CN1057105C - High luster impact-resistance excellent processing fluidity styrene series resin composition - Google Patents
High luster impact-resistance excellent processing fluidity styrene series resin composition Download PDFInfo
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- CN1057105C CN1057105C CN94109475A CN94109475A CN1057105C CN 1057105 C CN1057105 C CN 1057105C CN 94109475 A CN94109475 A CN 94109475A CN 94109475 A CN94109475 A CN 94109475A CN 1057105 C CN1057105 C CN 1057105C
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Abstract
The present invention discloses a styrene series resin composition of impact resistance, high brightness and favorable processing flowability, which comprises (I) 40 to 90 wt% of styrene series copolymer (A) and (II) 10 to 60 wt% of rubberlike graft copolymer (B), wherein the rubberlike graft copolymer (B) also comprises 65 to 95 wt% of rubber and 5 to 30 wt% of styrene series copolymer (B2), wherein in the styrene series copolymer (B2), the content of not grafted copolymer is less than 20 wt% of the total amount of the styrene series copolymer (B2), and the molecular weight of the grafted styrene series copolymer is 20000 to 150000.
Description
The present invention is about the good styrene resin composite of a kind of high gloss, shock-resistance and processibility.
Those skilled in the art understand, and styrene resin composite is to be scattered in a kind of impact resistant resin composition made in the styrene based copolymer with rubber like graft copolymer.On using, family's shell of electrical article and this used resinous materials of automobile moulded products need possess shock-resistant and performance such as high gloss simultaneously, and ABS resin is exactly the representative styrene resin composite material that meets above-mentioned requirements, therefore, extensively is used for many years.
Yet, the common shock-resistance high resin of healing, its glossiness is lower; On the contrary, the glossiness high resin of healing, its shock-resistance is then relatively poor; This is because the shock-resistance of resin is simultaneously relevant with rubber content or rubber size in the resin with glossiness.From in the past research as can be known, the rubber content in resin the more or rubber size bigger, its shock-resistance is stronger; And the rubber content in resin is healed low or rubber size is littler, and then its glossiness is higher.Therefore, how to make a kind of possess simultaneously high-luster and the good resin material of impact strength become the present technique field for a long time the utmost point wait to study the problem of breakthrough.
For making resin can have shock-resistance and high-luster concurrently, a kind of of traditional mode of ameliorating is to make the rubbery copolymer that contains two or more different rubber sizes in the resin combination, for example is exactly for Japanese kokai publication sho 59-202211 number.Perhaps, also have by gel (gel) content of rubbery copolymer in the restriction resin combination and achieve the goal, for example disclosedly be exactly for Japanese kokai publication sho 62-84109 number.But it is, therefore still very limited to the improvement effect of glossiness because of above-mentioned modification method all needs to use the rubbery copolymer that contains big particle diameter.In addition, once mentioned for Japanese kokai publication sho 62-201959 number, contained the rubbery copolymer of 0.04-0.15 μ m rubber size in the composition, can make the resin of high gloss and shock-resistance.Yet its shock-resistance does not reach practical level.
Physicals for fortified resin, another kind of traditional mode of ameliorating is the hard phase of graft phenylethene based copolymer on rubber, this mode is if will reach best physicals, for example: physicalies such as high impact, high glossiness, need make the grafting degree (graft level) of rubber graft copolymer high to a certain degree just reaching, otherwise can't obtain good shock strength and high gloss.But reactor capacity or the quantity required for the rubber graft copolymer that makes aforementioned high grafting degree are all bigger, therefore, can't obtain high efficiency production, also can cause production cost higher and do not have shortcomings such as economy; And when using emulsion polymerization method to prepare rubber graft copolymer, because high grafting degree can produce more waste water, exert an adverse impact for environment, therefore, how under high production efficiency, low cost and oligosaprobic situation, make the rubber graft copolymer of low grafting degree, and make it possess high-luster and the good phenylethylene resin series material of impact strength, become the problem that the utmost point for a long time waits to study breakthrough.
Main purpose of the present invention is under high-level efficiency, low cost and oligosaprobic preparation situation, and a kind of styrene resin composite that has shock-resistance, high glossiness and excellent processing fluidity concurrently is provided.
Feature of the present invention is, this impact polystyrene based resin composition with high gloss and excellent processing fluidity, mainly comprise: (I) 40-90wt% styrene based copolymer (A), this styrene based copolymer (A) are that other copolymerisable monomer of monomer and/or methacrylate ester monomer and 0-40wt% is formed by 50-90wt% vi-ny l aromatic monomers, 10-50wt% unsaturated nitrile; (II) 10-60wt% rubber like graft copolymer (B), this rubber like graft copolymer (B) comprising: 65-95wt% rubber (B
1) and 5-30wt% styrene based copolymer (B
2) (comprise grafting and be not grafted on person on the rubber), wherein styrene based copolymer (B
2) be that monomer and/or methacrylate ester monomer and other copolymerisable monomer of 0-40wt% are formed by 50-90wt% vi-ny l aromatic monomers, 10-50wt% unsaturated nitrile, and grafted styrene based copolymer content does not account for styrene based copolymer (B
2) below the 20wt% of total amount, and the molecular weight of grafted styrene based copolymer is 20,000-150,000.
According to above-mentioned composition, can make a kind of styrene resin composite that has shock-resistant characteristic and high-luster simultaneously.
Styrene based copolymer in the styrene resin composite of the present invention (A) is that other copolymerisable monomer of monomer and/or methacrylate ester monomer and 0-40wt% is formed by 50-90wt% vi-ny l aromatic monomers, 10-50wt% unsaturated nitrile; Wherein,
Vi-ny l aromatic monomers can be: vinylbenzene, alpha-methyl styrene, α-chloro-styrene, right-t-butyl styrene, p-methylstyrene, neighbour-chloro-styrene, right-chloro-styrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromo-benzene ethene and 2,5-Dowspray 9 etc., wherein, optimization styrene or alpha-methyl styrene.
Unsaturated nitrile is that monomer can be: vinyl cyanide, Alpha-Methyl vinyl cyanide, methacrylonitrile, anti-crotononitrile etc., wherein, preferred vinyl cyanide; The methacrylate ester monomer can be: methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, methacrylic dodecyl gallate, methacrylic acid 2-hydroxyl ethyl ester, glycidyl methacrylate and dimethylaminoethyl methacrylate etc., wherein, preferable methyl methyl acrylate.
Suitable copolymerisable monomer comprises that maleimide is a monomer, for example: 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-or 4-tolyl maleimide, N-2,3-or 4-ethylbenzene base maleimide, N-2,3-or 4-butylbenzene base maleimide, N-2,6-tolyl maleimide, N-2,3-or 4-chloro-phenyl-maleimide, N-2,3-or 4-bromophenyl Malaysia imide.
Other copolymerisable monomer also has: acrylic monomer, Maleic Acid, Anhydrous, anhydrous methyne Succinic Acid, anhydrous methyl-maleic acid, anhydrous neocerotic acid, ethene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, ethylene chloride, fork tetrafluoroethylene, a chlorine three are fluoridized ethene, hexafluoro propylene, divinyl, propenyl amine, isobutenyl amine, vinyl acetate between to for plastic, vinyl ether, vinyl ketone etc.
Account in the rubber like graft copolymer (B) of styrene resin composite gross weight 10-60wt% of the present invention, include rubber (B
1) and styrene based copolymer (B
2); Wherein,
Rubber (B
1) content is 65-95wt%, and preferred 75-90wt%, they can be polyhutadiene, butadiene-based interpolymer, ethylene-propylene copolymer (for example EPDM (ethylene-propylene-diene terpolymer) etc.) or acrylic ester polymer; Above-mentioned butadiene-based interpolymer has butadiene/styrene copolymers, butadiene/acrylonitrile copolymer etc.; The median size of rubber is 0.05-0.6 μ m, preferred 0.2-0.5 μ m, and as adopting the size distribution of double-peak type, wherein first group median size is 0.04-0.18 μ m, second group median size is 0.20-0.6 μ m.
Aforementioned rubber (B
1) can adopt emulsification, solution or the preparation of block polymerization, preferable methods is: the rubber latex that monomer is directly become 0.05-0.6 μ m with the emulsion polymerization method polymerization; After also monomer can being made the small particle size rubber latex of 0.05-0.20 μ m with emulsion polymerization method, again with freezing loose method or mechanical loose method or the loose method of additive with the loose rubber latex that becomes 0.22-0.6 μ m of above-mentioned small particle size rubber, in order to further carrying out graft copolymerization.Wherein, employed additive can be in the loose method of additive: acidic substance such as acetic anhydride, hydrogenchloride, sulfuric acid, or: salt-base substances such as sodium-chlor, Repone K, calcium chloride, magnesium chloride, sal epsom and (methyl) acrylic acid series-(methyl) acrylate based copolymer (as: methacrylic acid-butyl acrylate copolymer) etc. contain the acidic group polymer coagulant.
Styrene based copolymer (B in the rubber like graft copolymer (B)
2) comprise and be grafted on the rubber and be not grafted on person on the rubber, this styrene based copolymer (B
2) be that other copolymerisable monomer of monomer and/or methacrylate ester monomer and 0-40wt% is formed by 50-90wt% vi-ny l aromatic monomers, 10-50wt% unsaturated nitrile; The styrene based copolymer content that is not grafted on the rubber simultaneously accounts for styrene based copolymer (B
2) below the 20wt% of total amount; And the molecular weight that is grafted on the styrene based copolymer on the rubber is 20, and 000-150 is wherein preferred 40 between 000,000-120,000.
As previously mentioned, in rubber like graft copolymer of the present invention (B), rubber (B
1) account for 65-95wt%, and preferred 75-90wt%, styrene based copolymer (B
2) in, the styrene based copolymer content that is not grafted on the rubber accounts for styrene based copolymer (B
2) below the 20wt% of total amount, simultaneously, the molecular weight of grafted styrene based copolymer is 20,000-150,000, and preferred 40,000-120,000.Rubber (B in rubber like graft copolymer (B)
1) account for 65wt% when following, can't obtain the preparation efficiency height, cost is low and pollutes low resin, when this ratio is higher than 95wt%, not only dullness, rigidity and processing fluidity variation, shock-resistance and unit elongation also can sharply descend, and can't meet the requirement in the practicality.In addition, at rubber (B
1) account under the condition of 65-95wt%, the styrene based copolymer content that is not grafted on the rubber accounts for styrene based copolymer (B
2) when the 20wt% of total amount is above, cause the cohesion that rubber is bad easily, make that the dispersiveness between rubber particles is not good, can't be evenly dispersed in the styrene based copolymer hard mutually in, cause its deterioration of impact resistance, and glossiness do not see improvement yet, rigidity is also had bad influence.Styrene based copolymer (B in rubber like graft copolymer
2) molecular weight be lower than at 20,000 o'clock, can't obtain good impact strength and rigidity.Otherwise the molecular weight of above-mentioned styrene based copolymer is higher than 150,000, and the glossiness of composition can descend, and processing fluidity is variation also.
The styrene based copolymer of styrene resin composite of the present invention (A) can be according to any traditional polymerization process, for example suspension polymerization, block suspension polymerization or block polymerization preparation.
The rubber like graft copolymer of styrene resin composite of the present invention (B) can be by known method preparation, for example block polymerization, suspension polymerization, bulk-suspension polymerization, solution polymerization or letex polymerization etc., wherein, the preferred emulsion polymerization.And in the preparation process of graft copolymer, styrene based copolymer (B
2) can in reaction, directly form, styrene based copolymer can be grafted on rubber (B
1) on, also the grafted free state does not exist.
Polymerization initiator of the present invention can use initiator commonly used on the conventional art, for example dibenzoyl peroxide (benzoyl peroxide), hydrogen peroxide diisopropyl benzene (diiso-propyl benzene hydroperoxide), hydrogen peroxide isopropyl benzene (cumene hy-droperoxide), tertbutyl peroxide (tert-butyl hydroperoxide), Potassium Persulphate (potassium persulfate) etc., wherein, preferred organic hydroperoxide kind.
The present invention can also use the activator on the conventional arts such as the activator of redox-catalyst system or iron ion, for example: trisodium phosphate dextrose (sodium pyrophosphate-dextrose), sodium sulfoxylate formaldehyde (sodium formaldehyde sulfoxylate), xitix (ascorbic acid), otan (dihydroxy acetone), etc. all can use; Also can add edetate (ethylene diamine tetraaceticacid salt) in addition and promote its effect; Iron(ic) chloride or ferrous sulfate can be used in the source of iron ion.
Be not grafted on the styrene based copolymer content on the rubber, can be controlled by polymerizing condition, for example: kind and consumption, the monomeric addition means etc. of polymerization temperature, initiator, emulsifying agent, chain-transfer agent are controlled.
In addition, also can add the molecular weight that chain-transfer agent is adjusted graftomer according to conventional art, for example: normal-butyl mercaptan (n-bytyl mercaptan), n-octyl mercaptan (n-octyl mercaptan), n-dodecyl mercaptan (n-dodecylmercaptan), uncle-lauryl mercaptan (tert-dodecyl mercaptan).
The molecular weight of graftomer of the present invention also can be adjusted by the kind of polymerization temperature, initiator and the change of polymerizing conditions such as consumption, monomeric addition means.
The temperature of reaction that the present invention suits is below 90 ℃, preferred 30-80 ℃.
Styrene resin composite of the present invention can add other material as required, example as this kind material has: antioxidant, lubricant, UV light absorber, ultra-violet stabilizer, charged preventor, weighting agent, reinforcer, tinting material, fire retardant, flame retardant, thermo-stabilizer, coupler or other additive etc., above-mentioned additive can be in polyreactions, after the polyreaction or solidify preceding and extrude in the mixing process and add in passing.
It is that antioxidant, thioether are materials such as antioxidant, phosphorous antioxidant, chelating that antioxidant uses usually as phenol; Representative phenol is that antioxidant has: octadecyl (3,5-dual-tert-butyl-4-hydroxyphenyl) propionic ester, triethylene glycol two (3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester), (3-(3 for five moss alcohol four, 5-dual-tert-butyl-4-hydroxyphenyl) the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxyl-6-methylbenzene methyl)-4-aminomethyl phenyl acrylate, 2 propionic ester),, 2 '-methylene-bis (4-methyl-6-tert butyl phenol) and 2,2 '-sulphur two (4-methyl-6-tert butyl phenol) etc.
Representative thioether is that antioxidant has: two hard ester acyl thiodipropionic acid esters, two palmityl thiodipropionic acid esters, five tetrahydroxybutanes-four-(β-ten dimethyl-sulphur propionic ester), two octadecyl thioethers etc.
Phosphorous antioxidant is that phosphite is an antioxidant, representative has: three (nonyl phenyl) phosphite, dodecyl phosphite, ring-type neopentane tetralyl two (octadecyl phosphite), 4,4 '-butylidene two (3-methyl-6-tert butyl phenyl-double tridecyl phosphite), three (2, the 4-tert-butyl-phenyl) phosphite or four (2, the 4-tert-butyl-phenyl)-4,4 '-stretch xenyl phosphoric acid salt, oxidation 9,4-dihydro-9-oxy-10-phosphoric acid phenanthrene etc.
Representative sequestrant has: the sodium salt of phenyl phenacyl ketone, diethylamine four acetic acid etc.
The addition of above-mentioned antioxidant adds up to 0.03-1.6wt% usually with respect to total phenylethylene resin series.
Representative lubricant has: the compound of the metallic soaps of sodium stearate, Magnesium Stearate, lithium stearate etc., ethylene distearyl acid amides, methylene distearyl acid amides, palmitic amide, butyl stearate, stearic acid palm ester, poly-propionic acid alcohol tristearate, behenic acid, stearic acid etc., polyethylene wax, octocosoic acid wax, babassu (Carnauba) wax, petroleum wax etc.; The addition of lubricant adds up to 0.03-5.0wt% usually with respect to total phenylethylene resin series.Representative UV light absorber has: benzotriazole based compound, benzophenone based compound, and representative ultra-violet stabilizer has: the retardance amine compound; The addition of aforementioned substances adds up to 0.02-2.0wt% usually with respect to total phenylethylene resin series.
Representative charged preventor has: the low molecule based compound of tertiary amine based compound, quaternary ammonium salt based compound etc. or polymeric amide polyethers, as the macromolecular material of permanent charged the preventing property of the polymeric tool of epichlorohydrin.
Representative weighting agent has: lime carbonate, tripoli, mica.
Representative reinforcer has: glass fibre, carbon fiber, various brilliant silk (whisker) class.
Representative tinting material has: ferric oxide, ferric oxide, graphite, phthalocyanine pigment.
Representative fire retardant or flame retardant have: decabrominated dipheny base ether, tetrabromo-bisphenol, brominated Polystyrene oligomerization zoarium, brominated epoxy resin, hexabromocyclododecane, chlorinatedpolyethylene, triphenyl phosphoric acid, red phosphorus, weisspiessglanz, antimony hydroxide, magnesium hydroxide, zinc borate, melamine, silica oil, polytetrafluorethylepowder powder, expansile graphite etc.
Representative stablizer has: dibutyl tin maleate, alkali magnalium hydroxyl carbonate etc.Representative coupler has: silane system, admire acid esters, germanic acid ester based compound.
In styrene resin composite of the present invention for modification, can suitably use the additive of polymerization system, the example of above-mentioned representative polymerization system additive as: be various propylene base system polymers (being called as processing aid), ethylene chloride resin, polymethylmethacrylate, polycarbonate resin, the polyamide resin, poly-that improves the extrusion moulding processibility to the sour butene esters of admiring, ethylene series polymer, polystyrene plasticity-elastomerics, low-molecular-weight phenylethylene-maleic anhydride interpolymer, silica oil, various phase solvations etc.
Styrene based copolymer (B in rubber like graft copolymer (B)
2) in be not grafted on ratio on the rubber, be to measure with following method, that is: the sample with the 1g rubber like graft copolymer is dissolved in the 35g acetone, stir after 2 hours, under the 15000rpm rotating speed, high speed centrifugation 1 hour, then clear liquor is filtered, dry insolubles again and weigh, just can obtain percentage of grafting, and then try to achieve the not ratio of grafted styrene based copolymer by the rubber content in percentage of grafting and the sample by the rubber content in the sample.
Research according to people such as Dinges (can be with reference to Die Makromol.Chemie101,1967, the 200-213 page or leaf), the molecular weight of graft copolymer the and molecular weight of grafted multipolymer is not identical, therefore measure the not molecular weight of grafted styrene based copolymer, just can obtain the molecular weight of grafted styrene based copolymer indirectly.In the present invention, the measuring method of the molecular weight of grafted styrene based copolymer is not, sample with the 3g rubber like graft copolymer is dissolved in the 100g acetone earlier, stir after 2 hours, high speed centrifugation 1 hour under the rotating speed of 15000rpm is more then analyzed in the clear liquor the not molecular weight of graft phenylethene based copolymer with GPC (gas permeation chromato-graph).
By embodiment and the prepared styrene resin composite of Comparative Examples, the measuring method of its various rerum naturas is as follows: 1. melting index (MI is the index of processing fluidity):
Examine and determine according to ASTM-D1238G.2. Ai Zuode impact strength (Izod):
Record according to ASTM-D256.3. tensile strength (tensile strength):
Method according to ASTM-D638 records.4. glossiness:
Method according to ASTM-D523 records.
In the following Examples and Comparative Examples, except as otherwise noted, otherwise all umbers and per-cent (%) all are benchmark with weight.Embodiment 1
In stirred reactor, add 250 parts of rubber latexs (composition: polyhutadiene solid 30%, gel content 75%, median size 0.26 μ m).Temperature of reaction is heated to 70 ℃.Add 3.0 part of 0.2% copperas solution, 0.9 part of 10% formaldehyde sulfoxylate sodium solution and 3.0 part of 0.25% edta solution.Divide 6 hourly averages to splash into monomer solution and initiator solution.Monomer solution contains 18.75 parts of vinylbenzene, 6.25 parts of vinyl cyanide, 2.0 parts of uncle-lauryl mercaptans.Initiator solution then contains 30 parts of deionized waters, 3.0 parts of hydrogen peroxide isopropyl benzenes and 3.0 part of 10% sodium dodecyl sulfate solution.After monomer solution and initiator solution drip off, continue insulated and stirred again 2 hours, can obtain a kind of rubber like graft copolymer (being composition (B)).
In the rubber like graft copolymer (composition (B)) of gained, add octadecyl-3-(3 again, 5-two-tertiary butyl-4-hydroxy-phenyl)-(Ciba Geigy produces propionic ester, trade name IRGANOX 1076) 0.5 part, 1.0 parts two-stearyl sulfo--two-propionic salts (di-stearyl thio-di-propionate), mix after 20 minutes, add 2% calcium chloride solution again, be allowed to condition at 85 ℃ and condense, filter again, dewater, then in 60 ℃ of following vacuum-dryings.
Dried rubber like graft copolymer powder, its not grafted styrene based copolymer (AS) account for styrene based copolymer (B
2) total amount 9%, the molecular weight of grafted styrene based copolymer is 56,000.
Dried rubber like graft copolymer powder mixes with AS resin (being composition (A)) again, (the monomer whose weight ratio is: vinyl cyanide/vinylbenzene=30/70, molecular weight is 120,000), making becomes 17% the styrene resin composite that rubber content accounts for the composition gross weight; Add 3.0 parts of lubricants and stablizer again, and under 200 ℃, extrude mixing granulation, ejection formation then, and measure its rerum natura.Embodiment 2
Repeat embodiment 1 described process, but use following prescription: rubber latex (composition is as described above): 266.7 part of 0.2% copperas solution: 2.4 part of 10% formaldehyde sulfoxylate sodium solution: 0.7 part of 0.25% edta solution: 2.4 parts of monomer solutions:
Vinylbenzene: 14 parts
Vinyl cyanide: 6 parts
Uncle-lauryl mercaptan: 1.6 parts of initiator solution:
Deionized water: 30 parts
Hydrogen peroxide isopropyl benzene: 2.4 parts
10% sodium dodecyl sulfate solution: in the rubber like graft copolymer of 2.4 parts of gained (composition (the B)) powder:
(1) grafted styrene based copolymer (AS) does not account for styrene based copolymer (B
2) per-cent of total amount: 12%
(2) molecular weight of grafted styrene based copolymer: 63,000, the monomer weight ratio in the used AS resin (composition (A)):
Vinyl cyanide/vinylbenzene=30/70, molecular weight 120000
(3) rubber content in the gained styrene resin composite: 17% embodiment 3
Repeat embodiment 1 described process, but use following prescription: rubber latex (composition is as described above): 283.3 part of 0.2% copperas solution: 1.8 part of 10% formaldehyde sulfoxylate sodium solution: 0.5 part of 0.25% edta solution: 1.8 parts of monomer solutions:
Vinylbenzene: 11 parts
Vinyl cyanide: 4 parts
Uncle-lauryl mercaptan: 1.2 parts of initiator solution:
Deionized water: 30 parts
Hydrogen peroxide isopropyl benzene: 1.8 parts
10% sodium dodecyl sulfate solution: in 1.8 parts of gained rubber like graft copolymer (composition (B)) powder:
(1) grafted styrene based copolymer (AS) does not account for styrene based copolymer (B
2) per-cent of total amount: 10%
(2) molecular weight of grafted styrene based copolymer: 61,000, the monomer weight ratio in the used AS resin (composition (A)):
Vinyl cyanide/vinylbenzene=30/70, molecular weight 120000
(3) rubber content in the gained styrene resin composite: 17% embodiment 4
Repeat embodiment 1 described process, but use following prescription: rubber latex (composition is as described above): 266.7 part of 0.2% copperas solution: 2.4 part of 10% formaldehyde sulfoxylate sodium solution: 0.7 part of 0.25% edta solution: 2.4 parts of monomer solutions:
Vinylbenzene: 14 parts
Vinyl cyanide: 6 parts
Uncle-lauryl mercaptan: 4.5 parts of initiator solution:
Deionized water: 30 parts
Hydrogen peroxide isopropyl benzene: 2.4 parts
10% sodium dodecyl sulfate solution: 5 parts
In addition, when preparation rubber like graft copolymer (composition (B)), temperature of reaction is 80 ℃, and monomer solution and initiator solution are that branch 5 hourly averages splash in the stirred reactor.In gained rubber like graft copolymer (composition (the B)) powder:
(1) grafted styrene based copolymer (AS) does not account for styrene based copolymer (B
2) per-cent of total amount: 10%
(2) molecular weight of grafted styrene based copolymer: 36,000, the monomer weight ratio in the used AS resin (composition (A)):
Vinyl cyanide/vinylbenzene=30/70, molecular weight 120000
(3) rubber content in the gained styrene resin composite: 17% embodiment 5
Repeat embodiment 1 described process, but use following prescription: rubber latex (composition is as described above): 266.7 part of 0.2% copperas solution: 2.4 part of 10% formaldehyde sulfoxylate sodium solution: 0.7 part of 0.25% edta solution: 2.4 parts of monomer solutions:
Vinylbenzene: 14 parts
Vinyl cyanide: 6 parts
Uncle-lauryl mercaptan: 1.2 parts of initiator solution:
Deionized water: 30 parts
Hydrogen peroxide isopropyl benzene: 2.4 parts
10% sodium dodecyl sulfate solution: 1 part
In addition, when preparation rubber like graft copolymer (composition (B)), temperature of reaction is 60 ℃, and monomer solution and initiator solution are that branch 8 hourly averages splash in the stirred reactor.In gained rubber like graft copolymer (composition (the B)) powder:
(1) grafted styrene based copolymer (AS) does not account for styrene based copolymer (B
2) per-cent of total amount: 10%
(2) molecular weight of grafted styrene based copolymer: 112,000, the monomer weight ratio in the used AS resin (composition (A)):
Vinyl cyanide/vinylbenzene=30/70, molecular weight 120000
(3) rubber content in the gained styrene resin composite: 17% embodiment 6
Repeat embodiment 1 described process, but use following prescription: rubber latex (composition is as described above): 266.7 part of 0.2% copperas solution: 2.4 part of 10% formaldehyde sulfoxylate sodium solution: 0.7 part of 0.25% edta solution: 2.4 parts of monomer solutions:
Vinylbenzene: 14 parts
Vinyl cyanide: 3 parts
Methyl methacrylate: 3 parts
Uncle-lauryl mercaptan: 1.6 parts of initiator solution:
Deionized water: 30 parts
Hydrogen peroxide isopropyl benzene: 2.4 parts
10% sodium dodecyl sulfate solution: in 2.4 parts of gained rubber like graft copolymer (composition (B)) powder:
(1) grafted styrene based copolymer (AS) does not account for styrene based copolymer (B
2) per-cent of total amount: 12%
(2) molecular weight of grafted styrene based copolymer: 73,000, the monomer weight ratio in the used AS resin (composition (A)):
Vinyl cyanide/vinylbenzene=30/70, molecular weight 120000
(3) rubber content in the gained styrene resin composite: 17% embodiment 7
Repeat embodiment 1 described process, but use following prescription: rubber latex (composition is as described above): 266.7 part of 0.2% copperas solution: 2.4 part of 10% formaldehyde sulfoxylate sodium solution: 0.7 part of 0.25% edta solution: 2.4 parts of monomer solutions:
Vinylbenzene: 14 parts
Vinyl cyanide: 6 parts
Uncle-lauryl mercaptan: 1.6 parts of initiator solution:
Deionized water: 30 parts
Hydrogen peroxide isopropyl benzene: 2.4 parts
10% sodium dodecyl sulfate solution: in 2.4 parts of gained rubber like graft copolymer (composition (B)) powder:
(1) grafted styrene based copolymer (AS) does not account for styrene based copolymer (B
2) per-cent of total amount: 12%
(2) molecular weight of grafted styrene based copolymer: 63,000, the monomer weight ratio in the used AS resin (composition (A)):
Vinyl cyanide/vinylbenzene/N-phenylmaleimide=29.1/67.9/3.0, molecular weight 120000
(3) rubber content in the gained styrene resin composite: 17% Comparative Examples 1
Repeat embodiment 1 described process, but use following prescription: rubber latex (composition is as described above): 266.7 part of 0.2% copperas solution: 2.4 part of 10% formaldehyde sulfoxylate sodium solution: 0.7 part of 0.25% edta solution: 2.4 parts of monomer solutions:
Vinylbenzene: 14 parts
Vinyl cyanide: 6 parts
Uncle-lauryl mercaptan: 1.6 parts of initiator solution:
Deionized water: 30 parts
Hydrogen peroxide isopropyl benzene: 2.4 parts
10% sodium dodecyl sulfate solution: 5 parts
In addition, when preparation rubber like graft copolymer composition (B), temperature of reaction is 55 ℃, and monomer solution and initiator solution are that branch 3 hourly averages splash in the stirred reactor.In gained rubber like graft copolymer (composition (the B)) powder:
(1) grafted styrene based copolymer (AS) does not account for styrene based copolymer (B
2) per-cent of total amount: 33%
(2) molecular weight of grafted styrene based copolymer: 56,000, the monomer weight ratio in the used AS resin (composition (A)):
Vinyl cyanide/vinylbenzene=30/70, molecular weight 120000
(3) rubber content in the gained styrene resin composite: 17% Comparative Examples 2
Repeat embodiment 1 described process, but use following prescription: rubber latex (composition is as described above): 266.7 part of 0.2% copperas solution: 2.4 part of 10% formaldehyde sulfoxylate sodium solution: 0.7 part of 0.25% edta solution: 2.4 parts of monomer solutions:
Vinylbenzene: 14 parts
Vinyl cyanide: 6 parts
Uncle-lauryl mercaptan: 0.2 part of initiator solution:
Deionized water: 30 parts
Hydrogen peroxide isopropyl benzene: 2.4 parts
10% sodium dodecyl sulfate solution: 2.4 parts
In addition, when preparation rubber like graft copolymer composition (B), temperature of reaction is 60 ℃, and monomer solution and initiator solution are that branch 6 hourly averages splash in the stirred reactor.In gained rubber like graft copolymer (composition (the B)) powder:
(1) grafted styrene based copolymer (AS) does not account for styrene based copolymer (B
2) per-cent of total amount: 10%
(2) molecular weight of grafted styrene based copolymer: 19,5000, the monomer weight ratio in the used AS resin (composition (A)):
Vinyl cyanide/vinylbenzene=30/70, molecular weight 120000
(3) rubber content in the gained styrene resin composite: 17% Comparative Examples 3
Repeat embodiment 1 described process, but use following prescription: rubber latex (composition is as described above): 320 part of 0.2% copperas solution: 0.6 part of 10% formaldehyde sulfoxylate sodium solution: 0.2 part of 0.25% edta solution: 0.6 part of monomer solution:
Vinylbenzene: 3 parts
Vinyl cyanide: 1 part
Uncle-lauryl mercaptan: 0.4 part of initiator solution:
Deionized water: 30 parts
Hydrogen peroxide isopropyl benzene: 0.6 part
10% sodium dodecyl sulfate solution: in 0.6 part of gained rubber like graft copolymer (composition (B)) powder:
(1) grafted styrene based copolymer (AS) does not account for styrene based copolymer (B
2) per-cent of total amount: 9%
(2) molecular weight of grafted styrene based copolymer: 58,000, the monomer weight ratio in the used AS resin (composition (A)):
Vinyl cyanide/vinylbenzene=30/70, molecular weight 120000
(3) rubber content in the gained styrene resin composite: 17%
Table 1 has been listed the composition of styrene based copolymer used in above-mentioned all embodiment and the prepared composition of styrene resin of Comparative Examples (composition (A)) and rubber like graft copolymer (composition (B)), total composition of gained styrene resin composite and the rerum natura of these embodiment and Comparative Examples gained styrene resin composite.In table 1, the meaning of each symbol representative is as follows: AN: vinyl cyanide SM: styrene monomer BD: polyhutadiene MMA: methyl methacrylate gloss%: glossiness (%) IZ: Ai Zuode impact strength (kg-cm/cm) MI: melting index (g/10min) TS
y: yield-point tensile strength (kg/cm
2) EL: unit elongation (%)
Therefore really can have high glossiness, impact strength and good processing flowability simultaneously according to styrene resin composite of the present invention, be very suitable for the goods that shell that machine-shaping is tame electrical article and automobile moulding product etc. must possess impact strength and high gloss characteristics simultaneously.In sum, the present invention is real to have broken through the restriction that traditional phenylethylene resin series institute when low grafting degree can't have impact strength and high-luster simultaneously concurrently, so its progressive really, practicality and novel invention.
Table 1
| Embodiment | Comparative Examples | |||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 | |||
| Rubber like graft copolymer (B) | Content wt% | 22.67 | 21.25 | 20 | 21.25 | 21.25 | 21.25 | 21.25 | 21.25 | 21.25 | 21.25 | |
| Form | AN％ | 6.25 | 6 | 4 | 6 | 6 | 3 | 6 | 6 | 6 | 1 | |
| SM％ | 18.75 | 14 | 11 | 14 | 14 | 14 | 14 | 14 | 14 | 3 | ||
| BD％ | 75 | 80 | 85 | 80 | 80 | 80 | 80 | 80 | 80 | 96 | ||
| MMA％ | - | - | - | - | - | 3 | - | - | - | - | ||
| Rerum natura | Gloss％ | 96 | 94 | 94 | 96 | 93 | 96 | 95 | 89 | 87 | 80 | |
| IZ | 25.2 | 25.0 | 22.9 | 21.2 | 24.7 | 22.0 | 22.3 | 18.2 | 17.5 | 9.5 | ||
| MI | 1.55 | 1.64 | 1.71 | 1.78 | 1.54 | 1.66 | 1.52 | 1.55 | 1.35 | 1.36 | ||
| TS y | 450 | 455 | 458 | 435 | 460 | 440 | 460 | 420 | 440 | 403 | ||
| EL | 22 | 25 | 26 | 16 | 24 | 19 | 21 | 16 | 19 | 7 | ||
Claims (3)
1. styrene resin composite, comprise: (I) 40-90wt% styrene based copolymer (A), this styrene based copolymer (A) are that other copolymerisable monomer of monomer and/or methacrylate ester monomer and 0-40wt% is formed by 50-90wt% vi-ny l aromatic monomers, 10-50wt% unsaturated nitrile; (II) 10-60wt% rubber like graft copolymer (B), this rubber like graft copolymer (B) comprising: 65-95wt% rubber (B1) and comprise grafting and be not grafted on 5-30% styrol copolymer (B2) on the rubber, wherein styrene based copolymer (B2) is that monomer and/or methacrylate ester monomer and other copolymerisable monomer of 0-40wt% are formed by 50-90wt% vi-ny l aromatic monomers, 10-50wt% unsaturated nitrile, and grafted styrene based copolymer content does not account for styrene based copolymer (B
2) below the 20wt% of total amount, and the molecular weight of grafted styrene based copolymer is 20,000-150,000.
2. according to the styrene resin composite of claim 1, the rubber (B in the rubber like graft copolymer (B) wherein
1) content is 75-90wt%.
3. according to the styrene resin composite of claim 1, the contained styrene based copolymer (B of rubber like graft copolymer wherein
2) in, the molecular weight of grafted styrene based copolymer is 40,000-120,000.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94109475A CN1057105C (en) | 1994-08-15 | 1994-08-15 | High luster impact-resistance excellent processing fluidity styrene series resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94109475A CN1057105C (en) | 1994-08-15 | 1994-08-15 | High luster impact-resistance excellent processing fluidity styrene series resin composition |
Publications (2)
| Publication Number | Publication Date |
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| CN1121938A CN1121938A (en) | 1996-05-08 |
| CN1057105C true CN1057105C (en) | 2000-10-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100358944C (en) * | 2005-06-03 | 2008-01-02 | 中化国际余杭高分子材料研发设计有限公司 | Composition of cinnamene resin with good light sensation and plasticity |
| CN101565532B (en) * | 2008-04-22 | 2011-01-05 | 奇美实业股份有限公司 | Resin composition of rubber modified (methyl) acrylic ester |
| JP5688975B2 (en) * | 2009-01-16 | 2015-03-25 | 電気化学工業株式会社 | Rubber-modified thermoplastic resin composition, injection-molded body thereof, and lid of washing machine using the same |
| TWI481655B (en) * | 2012-12-28 | 2015-04-21 | Chi Mei Corp | Rubber modified methacrylate-based resin composition |
| TWI455983B (en) * | 2012-12-28 | 2014-10-11 | Chi Mei Corp | Rubber-modified methacrylate-based resin composition |
| CN109071702A (en) * | 2016-04-29 | 2018-12-21 | Sabic环球技术有限责任公司 | Method for producing copolymer |
| CN108285609B (en) * | 2018-01-09 | 2020-10-02 | 佳易容聚合物(上海)有限公司 | High melt strength styrene resin composition and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1005689B (en) * | 1986-09-19 | 1989-11-08 | 东北重型机械学院 | Hot rolling process for h-shaped steel beam with corrugated web |
| EP0505153A1 (en) * | 1991-03-18 | 1992-09-23 | Japan Synthetic Rubber Co., Ltd. | Rubber-reinforced styrene resin composition and process for producing the same |
-
1994
- 1994-08-15 CN CN94109475A patent/CN1057105C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1005689B (en) * | 1986-09-19 | 1989-11-08 | 东北重型机械学院 | Hot rolling process for h-shaped steel beam with corrugated web |
| EP0505153A1 (en) * | 1991-03-18 | 1992-09-23 | Japan Synthetic Rubber Co., Ltd. | Rubber-reinforced styrene resin composition and process for producing the same |
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| Publication number | Publication date |
|---|---|
| CN1121938A (en) | 1996-05-08 |
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