thermal stability 2 ►-Η Extruder die temperature (° C) Extruder raw material tank temperature (° C) ί © m CO GO (f) Thermoplastic styrenic copolymer (A-7) (e) Thermoplastic styrenic copolymer (A-6) ⑹ Thermoplastic styrenic copolymer (A-3) (c) Thermoplastic styrenic copolymer (A-1) ⑻Rubber graft copolymer (D-2) (a) Rubber graft copolymer (D-1) 〇〇- v〇K) 200-220 2: b-〇U) ο ο ο μ 〇KJ \ Example 8 〇〇〇 \ μ ο 220-240 bo U) ο ο ο / 0 ^ 〇 Example 9 〇〇K) fo υ〇bJ M 200-220 2: b 〇〇o U) ο ο ο 2 〇Ν 〇I (C-7) 1 Example 10 〇〇U) ίδ Lh Κ) to ο 220-240 \ z: b 00 o U) ο ο 2 ο U) Os 〇 ^ 00 Example 11 XXK ) 6 r Κ) Μ 1 200-220 j 2: bo U) ο ο ο UJ Ο ί (C-9) 1 Compare Example 5 X 〇 $ ON to Κ) to ο 200-220 On-o Lk) ο ο ο 1 Ο Comparative Example 6 XX 〇to to 200-220 2: b 00 o U) ο ο ο U) 〇 \ 〇 Comparison Example 7 X 〇5; Κ) Os b to 200-220 〇〇o OJ 2 ο ο ο OJ Os 〇ίο Comparative Example 8

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Claims (1)

public j 虎 9012977Π Year A — $ Acid-based monomer derivative, methacrylate-based monomer derivative, and monofunctional maleimide-based imide Qin body ^ In the-·-According to the 5th scope of the patent application The thermoplastic resin has a content of copolymerizable ethylene-based monomer derivatives of 2 to 40 parts by weight. 8 Residual polyfunctional maleimide based on the thermoplastic resin described in item 5 of the scope of patent application. Single system below 1000 ppm. The average molecular weight / weight average molecular weight (MZ / MW) of the thermoplastic resin according to item 5 of the scope of patent application is 2 to 8. 1 〇Measured according to the thermoplastic resin described in item 5 of the scope of the patent application using a gel dialysis chromatography (GPC) series multi-angle laser light scattering system ALLS) 'dang moer mass) = ixi〇6g / For moles (g / mole), the branching ratio (gM) = 0.45 to 0.95, where gM = Pi (r2) b: the radius of rotation of the branching molecules, and (r2) i: a linear molecule The radius of rotation. 11 A thermoplastic styrenic resin composition, 30 to 100 parts by weight of a stupid vinyl monomer derivative /, 0 to 45 parts by weight of a nitrile vinyl monomer derivative, and 0 to 40 parts by weight The copolymerizable B counts 10.重量 份 和 0.00 05] 。. Thermoplastic melamine composed of amine-based monomer derivatives is a continuous phase, and the thermoplastic benzene composed of rubber particles and copolymers acts as a knife phase. Face Page 41 567191