CN1152004A - Thermoplastic resin composite - Google Patents
Thermoplastic resin composite Download PDFInfo
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- CN1152004A CN1152004A CN 95120405 CN95120405A CN1152004A CN 1152004 A CN1152004 A CN 1152004A CN 95120405 CN95120405 CN 95120405 CN 95120405 A CN95120405 A CN 95120405A CN 1152004 A CN1152004 A CN 1152004A
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Abstract
The thermoplastic resin composition comprises graft copolyrer C of 5-90 wt%, which is produced through polymerization of graft copolymer A, diene rubber, propenyl copolymer and a monomer mixture; graft copolymer D of 10-95 wt%, which is produced through emulsion and grafting polymerization of rubber emulsion and a monomer mixture; copolymer E of 0-60 wt%, which is produced through the copolymerization of a monomer mixture; and polycarbonate E. The said monomer mixture includes styrene monomer, vinyl cyanide monomer and copolymering monomer.
Description
The invention relates to a kind of thermoplastic resin composite, refer to a kind ofly have superior joint line intensity especially, and have good flowability simultaneously, to improve the resin combination of processing forming.
General by polycarbonate resin and the mixing adulterant that forms of phenylethylene resin series, except having excellent machinery and electrical specification, also have higher thermotolerance and shock-resistance, therefore, be used in for example TV widely, electric products such as CRT, various computer products, on OA machinery and the tame electrical article, but because the flowability of polycarbonate is poor, notched Izod impact strength is not good, therefore often need during fabrication to add processing or impact modification agent and improve, for example promptly mention in No. 3130177 case of U.S.'s patent of invention, the rubber like graft copolymer that adds styrene butadiene-acrylonitrile resin for example in polycarbonate is mixing, can improve the thermoplastically of polycarbonate, and promote its processibility.
Then mention in No. 3663471 case of U.S.'s patent of invention, the rubber graft copolymer of polycarbonate and for example styrene butadiene-acrylonitrile resin is mixing, can improve notched Izod impact strength, particularly Ai Zuode (IZOD) shock strength of moulding product; Mention then in No. 4855357 case of U.S.'s patent of invention that weight-average molecular weight when the styrene butadiene-acrylonitrile copolymer more than 130,000 is mutually mixing, can be improved hitting property in the low temperature of moulding product in the polycarbonate more than 35,000 and weight-average molecular weight; But as can be known by the exposure of aforementioned many prior arts, though improve by polycarbonate resin and the phenylethylene resin series adulterant shock strength that forms of mixing, but the flowability of aforementioned adulterant is still on the low side, also be not easy in the processing, and the intensity at the joint line place of moulding product often a little less than, sometimes even can produce the situation of slight crack.
In view of this, this case contriver is at aforementioned disappearance, develops the thermoplastic resin composite that a kind of phenylethylene resin series and polycarbonate resin mix and form.
Therefore, main purpose of the present invention provides a kind ofly promotes joint line intensity, and has good fluidity, to improve the thermoplastic resin composite of processing forming.
Thermoplastic resin composite of the present invention comprises:
(1) graft copolymer of 5-90 weight part (C), this graft copolymer (C) obtains as follows: the weight average particle diameter (weight average particle size) of 0.1-10 weight part is the rubber graft copolymer (A) of 0.05-0.8 μ m, the propenyl based copolymer (B) of the diene series rubber of 2-25 weight part and 0.1-10 weight part, with gross weight be the following monomer mixture of 100 weight parts: the styrenic monomers of 45-80 weight part, the acrylic monomer of 15-50 weight part and optionally and the copolymerizable monomer of optional 0-40 weight part is carried out body and/or solution copolymerization;
(2) graft copolymer of 10-95 weight part (D), this graft copolymer (D) obtains as follows: with the weight average particle diameter of 50-85 weight part (dry weight) is that the rubber latex of 0.05-0.8 μ m and styrenic monomers, the acrylic monomer of 15-50 weight part and the copolymerizable monomer mixture of optionally choosing wantonly carry out the emulsification graft polymerization;
(3) multipolymer of 0-60 weight part (E), this multipolymer (E) obtains as follows: with the styrenic monomers of 50-80 weight part, the acrylic monomer of 20-50 weight part, and optionally and the copolymerizable monomer of optional 0-40 weight part is carried out copolymerization; And
(4) with respect to total amount be graft copolymer (C), graft copolymer (D) and the multipolymer (E) of 100 weight parts, the polycarbonate of 40-200 weight part (F).
Rubber graft copolymer of the present invention (A) is made by emulsion polymerization method, preferable manufacture method is that diene monomer and other copolymerizable monomer are directly aggregated into the rubber latex that weight average particle diameter is 0.05-0.8 μ m with emulsion polymerization method, after also aforementioned monomer can being made the small particle size rubber latex that weight average particle diameter is 0.05-0.2 μ m with emulsion polymerization method, again with freezing agglomeration technique (Cryogenic agglomeration) or mechanical agglomeration technique or additive agglomeration technique, aforementioned small particle size rubber latex is agglomerated into the rubber latex that weight average particle diameter is 0.15-0.8 μ m, wherein, the employed additive of additive agglomeration technique can be: acetic anhydride, hydrogenchloride, acidic substance such as sulfuric acid, or be sodium-chlor, Repone K, salt-base substances such as calcium chloride, and (methyl) acrylic acid series-(methyl) acrylate is that multipolymer is (as methacrylic acid-butyl acrylate copolymer, methacrylic acid-ethyl propenoate) etc. the polymer coagulant that contains the carboxylic acid group.
With aforementioned rubber latex of 50-85 weight part and 15-50 parts by weight of styrene is the mixture of monomer, acrylic monomer, other copolymerizable monomer, and an amount of emulsifying agent and initiator carry out graft polymerization should; Above-mentioned initiator can use initiator common in this area, for example: benzoyl peroxide (benzoyl peroxide), diisopropyl benzene hydrogen peroxide (diisopropyl benzene hydroperoxide), cumene hydroperoxide hydrogen (cumene hydroperoxide), tertbutyl peroxide (tert-butyl hydroperoxide), Potassium Persulphate (potassium persulfate) etc. are good with the organic hydroperoxide class again wherein.
Graft copolymer of the present invention (A) can use the activator of redox catalysis system when polymerization, or the activator on the known techniques such as iron ion, for example (sodium pyrophosphate-dextrose), sodium sulfoxylate formaldehyde (sodium for maldehyde suluxylate), xitix (ascorbic acid), (dihydroxy acetone etc. all can use otan trisodium phosphate-dextrose.In addition, can add that also edetate (ethylene diamine tetracetic acid salt) promotes its effect; And iron(ic) chloride or ferrous sulfate can be used in the source of iron ion.
The percentage of grafting of aforementioned rubber graft copolymer (A) can be controlled by polymeric reaction condition, for example: by the controlled polymerization temperature, the consumption of initiator, emulsifying agent, chain-transfer agent and kind, monomeric addition meanss etc. are controlled; Also can add the molecular weight that chain-transfer agent is adjusted graftomer according to known techniques, common chain-transfer agent has: n-butyl mercaptan (n-butyl mercaptan), n-octyl mercaptan (n-octyl mercaptan), just-lauryl mercaptan (n-dodecyl mercaptan), uncle-lauryl mercaptan (tert-dodecyl mercaptan); The molecular weight of above-mentioned rubber graft copolymer (A) also can be by polymerization temperature, the kind of initiator and consumption, and the change of polymerizing conditions such as monomeric addition means is adjusted, and the temperature of reaction of its graft polymerization is below 90 ℃, preferably between 30-80 ℃; The graft polymerization monomer can once add, and also can add in batches, also can add continuously or with the segmentation graft polymerization in batches of various monomers, so can obtain rubber graft copolymer (A) emulsion; Again with aforementioned graft copolymer (A) emulsion via traditional dehydration condensation, drying and other steps, and obtain the rubber graft copolymer that weight average particle diameter required for the present invention is 0.05-0.8 μ m (A).
Rubber graft copolymer among the present invention (A) to improve the principle of making efficient, preferably adopts the rubber latex of agglomeration method preparation based on the polymerization time that shortens rubber latex though can use aforementioned the whole bag of tricks to make; Wherein, based on the homogeneity of agglomeration particle diameter and the purpose of minimizing coagulated lumps, more preferably add the polymer coagulant that contains the carboxylic acid group and carry out agglomerationization and obtain rubber latex.
Employed styrenic monomers can be vinylbenzene, alpha-methyl styrene, α-chloro-styrene, p-t-butyl styrene, p-vinyl toluene, o-chloro-styrene, p-chloro-styrene, 2 in the rubber graft copolymer of the present invention (A), 5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromo-benzene ethene, 2,5-Dowspray 9s etc. wherein, preferably adopt vinylbenzene or alpha-methyl styrene.
Spendable acrylic monomer can be: vinyl cyanide, Alpha-Methyl vinyl cyanide etc.; Preferred vinyl cyanide.
Other copolymerizable monomer of being added can be: (methyl) acrylic ester monomer or maleimide are monomer etc.; Wherein, (methyl) acrylic ester monomer can be: methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate and dimethylaminoethyl methacrylate etc., wherein preferable methyl methyl acrylate.
Described maleimide is that monomer can be: 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-2,3-tolyl maleimide, N-2,4-tolyl maleimide, N-2,3,-butyl maleimide, N-2, the 4-butyl maleimide, N-2,6-tolyl maleimide, N-2,3-chloro-phenyl-maleimide, N-2,4-chloro-phenyl-maleimide, N-2,3-bromophenyl Malaysia imide, N-2,4-bromophenyl Malaysia imide etc.
Propenyl based copolymer (B) among the present invention is by at least a monomer that 10-100% (weight) selects from (methyl) acrylic ester monomer and acrylic monomer, 0-80% (weight) styrenic monomers, and other copolymerizable monomer of 0-30% (weight) are carried out polymerization and obtained; Monomeric species when above-mentioned monomeric species and preparation rubber graft copolymer (A) is roughly the same, and difference is: it is monomer that other copolymerizable monomer in the propenyl based copolymer (B) do not comprise maleimide.Its polymerization methods can be solution, body, emulsion or suspension polymerization etc., preferred solution or mass polymerization.
The diene series rubber that uses in the graft copolymer of the present invention (C) is: at the polymer below-20 ℃, preferred diene series rubber for example comprises the diene monomer composition: divinyl rubber, synthetic polyisoprene, neoprene etc. through second-order transition temperature after the ionic polymerization; Wherein, divinyl rubber has the branch of high-cis (Hi-Cis) and low cis (Low-Cis); In the high-cis rubber, the typical weight of its cis (Cis)/vinyl (Vinyl) consists of 94-98%/1-5%, and all the other compositions then are trans (Trans) structure; Its Mooney viscosity is between 20-120, and molecular weight ranges is preferably 100,000-800,000; In the low cis rubber, the typical weight compositing range of cis/vinyl is at 20-40%/1-20%, and all the other are transconfiguration, and its Mooney viscosity is between 20-120.Other suitable elastomeric materials also have: acrylic-nitrile rubber, styrene/butadiene rubbers, or the mixture of above-mentioned different rubber; The SBR that styrene/butadiene rubbers promptly is commonly called as.Be suitable for phenylethylene/butadiene copolymerization rubber of the present invention, its polymerization pattern can be two-section type (di-block) multipolymer, syllogic (tri-block) multipolymer, random copolymers (random) or radial copolymer (star type).The part by weight scope of styrene/butadiene rubbers is preferably 5/100 to 80/20, and molecular weight ranges is preferably 50,000-600,000.Above-mentioned rubber of the present invention preferably divinyl rubber and the styrene/butadiene rubbers of being applicable to, preferred especially divinyl rubber.
Graft copolymer of the present invention (C) makes like this: with the rubber graft copolymer (A) of 0.1-10 weight part, the diene series rubber of 2-25 weight part, 0.1-10 the propenyl based copolymer (B) of weight part, with the 45-80 parts by weight of styrene be that monomer, 15-50 parts by weight of acrylonitrile are monomer and 0-40 weight part copolymerizable monomer carries out body and/or solution polymerization obtains.
Specifically, the present invention is with above-mentioned styrenic monomers, acrylic monomer and as required and optional copolymerizable monomer and described graft rubber polymer (A), diene series rubber, propenyl based copolymer (B), and according to need and the solvent of selecting is dissolved the material solution that is become and sent into polymerization in the reactor; Perhaps with part aforementioned monomer, graft rubber polymer (A) and propenyl based copolymer (B), and the solvent selected for use according to need is dissolved into a material solution independently, again remaining monomer is become another material solution with the diene series rubber mixed dissolution, two material solutions are sent into respectively carried out polyreaction in the reactor then.
The aforementioned base materials mixture can dissolve in traditional dissolving tank with shearing force, high stirring velocity, this dissolving tank can use have ribbon spiral formula agitating vane, propeller formula agitating vane or other can produce agitating vane of shearing force etc., under the sufficiently long time, above-mentioned diene series rubber or graft rubber polymer (A), propenyl based copolymer (B) can be dissolved into fully the state of rubber solutions, carry out to make things convenient for pump delivery to the operation of reactor; With aforementioned base materials solution respectively successive feed in first reactor and/or second reactor and/or its follow-up reactor, and after adding chain-transfer agent and free agent, initiator, react.
When reaction mixture continued from first reactor, take out the time, its speed is equivalent to the feed rate of material solution, the reaction mixture of taking-up feed again second or more a plurality of subsequent reactor in carry out further polyreaction; The form of aforesaid one or more reactors has no particular limits, but dispersion state based on graft copolymer (C), and the factors such as control of the phase reversion of diene series rubber and size thereof, size distribution, first reactor preferably adopts complete mixed type (CSTR) reactor.Through the reaction of aforementioned each reactor, its transformation efficiency is reached till the 40-90% (weight), more reacted reaction mixture is delivered to volatilization device at last to remove unreacted monomer and solvent, can make graft copolymer of the present invention (C).
The weight average particle diameter of graft copolymer of the present invention (C) is between 0.5-10 μ m, preferably between 0.8-6 μ m.The content of graft copolymer (C) is 100 weight parts in the total middle amount of graft copolymer (C), graft copolymer (D), multipolymer (E), is the 5-90 weight part, is preferably the 10-70 weight part.When its content was lower than 5 weight parts, resin of the present invention did not have superior joint line intensity, also can't increase resin flow simultaneously; But if its content is greater than 90 weight parts, the resin and the joint line intensity that then can't obtain to have higher gloss are not good.
The usage quantity of rubber graft copolymer (A) is 100 weight parts in the total monomer weight in the graft copolymer (C), is the 0.1-10 weight part, is preferably the 0.5-8 weight part.If the usage quantity of described rubber graft copolymer (A) is higher than 10 weight parts, can produce disappearances such as feedstock solution viscosity is too high, dissolving difficulties in dispersion, pumpdown difficulty.The usage quantity of propenyl based copolymer used in the present invention (B) is 100 weight parts in the total monomer weight in the graft copolymer (C), is 0.1～10 weight part, is preferably the 0.5-8 weight part.If its consumption is lower than 0.1 weight part, polymkeric substance is agglomerated together easily, and fall in the solution, and can't be fully by dispersing and dissolving in solution, thereby cause the pump delivery operational difficulty, coarse particles also can be contained in prepared resin inside, reaction back, and finished product then can produce the surface spots of flake (fish eye), and is undesirable in appearance; If its consumption is higher than 10 weight parts, then feedstock solution viscosity is too high, operation is difficult, and a large amount of propenyl based polymers (B) heavily covers polymerization reprocessing and also is not inconsistent economic benefit.When the usage quantity of rubber graft copolymer (A) in graft copolymer (C) material solution and propenyl based polymer (B) all is less than 0.1 weight part, when polymerization fusion thereafter, can't obtain higher joint line intensity, this is its maximum shortcoming.
The percentage of grafting of rubber graft copolymer of the present invention (A) is 10-40%, and the molecular weight that is grafted on the hard multipolymer on the rubber is 40, and 000-120, can make composition obtain preferable shock strength with mobile at 000 o'clock; Above-mentioned percentage of grafting is meant the hard multipolymer that grafts on the rubber and the ratio of rubber, and this hard multipolymer is styrenic monomers, acrylic monomer and copolymerizable monomer in the present invention.
The manufacture method of graft copolymer of the present invention (D) is identical with the manufacturing instructions of rubber graft copolymer (A), and its composition also can be identical with rubber graft copolymer (A).But, to consider based on rerum natura balance between preferable shock strength, rigidity and flowability, the percentage of grafting of this graft copolymer (D) is preferably between 18-80%, and the molecular weight of its grafted hard multipolymer is preferably 40,000-200,000.When percentage of grafting be lower than 18% or the molecular weight of grafted hard multipolymer be lower than at 40,000 o'clock, the shock strength of resin and rigidity are all not good; And when percentage of grafting greater than 80%, molecular weight is higher than at 200,000 o'clock, resin flow is poor; The usage quantity of above-mentioned graft copolymer (D) is 100 weight parts in the gross weight of graft copolymer (C), graft copolymer (D), multipolymer (E), is the 10-95 weight part, is preferably the 15-60 weight part.When the content of graft copolymer (D) is lower than 10 weight parts, the shock strength deficiency of resin combination; And when its consumption was higher than 95 weight parts, resin flow was poor, joint line intensity is also not enough.
Multipolymer of the present invention (E) is to be that monomer, 20-50 parts by weight of acrylonitrile are monomer by the 50-80 parts by weight of styrene, and optionally and optional 0-40 weight part copolymerizable monomer is carried out polymerization and obtained.Described styrenic monomers, acrylic monomer and copolymerizable monomer are identical with the monomer explanation in the rubber graft copolymer (A), and aforementioned multipolymer (E) can adopt body, solution, suspension, emulsion polymerization method to make, preferred body or solution polymerization process.The molecular weight of described multipolymer (E) is 60,000-400, and between 000, preferably 80,000-300 is between 000.The content of described multipolymer (E) is 100 weight parts in the gross weight of graft copolymer (C), graft copolymer (D), multipolymer (E), is the 0-60 weight part.
Polycarbonate in the thermoplastic resin composite of the present invention (F) can be any homo-polycarbonate as known in the art or Copolycarbonate.Described polycarbonate (F) can prepare according to any known method in this area, for example adopt interface fasculation method (interfacial polycondensation process), utilize homopolyeondensation effect (polycondensation in ahomogeneousphase) or utilize over-churning effect (transesterification), these preparation methods and composite reaction thing, polymkeric substance, catalyzer, solvent and condition are known in the prior art, and are illustrated in U.S.'s patent of invention the 2964974th, 2970137,2999835,2999846,3028365,3153008,3187065,3215668, in the patents such as 3258414 and 505162.Suitable polycarbonate can be selected from following bisphenols: dihydroxybiphenyl, two-(hydroxyphenyl)-alkane, two-(hydroxyphenyl)-naphthenic hydrocarbon, two-(hydroxyphenyl) sulfide, two-(hydroxyphenyl)-ether, two-(hydroxyphenyl)-ketone, two-(hydroxyphenyl)-sulfoxide, two-(hydroxyphenyl)-sulfone, alkyl cyclohexylene bis-phenol, right-(hydroxyphenyl)-diisopropyl benzene, and the nuclear alkanisation of aforesaid compound (nucleus alkylation), nuclear halogenation (nucleus halogenation) derivative with and composition thereof.
The specific examples of aforementioned bisphenol compound has: 4,4 '-dihydroxybiphenyl, 2,2,-two (4-hydroxyphenyl)-propane, 2,4-pair-(4-hydroxyphenyl)-2-methylbutane, 1,1-pair-(4-hydroxyphenyl)-hexanaphthene, α, α-two-(4-hydroxyphenyl)-diisopropyl benzene, 2,2-pair-(3-methyl-4-hydroxyphenyl)-propane, 2,2-pair-(3-chloro-4-hydroxyphenyl)-propane, two-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-pair-(3,5-dimethyl-4-hydroxyphenyl)-propane, two-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, 2,4-two-(3,5-dimethyl-4-hydroxyphenyl)-the 2-methylbutane, 1,1-pair-(3,5-dimethyl-4-hydroxyphenyl)-hexanaphthene, α, α-two-(3,5-dimethyl-4-hydroxyphenyl)-right-diisopropyl benzene, 2,2-pair-(3,5-two chloro-4-hydroxyphenyl)-propane and 2,2-pair-(3,5-two bromo-4-hydroxyphenyl)-propane; Particularly suitable bisphenol compound is 2,2 ,-two-(4-hydroxyphenyl)-propane, and the dihydroxyphenyl propane that promptly generally is commonly called as (bisphenol A), aforementioned bisphenol compound can photoreactive gas (phosgene) reaction produce aromatic copolycarbonate; Also can specially permit the method for making of flat 1-158033 patent case in addition as the day disclosure, it is that bisphenol compound is reached two hydroxyphenyl carbonate monomers polymerization composition low-molecular weight polymer in advance, carries out solid-state polymerization (solid polymerization) and obtains polycarbonate through crystallisation procedure does again.
With the described graft copolymer of 5-90 weight part (C), the described graft copolymer of 10-95 weight part (D), 0-60 weight part multipolymer (E), and be 100 weight parts in the gross weight of described graft copolymer (C), graft copolymer (D) and multipolymer (E), the 40-200 weight part, be preferably 70-150 weight part polycarbonate (F), with the general known device blending of mixing, can make and have excellent joint line intensity, and can increase its flowability and make the easier resin combination that carries out of the course of processing.
The aforementioned device that generally mixes comprises list and twin screw extruder, mix in mix cylinder and inside device etc., and can comprise or not comprise various known additives in the thermoplastic resin composite, for example: stablizer, lubricant, FLOW IMPROVERS, antioxidant, static inhibitor, weighting agent, glass fibre, pigment and analogue thereof.
For further describing the present invention in detail, be described as follows with embodiment and physical property measurement again, unless specifically stated otherwise, the consumption of various compositions is all represented with weight part in the following example.
＜preparation example 1〉preparation of rubber graft copolymer (A-1): composition weight part 1,3-butadiene 150.00 potassium persulfate solutions (1%) 15.00 sodium dodecyl sulfate solution (10%) 20.00 distilled water 190.00 ethylene glycol dimethacrylates 0.13
65 ℃ of down reactions 12 hours, obtain transformation efficiency and be 94%, solids content is about 40%, weight average particle diameter is the synthetic rubber latex of 0.1 μ m according to above prescription.
In addition, the polymer coagulant that contains the hydroxy acid base with following formulation: composition parts by weight of acrylic acid ethyl ester 90.0 vinylformic acid 10.0 potassium persulfate solutions (1%) 0.5 sodium dodecyl sulfate solution (10%) 0.5 distilled water 200.0
According to above prescription 75 ℃ of down reactions 5 hours, obtain that transformation efficiency is about 95%, the pH value be 6.0 contain hydroxy acid based high molecular agglutinant.
Afterwards, with the synthetic rubber latex that carboxylic acid group's polymer coagulant (dry weight) comes agglomeration 100 weight parts that contains of 3 weight parts, the pH value of resulting agglomeration rubber latex is 8.5, and the weight average particle diameter of its rubber particles is about 0.31 μ m.
At last; Carry out graft polymerization reaction with aforementioned agglomeration rubber latex according to following prescription again, to make rubber graft copolymer (A-1). composition weight portion agglomeration rubber latex (dry weight) 100.0 styrene 25.0 acrylonitrile 8.3 uncle's lauryl mercaptans 2.0 diisopropyl benzene hydrogen peroxide 3.0 copperas solutions (0.2%) 3.0 formaldehyde sodium sulfoxylate solution (10%) 0.9 edta solution (0.25%) 3.0
Fill a prescription prepared rubber graft copolymer emulsion again through dewatering, being dried to water content below 2% according to last table, just can make the rubber graft copolymer of wanting required for the present invention (A-1) (rubber content 75% (weight)), the weight average particle diameter of its rubber particles is that 0.3 μ m, percentage of grafting are 30.5%, the molecular weight that is grafted on the styrene-acrylonitrile copolymer on the rubber is 63,000.
＜preparation example 2〉preparation of rubber graft copolymer (A-2):
Take＜preparation example 1〉prepared synthetic rubber latex (the rubber particles weight average particle diameter is as 0.1 μ m); Agglomeration process without polymer coagulant; Directly carry out graft polymerization reaction, the glycerol polymerization prescription is as follows: composition weight portion synthetic rubber latex (0.1 μ m) (dry weight) 100.0 styrene 20.0 acrylonitrile 8.3 methyl methacrylates 5.0 uncle's lauryl mercaptans 2.0 diisopropyl benzene hydrogen peroxide 3.0 copperas solutions (0.2%) 3.0 formaldehyde sodium sulfoxylate solution (10%) 0.9 edta solution (0.25%) 3.0
The rubber graft copolymer emulsion that makes is with system＜preparation example 1〉aftertreatment, the weight average particle diameter of above-mentioned rubber graft copolymer (A-2) is 0.1 μ m, percentage of grafting is 26.8%, and the molecular weight of grafted styrene-acrylonitrile-methylmethacrylate copolymer is 58,000.
＜preparation example 3) preparation of propenyl based copolymer (B-1):
Mixed with the speed of 12kg/hr raw material 50 parts by weight of styrene, 18 parts by weight of acrylonitrile, 32 parts by weight of methylmethacrylate, again speed, benzoyl peroxide and uncle lauryl mercaptan and the aftermentioned recovery liquid of ethylene distearyl acid amides with 3.0g/hr is merged as feeding feeding, with infeed internal temperature remain on 108 ℃ and volume be 45 liters with in the still type polymerization tank of agitator, and make the toluene ratio in the reaction solution remain on 15%, and percent polymerization remain on 55%.
After reaction solution is removed volatile component by volatilization device, can obtain the particle of the propylene base system copolymer of wanting required for the present invention; On the other hand, the volatilization composition of being removed with condenser condenses as reclaiming liquid, and continuously with the aforementioned base materials mixed solution so that its repeated use.This method can be adjusted speed of response by the amount of benzoyl peroxide, or adjusts the amount of uncle's lauryl mercaptan; At last making melt flow index with the speed of about 12kg/hr is methyl methacrylate-acrylonitritrile-styrene resin (B-1) of 1.
＜preparation example 4〉preparation of propenyl based copolymer (B-2):
Directly adopt the methyl methacrylate (trade(brand)name: ACRYREC CM-205) of applicant company manufacturing.
＜preparation example 5〉preparation of graft copolymer (C):
(company of Asahi Chemical Industry produces to use the polyhutadiene of 7 weight parts, trade(brand)name--Asadene 55AS) is used as the uncle's lauryl mercaptan of diene series rubber, 0.1 weight part and the benzoyl peroxide of 0.07 weight part and works as initiator, and the propenyl based polymer (B-1) that makes rubber graft copolymer (A-1) (rubber content 75% (weight)), 1.4 weight parts of 1.4 weight parts is dissolved in the ethylbenzene of the vinyl cyanide of the vinylbenzene of 74.4 weight parts, 25.6 weight parts and 30 weight parts fully, and forms feedstock solution; Aforementioned feedstock solution is sent in first reactor continuously, the volume of this first reactor is 44 liters, temperature of reaction is 100 ℃, the stirring velocity of the spiral whipping appts that is provided with in it is 300rpm, be provided with the refrigeration cycle pipe in whipping appts, to take out and send in second reactor continuously through the mixture behind first reactor reaction, device is same as first reactor in this second reactor, when the transformation efficiency of mixture reaches 60%, again mixture is taken out and send into volatilization device to remove unreacted monomer and volatile matter, with its extruding pelletization, can obtain graft copolymer (C-1) particle of weight average particle diameter 1.1 μ m afterwards.
According to aforementioned preparation method and with the listed ratio of table 1, produce graft copolymer (C-2), (C-3), (C-4), (C-5), (C-6), (C-7), wherein, (C-2) change 150rpm into (C-5) stirring velocity in first reactor, and diene series rubber changes Asahi Chemical Industry's trade(brand)name that company produces--the rubber of Asadene 35AS into, and the weight average particle diameter of the rubber particles of aforementioned (C-2)-(C-7) is respectively: 4.7 μ m, 1.05 μ m, 0.9 μ m, 5 μ m, 0.5 μ m, 0.9 μ m.
＜preparation example 6) preparation of graft copolymer (D):
The preparation method of rubber latex is described identical with preparation example 1; But the agglomeration processing changes the synthetic rubber latex that the polymer coagulant that contains the carboxylic acid group of 3.5 weight parts comes agglomeration 100 weight parts into; The pH value of the rubber latex that obtains is 8.5; And the weight average particle diameter of the rubber grain that obtains is about 0.28 μ m.Carry out graft polymerization reaction according to following prescription, to obtain graft copolymer (D). composition weight portion agglomeration rubber latex (dry weight) 100.0 styrene 40.4 acrylonitrile 13.4 uncle's lauryl mercaptans 2.0 hydrogen peroxide diisopropyl benzenes 3.0 copperas solutions (0.2%) 3.0 formaldehyde sodium sulfoxylate solution (10%) 0.9 edta solution (0.25) 3.0
The weight average particle diameter of above-mentioned graft copolymer (D) is 0.28 μ m, and percentage of grafting is 42%, and the molecular weight of grafted styrene-acrylonitrile copolymer is 80,000.
＜preparation example 7〉preparation of multipolymer (E):
Mixed with the speed of 12kg/hr raw material 76 parts by weight of styrene, 24 parts by weight of acrylonitrile, again with speed, benzoyl peroxide and the uncle lauryl mercaptan of ethylene distearyl acid amides with 3.0g/hr, and aftermentioned is reacted the recovery liquid that the is reclaimed merging of the fugitive constituent of being removed as feeding feeding after condensation, obtaining melt flow index with the polymerization procedure of preparation example 3 is 1.2 styrene-acrylonitrile copolymer, i.e. multipolymer (E).
＜preparation example 8〉polycarbonate (F):
Polycarbonate resin is that commercially available Mitsubishi Gas Chemical Co., Ltd makes, and commodity are called excellent (Iupilon) S-2000F that must swell, and it is 56dl/g at 25 ℃ with methylene dichloride measured intrinsic viscosity (intrinsic viscosity) under solvent.
The testing standard of rerum natura that following embodiment and comparative example are measured and moulding product outward appearance is as follows:
* the mensuration of melt flow index (MI, Resin Flow): according to the ASTMD-1238 standard testing.
* Izod impact strength (IZOD, jagged and 1/8 inch test piece): according to the ASTMD-256 standard testing, unit represents with kg.cm/cm.
* softening point temperature (Vicat SofteningTemperature): according to the ASTMD-1525 standard testing, unit is with a ℃ expression.
* joint line intensity: among 150mm * 70mm * 1/8 inch, on the tabular thing of empty rectangle the rectangle hole of one 40mm * 50mm is set, and is provided with one at this plate object one end and penetrates the pan feeding sluice gate; When raw material is entered in the plate object of hollow by the pan feeding opening, can be away from forming a joint line on the hollow plate object with pan feeding sluice gate one end; On molding, form the testing plate that the joint line place has a lateral junction zygonema in the middle of cutting out (70mm * 10mm * 1/8 inch) afterwards again, and the shock strength of testing its non-notch (no notch), unit is kgcm/cm, that is, according to the ASTMD-256 standard test, but the test film central authorities of test usefulness do not establish breach.
* moulding product outward appearance: the test piece of moulding product, with visual detection, the flat appearance person is with zero expression, and there are particulate state prominence or flake person in the surface with * expression.Embodiment
＜embodiment 1 〉
After the prepared graft copolymer of table 1 (C-1) 20 weight parts, graft copolymer (D) 32 weight parts, multipolymer (E) 48 weight parts and polycarbonate (F) 100 weight parts are mixed, with Li Siruisi forcing machine (Leistritz Micro-18, L/D=40), behind 250 ℃ of extrusion granulators, drying is that 250 ℃ forcing machine is extruded and obtained testing plate with extrusion temperature promptly.Test result is recorded in the table 2.
＜embodiment 2 〉
According to the prescription of table 2 raw material is mixed the back and obtain each test according to the treatment process moulding of embodiment 1 and use test piece, the rerum natura result who records also lists in the table 2.
＜embodiment 3 〉
According to the prescription of table 2 raw material is mixed the back and obtain each test according to the treatment process moulding of embodiment 1 and use test piece, the rerum natura result who records also lists in the table.
＜embodiment 4 〉
According to the prescription of table 2 raw material is mixed the back and use test piece according to each test of treatment process moulding of embodiment 1, the rerum natura result who records also lists in the table 2.
＜embodiment 5 〉
According to the prescription of table 2 raw material is mixed the back and use test piece according to each test of treatment process moulding of embodiment 1, the rerum natura result who records also lists in the table 2.
＜embodiment 6 〉
According to the prescription of table 2 raw material is mixed the back and use test piece according to each test of treatment process moulding of embodiment 1, the rerum natura result who records also lists in the table 2.
＜comparative example 1 〉
With the operational condition of embodiment 1, difference is: do not add graft copolymer (C) in its prescription, prepared test film carries out the test of various rerum naturas equally, and the results are shown in Table 2 for it.
＜comparative example 2 〉
With the operational condition of embodiment 1, difference be its prescription in graft copolymer (C-5) in do not contain rubber graft copolymer (A) and propylene base system monomer (B), its rerum natura is tested in the gained test piece equally, the results are shown in Table 2.
＜comparative example 3)
Operational condition with embodiment 1, but the graft copolymer (C-1) in the prescription changes graft copolymer (C-6) into, rubber graft copolymer (A) in the above-mentioned graft copolymer (C-6) surpasses 10 weight parts, and the test piece of institute's moulding is tested equally, and the result also lists in the table 2.
＜comparative example 4 〉
With the operational condition of embodiment 1, but the graft copolymer (C-1) in the prescription changes graft copolymer (C-7) into, adds propenyl based copolymer (B) in this graft copolymer (C-7), and the test piece of moulding is tested equally, and the result also lists in the table 2.
＜comparative example 5 〉
With the operational condition of embodiment 1, but the usage quantity of graft copolymer (C-1) in the prescription is up to 94.2 weight parts, and the test piece of institute's moulding is tested equally, and its result also lists in the table 2.
By the test-results of comparative example 1 as can be known, among the present invention if do not add graft copolymer (C), to make the resin flow reduction, the joint line intensity of finished product is also significantly relatively poor, by the test result of comparative example 2 as can be known, when containing rubber graft copolymer (A) and propenyl based copolymer (B) in the graft copolymer (C), also can't obtain higher joint line intensity, and when the usage quantity of rubber graft copolymer (A) is higher than 10 weight parts in the composition, because melt flow index reduces, obvious particulate state prominence can appear in the finished product outward appearance, so the outward appearance of moulding product is not good, by the test result of comparative example 3 as can be known: and when not adding propenyl based copolymer (B) in the graft copolymer (C), though joint line intensity reduces few, because the rubber particles dispersion is inhomogeneous, the outward appearance of finished product type also has the particulate state prominence, its outward appearance is also undesirable, and this test-results by comparative example 4 shows; And show by the test-results of comparative example 5, when the addition of graft copolymer (C) during up to 95 weight parts, the shock strength of moulding product and the joint line intensity extreme difference that all becomes.
See embodiment 1-6 again, the present invention is through aforementioned each composition and use quantitative limitation, can improve the flowability of the adulterant of polycarbonate resin and phenylethylene resin series, and composition is more prone in the course of processing, the restriction of foregoing also can improve the intensity at moulding product joint line place, and can improve the adulterant processing of polycarbonate resin and phenylethylene resin series and the shortcoming of finished product, and can utilize on the industry.
It should be understood that above only is that the present invention will be described for mode with embodiment.For those skilled in the art, do not departing from various modifications or the change that essence of the present invention is done, all should be included in the protection domain that the application's claim limited.
Table 1 (weight part)
| The numbering of graft copolymer (C) | ????(C-1) | ????(C-2) | ????(C-3) | ???(C-4) | ???(C-5) | ??(C-6) | ????(C-7) |
| Rubber graft copolymer (A) | ????(A-1) ????1.4 | ????(A-1) ????1.4 | ????(A-2) ????1.4 | ???(A-2) ????2.9 | ????- ????0 | ??(A-1) ??14.0 | ????(A-1) ????2.7 |
| Propenyl based copolymer (B) | ????(B-1) ????1.4 | ????(B-2) ????3.6 | ????(B-1) ????2.3 | ????(B-1) ????4.3 | ????- ????0 | ??(B-1) ??3.5 | ????0 |
| Diene series rubber | ????7.0 | ????7.2 | ????7.0 | ????5.8 | ????9.8 | ??2.3 | ????5.5 |
| Vinylbenzene | ????74.4 | ????70.0 | ????72.1 | ????76.0 | ????74.4 | ??74.4 | ????76.0 |
| Vinyl cyanide | ????25.6 | ????24.0 | ????19.8 | ????24.0 | ????25.6 | ??25.6 | ????24.0 |
| Methyl methacrylate | ????0 | ????6.0 | ????2.3 | ????0 | ????0 | ??0 | ????0 |
| N-phenylmaleimide | ????0 | ????0 | ????5.8 | ????0 | ????0 | ??0 | ????0 |
Table 2
| Experiment numbers | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Composition | Graft copolymer (C) weight part | ????(C-1) ????20.0 | ????(C-1) ????40.0 | ????(C-2) ????20.0 | ????(C-3) ????60.0 | ????(C-1) ????20.0 | ????(C-1) ????20.0 | ????0 | ????(C-5) ????40.0 | ????(C-6) ????20.0 | ????(C-7) ????20 | ????(C-1) ????94.2 |
| Graft copolymer (D) weight part | ????32.0 | ????29.0 | ????32.0 | ????26.0 | ????32.0 | ????32.0 | ????40.0 | ????29.0 | ????32.0 | ????32.0 | ????5.8 | |
| Multipolymer (E) weight part | ????48.0 | ????31.0 | ????48.0 | ????14.0 | ????48.0 | ????48.0 | ????60.0 | ????31.0 | ????48.0 | ????48.0 | ????0 | |
| Polycarbonate (F) weight part | ????100.0 | ????100.0 | ????100.0 | ????100.0 | ????100.0 | ????120.0 | ????100.0 | ????100.0 | ????100.0 | ????100.0 | ????100.0 | |
| Test subject | Melt flow index (MI) | ????2.78 | ????3.10 | ????2.85 | ????3.22 | ????2.81 | ????2.6 | ????2.63 | ????2.94 | ????1.80 | ????2.8 | ????6.5 |
| Emhorn shock strength (kg-cm/cm) | ????52.8 | ????55.3 | ????51.0 | ????56.5 | ????52.3 | ????54.0 | ????54.5 | ????56.0 | ????45.0 | ????52.0 | ????25.0 | |
| Softening temperature (℃) | ????132.3 | ????130.8 | ????132.5 | ????134.3 | ????133.0 | ????134 | ????129.0 | ????132.8 | ????128.5 | ????131.2 | ????142.5 | |
| Joint line intensity (kg.cm/cm) | ????42.3 | ????39.7 | ????41.4 | ????43.5 | ????41.6 | ????42.0 | ????28.0 | ????26.5 | ????35.0 | ????36.0 | ????13.0 | |
| Moulding product outward appearance | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????× | ????× | ????○ | |
Claims (3)
1, a kind of styrene resin composite comprises:
(1) graft copolymer of 5-90 weight part (C), this graft copolymer (C) obtains as follows: with the weight average particle diameter of 0.1-10 weight part is that the rubber graft copolymer (A) of 0.05-0.8 μ m, the diene series rubber of 2-25 weight part and the propenyl based copolymer (B) of 0.1-10 weight part are the following monomer mixture of 100 weight parts with gross weight: the acrylic monomer of the styrenic monomers of 45-80 weight part, 15-50 weight part reaches the copolymerizable monomer of the 0-40 weight part of optionally choosing wantonly and carries out body and/or solution copolymerization;
(2) graft copolymer of 10-95 weight part (D), this graft copolymer (D) obtains as follows: with the weight average particle diameter of 50-85 weight part (dry weight) is that the rubber latex of 0.05-0.8 μ m and styrenic monomers, the acrylic monomer of 15-50 weight part and the copolymerizable monomer mixture of optionally choosing wantonly carry out the emulsification graft polymerization;
(3) multipolymer of 0-60 weight part (E), this multipolymer (E) obtains as follows: with the styrenic monomers of 50-80 weight part, the acrylic monomer of 20-50 weight part, and optionally and the copolymerizable monomer of optional 0-40 weight part is carried out copolymerization; And
(4) with respect to total amount be graft copolymer (C), graft copolymer (D) and the multipolymer (E) of 100 weight parts, the polycarbonate of 40-200 weight part (F).
2, according to the described styrene resin composite of claim 1, wherein said rubber graft copolymer (A) adopts emulsion polymerization method to obtain.
3, according to the described styrene resin composite of claim 1, the percentage of grafting of wherein said rubber graft copolymer (A) is between 10-40%, and the molecular weight of institute's grafted hard multipolymer is 40, and 000-120 is between 000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95120405A CN1108342C (en) | 1995-12-14 | 1995-12-14 | Thermoplastic resin composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95120405A CN1108342C (en) | 1995-12-14 | 1995-12-14 | Thermoplastic resin composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1152004A true CN1152004A (en) | 1997-06-18 |
| CN1108342C CN1108342C (en) | 2003-05-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95120405A Expired - Fee Related CN1108342C (en) | 1995-12-14 | 1995-12-14 | Thermoplastic resin composite |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744846A (en) * | 2013-12-27 | 2015-07-01 | 奇美实业股份有限公司 | Thermoplastic resin composition and molded article |
| CN108690339A (en) * | 2017-03-31 | 2018-10-23 | 奇美实业股份有限公司 | Thermoplastic resin composition and molded article |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8702603A (en) * | 1987-11-02 | 1989-06-01 | Stamicarbon | THERMOPLASTIC POLYMER MIXTURE. |
| DE4414762B4 (en) * | 1993-04-28 | 2009-02-12 | Mitsubishi Rayon Co., Ltd. | Thermoplastic resin composition |
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1995
- 1995-12-14 CN CN95120405A patent/CN1108342C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104744846A (en) * | 2013-12-27 | 2015-07-01 | 奇美实业股份有限公司 | Thermoplastic resin composition and molded article |
| CN104744846B (en) * | 2013-12-27 | 2018-02-02 | 奇美实业股份有限公司 | Thermoplastic resin composition and molded article |
| CN108690339A (en) * | 2017-03-31 | 2018-10-23 | 奇美实业股份有限公司 | Thermoplastic resin composition and molded article |
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| CN1108342C (en) | 2003-05-14 |
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