CN1057785C - Serial heat-resistant styrene resin composites - Google Patents
Serial heat-resistant styrene resin composites Download PDFInfo
- Publication number
- CN1057785C CN1057785C CN96120544A CN96120544A CN1057785C CN 1057785 C CN1057785 C CN 1057785C CN 96120544 A CN96120544 A CN 96120544A CN 96120544 A CN96120544 A CN 96120544A CN 1057785 C CN1057785 C CN 1057785C
- Authority
- CN
- China
- Prior art keywords
- weight
- monomer
- rubber
- resistant styrene
- resin composites
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a heat resisting styrene series resin composition capable of maintaining physical property balance and preventing a formed product from generating a black trace, which comprises 100 portions of heat resisting styrene series copolymer (1) by weight and 0.1 to 5 portions of low molecular weight polyolefin (C)(2) by weight, wherein the heat resisting styrene series copolymer is prepared from a continuous matrix phase of an imide group containing styrene series copolymer (A) and rubber particles (B) dispersed in the continuous matrix phase, and the rubber particles (B) account for 5 to 45 wt% of the resin composition; the viscosity-average molecular weight of the low molecular weight polyolefin (C) is from 500 to 10, 000; (A) is prepared by polymerizing a styrene series monomer, an acrylonitrile series monomer, a maleimide series monomer and other copolymerizable monomers. The weight-average particle diameter of (B) is from 0.05 to 0.8 mu m, and the total content of a dipolymer and a trimer which are formed by the styrene series monomer and/or the acrylonitrile series monomer in the resin composition is below 20, 000 ppm.
Description
The present invention is relevant a kind of rubber-modified serial heat-resistant styrene resin composites, is meant a kind of rerum natura balances such as flowability, thermotolerance of keeping especially, can improve the resin combination that the moulding product produce black trace phenomenon again.
Why phenylethylene resin series (as ABS resin etc.) is widely used on electrical equipment, electronics and the auto parts, mainly be because all there is good evaluation its processing forming, physical property and mechanical properties aspect, the good appearance of moulding product and the glossiness big characteristic of one especially especially; But, along with user's improving constantly to quality requirements, general phenylethylene resin series still has on shock strength and thermotolerance needs improved place, again, the machine-shaping dealer is in order to improve the cast gate outward appearance of ejection formed piece at present, and adopt full-automatic production, be to gradually adopt pin cast gate (Pin gate) to come ejection formation, this kind pin cast gate is because the duct is minimum, the higher resin melt of viscosity is difficult for flowing through the duct ejection formation, therefore, the requirement of the flowability of raising phenylethylene resin series is also strong day by day; On the other hand, though the ejection formation of automatization can reduce the manpower demand, and can a large amount of fast production, but phenylethylene resin series has black trace to occur at ejection formation often, makes product produce flaw; Therefore, how making thermal resistant styrene is the rerum natura balance that resin has good fluidity and thermotolerance etc., and resin is not given birth to black trace again when moulding, be the problem that this field needs to be resolved hurrily.
Main purpose of the present invention ties up to and provides a kind of and keep thermotolerance and mobile rerum natura balance, and does not produce the serial heat-resistant styrene resin composites of black trace when moulding.
The present invention ties up to provides a kind of rerum natura balance of keeping, and can prevent that again the moulding product from producing the serial heat-resistant styrene resin composites of black trace, and said composition comprises:
The thermal resistant styrene based copolymer of (1) 100 part of weight, it is the continuous matrix phase by the styrene based copolymer that contains imide (A), and is dispersed in this continuous matrix phase, and the rubber particles (B) that accounts for resin combination 5～45 weight % constitutes;
The viscosity-average molecular weight of (2) 0.1～5 parts of weight is 500～10,000 low-molecular-weight polyolefin (C);
Wherein, the styrene based copolymer (A) that contains imide is to be that monomer and other copolymerizable monomer are polymerized by styrenic monomers, acrylic monomer, maleimide, and the weight average particle diameter of rubber particles (B) is 0.05～0.8 μ m, and dipolymer that contained styrenic monomers and/or acrylic monomer are become in the above-mentioned serial heat-resistant styrene resin composites and trimeric total content are 20, below the 000ppm.
The styrene based copolymer (A) that contains imide of the present invention be by 89～20 parts of weight of styrenic monomers, acrylic monomer 10～50 parts of weight, maleimides be 1～30 part of weight of monomer and optionally and the choosing 0～40 part of weight polymerization of copolymerizable monomer and get, it can bulk, solution, outstanding turbid or emulsion polymerization method make, be good with bulk or solution polymerization process again wherein, the weight average molecular weight of the above-mentioned styrene based copolymer (A) that contains imide is 60,000～400, between 000, preferable is 80,000～300, between 000; Styrenic monomers among the present invention can be selected for use: vinylbenzene, alpha-methyl styrene,--chloro-styrene ,-t-butyl styrene ,-vinyl toluene, neighbour-chloro-styrene, right-chloro-styrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromo-benzene ethene or 2,5-Dowspray 9s etc. wherein, are preferable with vinylbenzene or alpha-methyl styrene.In serial heat-resistant styrene resin composites of the present invention, the polymerized unit of styrenic monomers (polymerized unit) content is 30～80 weight %.
The acrylic monomer that is used among the present invention can be: vinyl cyanide, Alpha-Methyl vinyl cyanide etc., and wherein preferable with vinyl cyanide; The present invention contains the copolymerizable monomer of using in the styrene based copolymer (A) of imide and can be: (methyl) acrylic ester monomer, vinylformic acid, methacrylic acid, Maleic Acid, Anhydrous etc., wherein, (methyl) acrylic ester monomer can be: methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, the methacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, methacrylic acid dodecane ester, methacrylic acid 2-hydroxyl ethyl ester, glycidyl methacrylate, Dimethylaminoethyl Methacrylate, methyl acrylate, butyl acrylates etc. are wherein with methyl methacrylate, butyl acrylate is good.
The maleimide that is used among the present invention 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-ethylbenzene base maleimide, N-2,4-ethylbenzene base maleimide, N-2,3-butylbenzene base maleimide, N-2,4-butylbenzene base 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 imides etc. wherein are again best with the N-phenylmaleimide.The polymerized unit content of maleimide monomer is 5～30 weight % in serial heat-resistant styrene resin composites of the present invention.
The preferable preparation method who contains the styrene based copolymer (A) of imide of the present invention, can finish by the reactor of continous way bulk or solution polymerization, above-mentioned reactor comprises: column flow reactor, continuous stirred tank reactor (CSTR) (CSTR), perhaps containing the pipe reactor of silent oscillation hybrid element etc., is good with continuous stirred tank reactor (CSTR) wherein; Above-mentioned reactor quantity can be one; also can and use two or more; when making the styrene based copolymer (A) that contains imide of the present invention; can the thermopolymerization mode or polymerization starter added in the reaction; this polymerization starter comprises acyl peroxide class, peroxyesters, ketal peroxide class, peroxycarbonates class; and having azo-compound of nitro and cyclohexane ring etc., the addition of above-mentioned polymerization starter is usually based on monomeric 0.01～1.0 weight % of 100 parts of weight.
The temperature of reaction of above-mentioned reactor system is controlled at 80～200 ℃, preferably be controlled in 90～160 ℃ the scope, and the pressure of reactor system is controlled at 1～5kg/cm
2Between, as for the time that material solution is trapped in the reactor should be between 1～5 hour; In addition, for the molecular weight of controlling polymers, just for example can use-lauryl mercaptan, the chain-transfer agent of uncle-lauryl mercaptan, terpinolene etc.
After the polymer monomer transformation efficiency reaches 40～80 weight %, usually system is heated to the highest temperature with prepared copolymer solution with preheater, and then with the volatilization step remove unreacted monomer and the volatilization composition, general volatilization step can use the device or the forcing machine de-gassing vessel of decompression degassing vessel to remove the volatilization composition, with condenser it is gathered into recovery liquid afterwards, and after will reclaiming moisture content in the liquid and removing, use as material solution again; With removing the polymerization melts extrusion granulator of volatilization composition, can obtain the styrene based copolymer (A) that contains imide of the present invention.
The present invention is dispersed in the rubber particles in the continuous matrix phase of the styrene based copolymer (A) that contains imide, account for 5～45 weight % of resin combination, and the rubber particles system that is dispersed in the matrix phase exists with the form of rubber graft copolymer, and promptly it is the graft copolymer of emulsified rubber particle (B).
The made graft copolymer of rubber particles of the present invention (B) can be emulsified rubber particle or solution (totally) rubber particles, it ties up to 45～85 parts of weight of diene series rubber emulsion and exists down, with by styrenic monomers 50～90 weight %, acrylic monomer 10～50 weight %, and 55～15 parts of weight of monomer mixture of other copolymerizable monomer 0～40 weight % composition, graft polymerization and the graft copolymer emulsion of emulsified rubber particle (B) of weight average particle diameter 0.05～0.8 μ m, or make the graft copolymer emulsion that particle diameter that different rubber weight average particle diameter mixes is the rubber particles (B) (its weight average particle diameter is respectively: 0.06～0.15 μ m and 0.16～0.6 μ m) of bimodal distribution, again through condensing, dehydration, drying and other steps, and make the graft copolymer of powder granulous emulsified rubber particle (B); Above-mentioned diene series rubber emulsion means and includes 100～60 weight % conjugate diene monomers and the formed homopolymer of monomer (homopolymer) is closed in the copolymerizable insatiable hunger of 0～40 weight %, or its multipolymer (copolymer), above-mentioned conjugate diene monomer can be represented by following formula:
Wherein, R can be hydrogen, methyl or chlorine etc., and copolymerizable insatiable hunger is closed monomer and be can be styrenic monomers, acrylic monomer, methacrylate ester monomer, acrylic ester monomer or its mixture.
Diene series rubber emulsion used in the present invention can be polyhutadiene, butadiene-styrene copolymer, perbutan, divinyl-methylmethacrylate copolymer, isoprene-butyl acrylate copolymer etc.; Above-mentioned diene series rubber emulsion can above-mentioned monomer direct polymerization becomes the form of weight average particle diameter 0.05～0.8 μ m, after also can aggregating into the small particle size rubber latex of 0.05～0.18 μ m earlier, again with the loose method of traditional rubber, with the loose rubber latex that becomes 0.2～0.8 μ m of the small particle size rubber of 0.05～0.18 μ m, the loose method of above-mentioned rubber can be adds organic acid or metal-salt or contains the chemical loose method of carboxylic acid group's polymer coagulant, the loose method of churned mechanically machinery or freezing loose method etc.; The polymer coagulant that the loose method of above-mentioned chemistry is adopted can use for example butyl acrylate-Sipacril 2739OF.
The preparation of the prepared graft copolymer of above-mentioned emulsified rubber particle (B) normally utilizes graft polymerization technique commonly used, in the presence of the rubber-like polymer, with styrenic monomers, acrylic monomer, and the copolymerizable monomer mixture that optionally adds carries out graft polymerization reaction, utilizes the combination of chemical or hard styrene based copolymer that at least a above-mentioned grafted monomer of grafting is constituted on diene series rubber; Usually all factors such as infiltration degree in advance, chain-transfer agent, emulsifying agent consumption and kind of the speed, monomer and the rubber that add of the polymerization temperature of graft polymerization reaction, the kind of initiator, the polymeric physics of rubber-like, chemical property (as copolymerization composition, the content of rubber swelling degree, rubber), size of particles, monomer all can influence the grafting thickness of hard styrol copolymer.
On diene series rubber, another partly then forms the multipolymer (free copolymer) of free shape to a part of system of the hard styrene based copolymer that above-mentioned emulsification graft polymerization monomer polymerization forms with chemical bonding; Observe with the electron micrograph of rubber graft copolymer again, can seal (Occlusion) above-mentioned hard styrene based copolymer in the rubber particles, also can not seal the hard styrene based copolymer fully, it is sealed degree and decides on rerum natura; Some hard styrene based copolymer is grafted on the rubber particles surface in addition.
Initiator that above-mentioned graft polymerization reaction added or catalyst can be preferably in 0.1～3.0 part of weight usually in 0.01～5.0 part of weight range of polymerization single polymerization monomer; Its addition is decided according to monomer and required polymerizing condition, but above-mentioned initiator increment add, make the carrying out that is beneficial to graft polymerization reaction.
The molecular weight size of above-mentioned graftomer again, can be controlled by the temperature of graft polymerization reaction, and/or the molecular weight regulator that cooperates quite less ratio to use always, for example: mercaptan, halogenating agent or terpenes etc. are regulated, and the comparatively concrete example of this molecular weight regulator has: just-and lauryl mercaptan, uncle-lauryl mercaptan, α-Jia Jibenyixierjuwu.
Above-mentioned graft polymerization reaction can utilize monomer mixture to add in the paradigmatic system with continuous or increment ground, and preferably continuous simultaneously or increment ground adding initiator; Above-mentioned initiator can use various known emulsification radical polymerization initiators, for example: superoxide (peroxy), azo-compound or persulfate compound; Suitable peroxide initiator is for example: cumyl superoxide (dicumyl peroxide dicumyl peroxide), tert-butyl peroxide (tert-butyl-peroxide), benzoyl peroxide (benzoylperoxide), isopropyl benzene hydrogen peroxide (cumene hydroperoxide), tertbutyl peroxide (tert-butyl hydroperoxide) etc.
The polyreaction of above-mentioned diene series rubber emulsion and monomer mixture is to stir under 20～100 ℃ rare gas element, and it also can be forced into 0～100psig (pound/square inch); Desire to make 90% monomer to be aggregated in the reaction, its polymerization time needs 2～10 hours usually, and is good with 3～8 hours.
The employed styrenic monomers of the made graft copolymer of emulsified rubber particle (B), acrylic monomer and copolymerizable monomer, except copolymerizable monomer can further comprise maleimide is the monomer, all the other illustrate identically with monomer in the styrene based copolymer that contains imide (A), do not give unnecessary details at this.
Can make the emulsion of emulsified rubber particle (B) of weight average particle diameter 0.05～0.8 μ m of rubber particles via above-mentioned graft polymerization reaction.
The weight average particle diameter of the so-called rubber particles of the present invention, mean resin ultrathin section(ing) or emulsion are smeared, dyed back is with 10, the transmission electron microscope of 000 multiplying power is taken a picture, with about 200～1,000 of the rubber dispersed particle that shines in the photograph, measure its particle diameter respectively, try to achieve weight average particle diameter with following formula again, that is:
n
i=rubber particles directly is D
iThe rubber particles number
Must add suitable condensing agent in the emulsion of above-mentioned emulsified rubber particle (B) again condenses, general employed condensing agent has acids, the alkaline earth salt of sulfuric acid, acetic acid etc., for example: the aluminium salt of the magnesium salts of the calcium salt of calcium chloride etc., magnesium chloride, sal epsom etc., Tai-Ace S 150 etc. is good with alkaline earth salt wherein; The polymer slurries that condenses after finishing is removed moisture content through dewatering process, and drying is handled again, can make the graft copolymer of powder shape emulsified rubber particle (B).
In addition, the present invention learns, dipolymer and trimeric total content that styrenic monomers that resin combination is contained and/or acrylic monomer r are become should be 20, below the 000ppm, when above-mentioned content is higher than 20, during 000ppm, resin moulding product when moulding have the vestige of black, and make the moulding product produce flaw; In the dipolymer and trimer that is become as for so-called styrenic monomers among the present invention and/or acrylic monomer, dipolymer comprises: AS, AA and SS, trimer then comprises: AAA, SSS, A
2S, S
2A, wherein A represents the acrylic monomer, and S represents styrenic monomers.
Low-molecular-weight polyolefin used in the present invention (C) is a kind of low-molecular-weight polyethylene, this low-molecular-weight polyethylene comprises the high-density (High density type) of non-modified, the polyethylene of low density (Low densitytype), and through various modified polyethylene, for example through acidic group modified polyethylene (Acid-modified type), through benzoic acid modified polyethylene (Aromatic acid-modified type), and through the high density polyethylene(HDPE) (Oxidation modification) of oxygen base modification; The high density polyethylene(HDPE) of non-modified then is to be polymerized separately by ethene, and the new LDPE (film grade) of non-modified is that (α-olefine) copolymerization forms by ethene and alpha-olefins; In addition, modified polyethylene is to be grafted on the molecular chain by for example oxygen base or acidic group isopolarity base, and its viscosity-average molecular weight is 500～10, and between 000, melt viscosity is recorded at 140 ℃ by the Brookfield-type viscometer, below 2000cps (centipoise).
When low-molecular-weight polyethylene usage quantity during greater than 5 parts of weight, can make the thermotolerance of resin descend, be not suitable for machine-shaping, in the resin combination if do not add low-molecular-weight polyethylene, then the moulding product can produce black trace because of resin flow is not good, are unfavorable for penetrating processing.
The present invention can further add phenol system as required or the sulphur propionic ester is an antioxidant, and obtaining having the resin combination of predetermined properties, the present invention also can suitably add in order to improve photostabilizer, UV light absorber, filling agent, colorant, lubricant, plasticizer and the antistatic agent of phenylethylene resin series formability; In addition, but the present invention is mixed polymer alloy resin also, for example: polycarbonate, polymeric amide, polyester (PET, PBT), polyphenylene oxide, polyvinyl chloride, polymethylmethacrylate, ethylene-methyl methacrylate methyl terpolymer, polypropylene, styrene butadiene block copolymer, hydrogenated acrylonitrile-butadienecopolymer, hydrogenated styrene-divinyl block copolymer etc. and use it, its allotment amount are generally with respect to 5～200 parts of weight of 100 parts of weight of resin combination.
For obtaining resin combination of the present invention, its blending means is representative to be: with the Han Xieer mixing machine of general use do mix after again with such as the mixing machine melting mixing of extruding mixing machine, kneader or Banbury mixer (Banburymixer) etc.
Resin combination of the present invention is applicable to jet forming method, extrusion moulding, compressed moulding method, blows forming methods such as prolonging the method for forming, hot-forming method, vacuum forming and slush molding method.
For further describing the present invention in detail, be described as follows with embodiment and rerum natura survey formula again, the composition unless specifically stated otherwise of following composition, otherwise be that umber by weight and the weight percent that accounts for whole composition weight are recently represented.
Below enumerate embodiment and describe the present invention in detail, but scope of the present invention is not exceeded with these embodiment.
＜preparation example〉＜preparation example I-1〉contain the preparation of the styrene based copolymer (A-1) of imide:
The raw material of vinylbenzene 68 weight %, vinyl cyanide 22 weight % and N-phenylmaleimide 10 weight % is mixed, again with ethylene distearyl acid amides 0.025 weight %, uncle-lauryl mercaptan, and volatilization composition formed recovery liquid after condensation that following reaction is removed merges as feeding feeding, remain on the continous way still type reactor with agitator of 45 liters of 145 ℃ and volumes with temperature in infeeding, and make the toluene ratio in the reaction solution remain on 15%, and percent polymerization remain on 56%.
When reaction solution is removed the volatilization composition by volatilization device after, can obtain containing the particle of the styrene based copolymer of imide; On the other hand, the volatilization composition of being removed is condensing as reclaiming liquid with condenser, and mixes with the above-mentioned raw materials mixed solution continuously and re-use it; Adjust the consumption of uncle-lauryl mercaptan and make the styrene based copolymer that contains imide (A-1) that the melt flow stream index is 1.0 (g/10min).＜preparation example I-2〉contain the preparation of the styrene based copolymer (A-2) of acyl industry amido:
The raw material of vinylbenzene 68 weight %, vinyl cyanide 22 weight % and N-phenylmaleimide 10 weight % is mixed, again with ethylene distearyl acid amides 0.025 weight %, uncle-lauryl mercaptan, and volatilization composition formed recovery liquid after condensation that following reaction is removed merges as feeding feeding, remain on the continous way still type reactor with agitator of 45 liters of 108 ℃ and volumes with temperature in infeeding, and make the toluene ratio in the reaction solution remain on 15%, and percent polymerization remain on 55%.
When reaction solution is removed the volatilization composition by volatilization device after, can obtain containing the particle of the styrene based copolymer of imide; On the other hand, the volatilization composition of being removed is condensing as reclaiming liquid with condenser, and mixes with the above-mentioned raw materials mixed solution continuously and re-use it; Adjust speed of response with this method by the consumption of benzoyl peroxide, or the consumption of adjustment uncle-lauryl mercaptan is made the styrene based copolymer that contains imide (A-2) that the melt flow stream index is 0.9 (g/10min).＜preparation example I-3〉contain the preparation of the styrene based copolymer (A-3) of imide:
The raw material of vinylbenzene 68 weight %, vinyl cyanide 22 weight % and N-phenylmaleimide 10 weight % is mixed, again with ethylene distearyl acid amides 0.025 weight %, uncle-lauryl mercaptan, and volatilization composition formed recovery liquid after condensation that following reaction is removed merges as feeding feeding, remain on the continous way still type reactor with agitator of 45 liters of 155 ℃ and volumes with temperature in infeeding, and make the toluene ratio in the reaction solution remain on 15%, and percent polymerization remain on 57%.
When reaction solution is removed the volatilization composition by volatilization device after, can obtain containing the particle of the styrene based copolymer of imide; On the other hand, the volatilization composition of being removed is condensing as reclaiming liquid with condenser, and mixes with the above-mentioned raw materials mixed solution continuously and re-use it; Adjust the consumption of uncle-lauryl mercaptan and make the styrene based copolymer that contains imide (A-3) that the melt flow stream index is 1.1 (g/10min).＜preparation example I-4〉contain the preparation of the styrene based copolymer (A-4) of imide:
According to＜preparation example I-1〉the preparation method, difference is: the raw material with vinylbenzene 45 weight %, vinyl cyanide 20 weight %, alpha-methyl styrene 34 weight % and N-phenylmaleimide 1 weight % mixes, 0.1 weight % reacts with ethylene distearyl acid amides, and can make the melt flow stream index is the styrene based copolymer that contains imide (A-4) of 1.4 (g/10min).＜preparation example I-5〉contain the preparation of the styrene based copolymer (A-5) of imide:
According to＜preparation example I-2〉the preparation method, difference is: the raw material with vinylbenzene 45 weight %, vinyl cyanide 20 weight %, alpha-methyl styrene 34 weight % and N-phenylmaleimide 1 weight % mixes, 0.1 weight % reacts with ethylene distearyl acid amides, and can make the melt flow stream index is the styrene based copolymer that contains imide (A-5) of 1.5 (g/10min).＜preparation example I-6〉preparation of styrene based copolymer (A-6):
According to＜preparation example I-3〉the preparation method, difference is: the raw material with vinylbenzene 45 weight %, vinyl cyanide 20 weight %, alpha-methyl styrene 35 weight % mixes, 0.1 weight % reacts with ethylene distearyl acid amides, can make the styrene based copolymer that the melt flow stream index is 1.7 (g/10min) (A-6).＜preparation example II〉preparation of graft copolymer of emulsified rubber particle (B):
Composition part weight
1,3-butadiene 95.0
Vinyl cyanide 5.0
Potassium persulfate solution 15.0
Potassium pyrophosphate 3.0
Potassium oleate 1.5
Distilled water 140.0
Uncle-lauryl mercaptan 0.2
Under 65 ℃ of temperature of reaction, reacted 12 hours according to above prescription, obtain that transformation efficiency 94%, solids content are about 40%, weight average particle diameter is the synthetic rubber latex of 0.1 μ m.
In addition, prepare carboxylic polymer coagulant (agglomerating agent) with following composition:
Composition part weight
N-ethyl propenoate 85
Vinylformic acid 15
Uncle-lauryl mercaptan 0.3
Potassium oleate 2.0
Dioctyl sodium sulphosuccinate 1.0
Isopropyl benzene hydrogen peroxidase 10 .4
Sodium formaldehyde sulphoxylate 0.3
Distilled water 200
Reacted 5 hours under 75 ℃ of temperature of reaction according to above prescription, obtain the carboxylic polymer coagulant of transformation efficiency 95%, pH value 6.0.
Afterwards, utilize the carboxylic polymer coagulant (dry weight) of 3 parts of weight to come the synthetic rubber latex (dry weight) of loose 100 parts of weight, the pH of resulting enlarged rubber emulsion directly is 8.5, and weight average particle diameter is 0.3 μ m.
At last, carry out graft polymerization reaction with the enlarged rubber emulsion according to following prescription again, to prepare emulsified rubber particle (B-1) graft copolymer:
Composition part weight
Enlarged rubber emulsion (dry weight) 100.0
Vinylbenzene 25.0
Vinyl cyanide 8.3
Potassium oleate 1.2
Uncle-lauryl mercaptan 0.2
Isopropyl benzene hydrogen peroxidase 10 .5
Copperas solution (0.2%) 3.0
Formaldehyde sodium sulfoxylate solution (10%) 3.0
Ethylene dinitrilotetra-acetic acid solution (0.25%) 20.0
Distilled water 200.0
Styrene/acrylonitrile in the above-mentioned prescription added in 5 hours with continuous addition manner polymerization makes the grafting rubbers emulsion of not condensing in the reactive system, with calcium chloride (CaCl
2) condense, dewater after, be dried to water content again below 2%, just can make emulsified rubber particle (B) graft copolymer of wanting required for the present invention (rubber content 75 weight %), the weight average particle diameter of its rubber particles is 0.3 μ m.
The physical property measurement standard of the embodiment of the invention and the obtained resin combination of comparative example is as follows:
One, melt flow stream index (MI):
, represent with 220 ℃ * 10kg test according to JIS K-7210 (Japanese Industrial Standards) regulation with g/10min.
Two, monomeric dipolymer of styrenic monomers and/or acrylic and trimeric total content testing method:
To be dissolved in the acetone through the serial heat-resistant styrene resin composites of rubber improvement, and this resin combination solution re-uses the numbering 5890A of Hewlett Packard (Hewlett-Packard) company with the gas chromatograph of the flame ionic detector mensuration that performs an analysis.
Three, tensile strength:
According to the test of ASTM D-638 regulation, with kg/cm
2Expression.
Four, softening point temperature (Vicat Softening Temperature):
Measure according to ASTM D-1525 regulation, unit is with a ℃ expression.
Five, black trace test: with the SM-90 ejaculator of serial heat-resistant styrene resin composites, to penetrate pressure 1000kg/cm via the production of the male company of shake
2, 240 ℃ of temperature, mould temperature penetrate 2 for 50 ℃ " * 3.5 " * 1/8 " test piece, whether have black (heterochromatic) trace, do not have black trace and be recorded as " O " if observing test piece, produce black trace or heterochromatic trace and then be recorded as " * ".
Embodiment＜embodiment 1 〉
Will be by＜preparation example I-1〉prepared styrene based copolymer (A-1) the 77.3 weight % that contain imide, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 22.7 weight % of prepared emulsified rubber particle (B), low molecular weight polyethylene (the Mitsui petrochemical iy produced that adds 2.0 parts of weight again, high-density aggretion type 200P, viscosity-average molecular weight=2000) and the lubricant of 0.6 part of weight, and with Werner ﹠amp; Pfleiderer ZSK 35 forcing machines can obtain the rubber-modified serial heat-resistant styrene resin composites of rubber content 17 weight % in 240 ℃ of mixing extrusion granulators; Then after penetrating test piece with the Jet forming machine that shakes the male factory number SM-90 of company under 240 ℃, measure rerum natura, and the visual black trace phenomenon of test piece of inspecting, and contained styrenic monomers and/or acrylic monomer are become in the analysed composition dipolymer and trimeric total content, the result is stated from table one.＜comparative example 1 〉
Will be by＜preparation example I-1〉prepared styrene based copolymer (A-1) the 77.3 weight % that contain imide, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 22.7 weight % of prepared emulsified rubber particle (B), do not add low molecular weight polyethylene, all the other conditions of molding are with embodiment 1, and the result is stated from table one.＜embodiment 2 〉
Will be by＜preparation example I-2〉prepared styrene based copolymer (A-2) the 77.3 weight % that contain imide, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 22.7 weight % of prepared emulsified rubber particle (B), add the low molecular weight polyethylene of 2.0 parts of weight and the lubricant of 0.6 part of weight again, all the other conditions of molding are with embodiment 1, and the result is stated from table one.＜embodiment 3 〉
Will be by＜preparation example I-2〉prepared styrene based copolymer (A-2) the 77.3 weight % that contain imide, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 22.7 weight % of prepared emulsified rubber particle (B), add the low molecular weight polyethylene of 4.0 parts of weight and the lubricant of 0.6 part of weight again, all the other conditions of molding are with embodiment 1, and the result is stated from table one.＜comparative example 2 〉
Will be by＜preparation example I-4〉prepared styrene based copolymer (A-4) the 76.0 weight % that contain imide, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 24.0 weight % of prepared emulsified rubber particle (B), the lubricant that adds 0.6 part of weight again, all the other conditions of molding are with embodiment 1, and the result is stated from table one.＜embodiment 4 〉
Will be by＜preparation example I-4〉prepared styrene based copolymer (A-4) the 76.0 weight % that contain imide, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 24.0 weight % of prepared emulsified rubber particle (B), add the low molecular weight polyethylene of 2.0 parts of weight and the lubricant of 0.6 part of weight again, all the other conditions of molding are with embodiment 1, and the result is stated from table one.＜embodiment 5 〉
Will be by＜preparation example I-5〉prepared styrene based copolymer (A-5) the 76 weight % that contain imide, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 24.0 weight % of prepared emulsified rubber particle (B), add the low molecular weight polyethylene of 2.0 parts of weight and the lubricant of 0.6 part of weight again, all the other conditions of molding are with embodiment 1, and the result is stated from table one.＜embodiment 6 〉
Will be by＜preparation example I-5〉prepared styrene based copolymer (A-5) the 76.0 weight % that contain imide, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 24.0 weight % of prepared emulsified rubber particle (B), add the low molecular weight polyethylene of 4.0 parts of weight and the lubricant of 0.6 part of weight again, all the other conditions of molding are with embodiment 1, and the result is stated from table one.＜comparative example 3 〉
Will be by＜preparation example I-1〉prepared styrene based copolymer (A-1) the 77.3 weight % that contain imide, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 22.7 weight % of prepared emulsified rubber particle (B), add the low molecular weight polyethylene of 7.0 parts of weight and the lubricant of 0.6 part of weight again, all the other conditions of molding are with embodiment 1, and the result is stated from table one.＜comparative example 4 〉
Will be by＜preparation example I-3〉prepared styrene based copolymer (A-3) the 77.3 weight % that contain acyl industry amido, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 22.7 weight % of prepared emulsified rubber particle (B), add the low molecular weight polyethylene of 2.0 parts of weight and the lubricant of 0.6 part of weight again, all the other conditions of molding are with embodiment 1, and the result is stated from table one.＜comparative example 5 〉
Will be by＜preparation example I-4〉prepared styrene based copolymer (A-4) the 76.0 weight % that contain acyl industry amido, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 24.0 weight % of prepared emulsified rubber particle (B), add the low molecular weight polyethylene of 7.0 parts of weight and the lubrication prescription of 0.6 part of weight again, the same example I of all the other conditions of molding, the result is stated from table one.＜comparative example 6 〉
Will be by＜preparation example I-6〉prepared styrene based copolymer (A-6) 76.0 weight %, by＜preparation example II 00 part of weight of thermal resistant styrene copolymer 1 of mixing of the graft copolymer 24.0 weight % of prepared emulsified rubber particle (B), add the low molecular weight polyethylene of 2.0 parts of weight and the lubricant of 0.6 part of weight again, all the other conditions of molding are with embodiment 1, and the result is stated from table one.
Test-results by comparative example 1,2 shows, do not use the serial heat-resistant styrene resin composites of low molecular weight polyethylene, its outward appearance can produce black trace because of Resin Flow is not good, be unfavorable for penetrating processing, and show that by the result of comparative example 3,5 when the low molecular weight polyethylene usage quantity in the resin combination was higher than 5.0 parts of weight, the softening point temperature of resin combination can reduce, be not suitable for the machine-shaping of heat-resisting level, its finished surface can produce black trace; And learn by the result of comparative example 4,6, dipolymer that is become when styrenic monomers and/or acrylic monomer and trimer total content are greater than 20, during 000ppm, after mixing low molecular weight polyethylene, the test piece surface has black (different) look current mark and produces, and can't be used in widely in the various processing.
Review embodiment 1～6, the usage quantity of the low molecular weight polyethylene in resin combination of the present invention is limited in 0.1～5.0 part of weight, and dipolymer that styrenic monomers and/or acrylic monomer are become and trimeric total content are 20, when 000ppm is following, not only can make resin combination between thermotolerance and flowability, keep good rerum natura balance, the test piece surface also can not produce black (different) look current mark, and make the resin combination of heat-resisting grade can be widely used in the ejaculation machine-shaping that need have the high softening-point temperature, so the present invention has the utility value on the industry really.
The above only is several preferable possible embodiments of the present invention, allly is familiar with this technology personage, and it is according to equal modification or change that the present invention's spirit scope is done, all ought to be included in the scope that technical scheme of the present invention contains.
Table one
| 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 | Comparative example 6 | ||||
| Anti-is that hot polymerization benzene closes second thing alkene | Styrene based copolymer (A) | Weight % | 77.3 | 77.3 | 77.3 | 76.0 | 76.0 | 76.0 | 77.3 | 76.0 | 77.3 | 77.3 | 76.0 | 76.0 | ||
| Kind | A-1 | A-2 | A-2 | A-4 | A-5 | A-5 | A-1 | A-4 | A-1 | A-3 | A-4 | A-6 | ||||
| The graft copolymers of emulsified rubber particle (B) | Weight % | 22.7 | 22.7 | 22.7 | 24.0 | 24.0 | 24.0 | 22.7 | 24.0 | 22.7 | 22.7 | 24.0 | 24.0 | |||
| The addition of low-molecular-weight polyolefin | Part weight | 2 | 2 | 4 | 2 | 2 | 4 | 0 | 0 | 7 | 2 | 7 | 2 | |||
| The rubber particles content of resin combination | Weight % | 17 | 17 | 17 | 18 | 18 | 18 | 17 | 18 | 17 | 17 | 18 | 18 | |||
| The dipolymer of vinylbenzene and/or vinyl cyanide and trimer total content | ppm | 10500 | 4940 | 4800 | 18160 | 9550 | 9480 | 10650 | 18050 | 10800 | 23500 | 17960 | 33100 | |||
| Black trace | Visual test piece | ○ | ○ | ○ | ○ | ○ | ○ | × | × | × | × | × | × | |||
| Rerum natura | The melt flow stream index | (g/10min) | 6.0 | 6.2 | 6.0 | 6.9 | 6.7 | 7.3 | 5. 3 | 5.6 | 7.1 | 6.5 | 7.3 | 7.5 | ||
| Tensile strength | (kg/cm 2) | 379 | 376 | 385 | 443 | 445 | 448 | 372 | 438 | 386 | 386 | 448 | 450 | |||
| Softening point temperature | (℃) | 125.1 | 124.9 | 125.0 | 113.8 | 113.7 | 113.5 | 124.8 | 113.7 | 112.5 | 119.7 | 106.0 | 107.8 | |||
Annotate: low-molecular-weight polyolefin is that the Mitsui petrochemical industry is made, high-density aggretion type 200P, viscosity-average molecular weight 2000.
Claims (7)
1, a kind of serial heat-resistant styrene resin composites is characterized in that comprising:
The thermal resistant styrene based copolymer of (1) 100 part of weight, it is the continuous matrix phase by the styrene based copolymer that contains imide (A), and is dispersed in this continuous matrix phase, and the rubber particles (B) that accounts for resin combination 5～45 weight % constitutes;
140 ℃ melt viscosity of (2) 0.1～5 parts of weight below 2000cps and viscosity-average molecular weight 500～10,000 low molecular weight polyethylene (C);
Wherein, the styrene based copolymer (A) that contains imide is to be that monomer and other copolymerizable monomer are polymerized by styrenic monomers, acrylic monomer, maleimide, and the weight average particle diameter of rubber particles (B) is 0.05～0.8 μ m, and dipolymer that contained styrenic monomers and/or acrylic monomer are become in the above-mentioned serial heat-resistant styrene resin composites and trimeric total content are 20, below the 000ppm.
2, serial heat-resistant styrene resin composites according to claim 1 is characterized in that rubber particles (B) is the emulsified rubber particle.
3, serial heat-resistant styrene resin composites according to claim 1, the rubber size that it is characterized in that rubber particles (B) are that double-peak type distributes, and its weight average particle diameter is respectively 0.06～0.15 μ m and 0.16～0.6 μ m.
4, serial heat-resistant styrene resin composites according to claim 1, the maleimide that it is characterized in that aggregating into the styrene based copolymer (A) that contains imide are that monomer is a N-phenylmaleimide.
5, serial heat-resistant styrene resin composites according to claim 1 is characterized in that the maleimide in the composition is that monomeric polymerized unit content is 5～30 weight %.
6, serial heat-resistant styrene resin composites according to claim 1 is characterized in that the styrenic monomers in the composition is vinylbenzene or alpha-methyl styrene.
7, serial heat-resistant styrene resin composites according to claim 1, the polymerized unit content that it is characterized in that styrenic monomers in the composition are 30～80 weight %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120544A CN1057785C (en) | 1996-12-06 | 1996-12-06 | Serial heat-resistant styrene resin composites |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120544A CN1057785C (en) | 1996-12-06 | 1996-12-06 | Serial heat-resistant styrene resin composites |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1184128A CN1184128A (en) | 1998-06-10 |
| CN1057785C true CN1057785C (en) | 2000-10-25 |
Family
ID=5126405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96120544A Expired - Fee Related CN1057785C (en) | 1996-12-06 | 1996-12-06 | Serial heat-resistant styrene resin composites |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1057785C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1167395B1 (en) * | 2000-06-19 | 2008-11-19 | Toagosei Co., Ltd. | Crosslinkable resin compositions |
| CN100429245C (en) * | 2005-12-16 | 2008-10-29 | 中国石油天然气股份有限公司 | Production of maleimide resin emulsion |
| CN101503551B (en) * | 2008-02-04 | 2011-02-09 | 中国石油天然气股份有限公司 | Maleimide heat resisting resin composition with improved glossiness and preparation thereof |
| CN103421255B (en) * | 2012-05-22 | 2016-04-20 | 韩国锦湖石油化学株式会社 | The close environment sash stuff composition of thermotolerance and tint permanence excellence |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6116955A (en) * | 1984-07-03 | 1986-01-24 | Mitsubishi Monsanto Chem Co | Heat-resistant, shock-resistant resin composition |
| EP0245856A2 (en) * | 1986-05-14 | 1987-11-19 | ENICHEM S.p.A. | Strengthened high impact styrenic polymers showing improved physical-mechanical properties |
-
1996
- 1996-12-06 CN CN96120544A patent/CN1057785C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6116955A (en) * | 1984-07-03 | 1986-01-24 | Mitsubishi Monsanto Chem Co | Heat-resistant, shock-resistant resin composition |
| EP0245856A2 (en) * | 1986-05-14 | 1987-11-19 | ENICHEM S.p.A. | Strengthened high impact styrenic polymers showing improved physical-mechanical properties |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1184128A (en) | 1998-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1118512C (en) | ABS resin formed body having good impact-resisting performance after being coated | |
| CA1189227A (en) | Multiphase core//shell polymers | |
| CN1147541C (en) | Processing aid for thermoplastic resin and thermoplastic resin composition containing the same | |
| CN1041318C (en) | Process for preparing rubber dispersed copolymer resin | |
| CN1795210A (en) | Method for preparing rubber-reinforced thermoplastic resin, and rubber-reinforced themoplastic resin composition using the same | |
| EP0051471B2 (en) | Tough thermoplastic nylon compositions and processes for preparing them | |
| CN1057785C (en) | Serial heat-resistant styrene resin composites | |
| CN101058621A (en) | Method of preparing ACS polymer based on continuous noumenon method | |
| CA1041245A (en) | Rubber modified high nitrile polymers and polymer blends produced thereby | |
| Zhang et al. | Acrylonitrile-styrene-acrylate particles with different microstructure for improving the toughness of poly (styrene-co-acrylonitrile) resin | |
| CN101058622A (en) | Method of preparing extinction injection moulding level ACS polymer based on continuous noumenon method | |
| CN1182448A (en) | Molding resin composition | |
| CN1057105C (en) | High luster impact-resistance excellent processing fluidity styrene series resin composition | |
| CN1091454C (en) | Thermoplastic resin composition, molded product and method for its production | |
| CN1048268C (en) | Rubber-modified polystyrene resin compounds | |
| CN1051565C (en) | Styrene series resin composition | |
| CN1260290C (en) | Polystyrene resin composition for chip plastic card | |
| CN1239601C (en) | Serial thermoplastic polystyrene resin compositions | |
| CN1063200C (en) | Phenylethylene resin composition | |
| CN1057784C (en) | Heat resistant polyvinyl resin combination with low surface glossiness | |
| CN1152005A (en) | Styrene resin composite | |
| JPH08134316A (en) | Thermoplastic polymer composition excellent in impact resistance | |
| JPH10298375A (en) | Rubber-modified heat-resistant styrene-based resin composition | |
| CN1174858A (en) | Flame-retarded phenylethylene series resin composition | |
| CN1172130A (en) | Phenylethylene resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |