CN1152006A - Styrene resin composite - Google Patents
Styrene resin composite Download PDFInfo
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- CN1152006A CN1152006A CN 95120407 CN95120407A CN1152006A CN 1152006 A CN1152006 A CN 1152006A CN 95120407 CN95120407 CN 95120407 CN 95120407 A CN95120407 A CN 95120407A CN 1152006 A CN1152006 A CN 1152006A
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Abstract
Polystyrene resin composition contains graft copolyrer C of 5-90 wt%, which is produced through polymerization of rubber graft copolymer A, propenyl copolymer B and a monomer mixture; graft copolymer D of 5-90 wt%, which is produced through polymerization of diene rubber and a monomer mixture; and copolymer E of 5-90 wt%, which is produced through the copolymerization of a monomer mixture. The said monomer mixture includes styrene monomer, vinyl cyanide monomer and copolymering monomer.
Description
Present invention is directed to a kind of styrene resin composite, more specifically, present invention is directed to a kind of have gloss homogeneous, the good characteristic of vacuum formability, and be fit to make the styrene resin composite of moulding converted products.
The personage who is familiar with this technical field knows that all 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.With regard to application, high gloss and low gloss goods respectively have the field of its application, but in r integrated planning design " theory under; no matter resin is ejection formation; perhaps with the additive method moulding, often is required to have surface gloss in various degree, so that the outward appearance of article surface is more coordinated.Therefore, the styrene resin composite of developing a kind of gloss homogeneous becomes present technique field utmost point problem to be broken through then.
In order to reduce the influence of processing conditions variation to moulding product surface gloss, to reach the purpose of each position gloss homogeneous of moulding product, known mode of ameliorating is to make the rubber graft copolymer in the resin combination contain three kinds of different-grain diameter distribution kenels, and for example No. 5041498 disclosed content of patent case of U.S.'s patent of invention is so.But above-mentioned improved method is limited for the lifting effect of gloss homogeneous, even under some benchmark, its effect is relatively poor on the contrary.
The personage who is familiar with this technical field again also knows, some is applied to styrene resin composite in the field of extrusion board and vacuum forming, for the demand that maximizes day by day in response to for example finished product such as refrigerator, container, resin with more excellent vacuum formability is also in the exploitation constantly, for example promptly mention in the Japanese kokai publication sho 60-20916 case, the weight ratio of vinylbenzene and vinyl cyanide is at 1.7～2.6 in the solvable composition of acetone in composition, and the storage spring rate of the insoluble glue composition of acetone is 0.9 * 10
9～4 * 10
9Dyne/cm
2Person in the scope can improve the vacuum formability of resin, however the effect of its improvement and not obvious.
In view of this, this case contriver is at aforementioned disappearance, develops a kind of styrene resin composite.
Therefore, main purpose of the present invention ties up in the styrene resin composite that a kind of gloss homogeneous is provided and has good vacuum formability.
Polystyrene oil/fat composition of the present invention mainly comprises:
(1) 5～90% (weight) graft copolymer (C), this graft copolymer (C) be the weight average particle diameter by 0.1～10 weight part be the rubber graft copolymer (A) of 0.05～0.8 μ m and 0.1～10 weight part propenyl based copolymer (B) and 100 weight parts to comprise (a) 45～80 parts by weight of styrene be monomer, (b) the acrylic monomer of 15～50 weight parts and (c) monomer mixture of the optional copolymerizable monomer of 0～40 weight part carry out body and/or solution polymerization obtains:
(2) 5～90% (weight) graft copolymer (D), this graft copolymer (D) are that the monomer mixture of the optional copolymerizable monomer of monomer and 0～40 weight part carries out body and/or solution polymerization obtains by styrenic monomers, 20～50 parts by weight of acrylonitrile of the diene series rubber of 5～25 weight parts and 50～80 weight parts;
The multipolymer of (3) 5～90% (weight) (E), this multipolymer (E) are that the monomer mixture of the styrenic monomers, acrylic monomer of the rubber latex of 0.05～0.8 μ m and 15～50 weight parts and optional copolymerizable monomer carries out the emulsification graft polymerization and obtains by the weight average particle diameter of 50～85 weight parts.
According to aforementioned component, can make one and have gloss homogeneity and the good styrene resin composite of vacuum formability simultaneously.
Rubber graft copolymer of the present invention (A) is that to make 50～80 weight parts of butadiene be that rubber latex and 15～50 parts by weight of styrene are monomer and acrylic monomer, and other optional copolymerizable monomer of 0～30 weight part are carried out graft polymerization and the weight average particle diameter that obtains is the emulsion of the rubber graft copolymer of 0.05～0.8 μ m, again through condense, dehydration, drying and other steps, and make granular rubber graft copolymer (A).Described butadiene-based rubber emulsion means the formed homopolymer of single unsaturated monomer (homopolymer) of the conjugate diene monomer and 0～40% (weight) that includes 60～100% (weight), or its multipolymer (copolymer).Described conjugate diene monomer can be represented by following formula:
Wherein, R can be hydrogen, methyl or chlorine etc., and single unsaturated monomer can be styrenic monomers, acrylic monomer and (methyl) acrylic ester monomer.
Butadiene-based rubber emulsion used in the present invention can be butadiene-styrene copolymer, perbutan, divinyl-methylmethacrylate copolymer etc.; Above-mentioned butadiene-based rubber emulsion can the aforementioned monomer direct polymerization and is obtained the form that weight average particle diameter is 0.05～0.8 μ m, after also can aggregating into the small particle size rubber latex that weight average particle diameter is 0.05～0.18 μ m earlier, with traditional rubber agglomeration technique, the small particle size rubber latex of 0.05～0.18 μ m is agglomerated into the rubber latex of 0.2～0.8 μ m again.Described rubber agglomeration technique can be chemical agglomeration method, churned mechanically mechanical agglomeration technique or the freezing agglomeration technique etc. that add organic acid or metal-salt or contain carboxylic acid group's polymer coagulant (agglomeration agent).The polymer coagulant that aforementioned chemical agglomeration method is adopted for example can be butyl acrylate-Sipacril 2739OF.
Graft polymerization reaction of the present invention is to be used for making the rubber graft copolymer that weight average particle diameter is 0.05～0.8 μ m.The preparation of described graft copolymer normally utilizes the graft polymerization technique of commonly using, make rubbery polymer and styrenic monomers, acrylic monomer, and optionally and optional (methyl) acrylic ester monomer mixture carries out graft polymerization, utilize chemical in conjunction with or at least a polymkeric substance of grafting on butadiene-based rubber.According to the ratio and the polymerizing condition of monomer and butadiene-based rubber, can obtain the hard copolymer grafted simultaneously on butadiene-based rubber, and the polymkeric substance with desirable grafting degree.Usually, factors such as the consumption of the speed that the polymerizing condition in the graft polymerization reaction, the chemical property of rubbery polymer, size of particles, monomer add, chain transfer agent, emulsifying agent and kind all can influence its grafted degree.
Initiator that aforementioned graft polymerization reaction added or catalyzer are 100 weight parts in the gross weight of the mixture of polymerisable monomer, usually in 0.01～5.0 weight part scope, preferably between 0.1～3.0 weight part.Its addition must the polymeric polyreaction according to monomer and institute and decide, and aforementioned initiator can be continuously or joined in the reactive system in batches, is beneficial to the carrying out of graft polymerization reaction.
The molecular weight size of aforementioned graftomer can be controlled by the temperature of graft reaction again, and/or the molecular weight regulator that cooperates quite a small amount of ratio to commonly use, and for example: mercaptan, fontanelle compound or obedient alkene etc. are regulated.The concrete example of described molecular weight regulator has: just-and lauryl mercaptan, uncle-lauryl mercaptan.
This graft polymerization reaction also can be controlled by changing the grafting amount of polymkeric substance on the rubber-like polymer.Usually, this effect can utilize monomer mixture to add in the polyreaction with continuous or increment ground, and preferably adds simultaneously initiator continuously or in batches.Described initiator can use various known emulsification Raolical polymerizable initiators, and for example: superoxide (peroxy) and azo-compound, its addition manner can adopt once and to add or to add continuously or in batches etc.; Suitable superoxide initiator is for example: alkali metal peroxide, persulphate, perborate, peracetate, percarbonate, hydrogen peroxide etc. also can use the oil soluble initiator in addition, for example: cumyl superoxide (dicumyl peroxide), tert-butyl peroxide (tert-butyl peroxide), isopropyl benzene hydroperoxide (cumene hydroperoxide) etc.The polyreaction of aforementioned butadiene-based rubber emulsion and monomer mixture is to carry out under stirring in 20～100 ℃ inert gas atmosphere, and it also can be forced into 0～100P.S.I.G..Desire to make 90% monomer to be aggregated in the reaction, its polymerization time needs 2～10 hours usually, preferably between 4～8 hours.
Styrenic monomers used in the present invention can be vinylbenzene, alpha-methyl styrene, α-chloro-styrene, p-t-butyl styrene, p-vinyl toluene, o-chloro-styrene, p-chloro-styrene, 2,5-dichlorostyrene, 3,4-two. chloro-styrene, 2,4,6 ,-tribromo-benzene ethene, 2,5-Dowspray 9 etc., wherein, preferably use vinylbenzene or alpha-methyl styrene.
Employed acrylic monomer can be: vinyl cyanide, Alpha-Methyl vinyl cyanide etc.; Vinyl cyanide preferably wherein.
The copolymerizable monomer of using in the rubber graft copolymer of the present invention (A) can be: (methyl) acrylic ester monomer, maleimide are monomer, vinylformic acid, Maleic Acid, Anhydrous, methacrylic acid glycol ester (Ethylene glycolmethacrylate) etc.Wherein (methyl) acrylic ester monomer can be: methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid benzene methyl, methacrylic acid be ester, methacrylic acid cyclohexyl ester, lauryl methacrylate, methacrylic acid 2-hydroxyl ethyl ester, glycidyl methacrylate and dimethylaminoethyl methacrylate etc., wherein methyl methacrylate preferably.
Maleimide is that monomer can be: maleimide, N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, the basic maleimide of N-, 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 imide etc., wherein preferred N-methyl maleimide.
Can make the rubber graft copolymer that weight average particle diameter is 0.05～0.8 μ m (A) emulsion by aforementioned graft polymerization.
Must add suitable condensing agent in the emulsion of described rubber graft copolymer (A) again condenses, general employed condensing agent has acids, alkaline earth metal salts such as sulfuric acid, acetic acid, for example: calcium salt such as calcium chloride, magnesium salts such as magnesium chloride, sal epsom, aluminium salt such as Tai-Ace S 150, wherein, preferred bases earth metal salt.The polymer slurries of finishing that condenses is sloughed moisture content through dewatering process, and drying is handled again, can make granular rubber graft copolymer (A).
Propenyl based copolymer of the present invention (B) is to be that at least a monomer, 0～80% (weight) styrenic monomers and other optional copolymerizable monomer of 0～30% (weight) of selecting monomer and the acrylic monomer are formed by: 10～100% (weight) from (methyl) propylene vinegar; And propenyl based copolymer (B) can be styrene-acrylonitrile copolymer, methyl methacrylate-styrene-acrylonitrile copolymer, polymethylmethacrylate and styrene-methylmethacrylate copolymer etc.The polymeric mode can be various polymerization methodses such as solution, body, emulsion or suspension polymerization.
Employed styrenic monomers in the aforesaid propylene base system polymer (B), acrylic monomer, (methyl) acrylic ester monomer are identical with rubber graft copolymer (A) place exponent, are not described in detail in this.And optionally and other optional copolymerizable monomers to can be vinylformic acid, Maleic Acid, Anhydrous, methacrylic acid glycol ester and maleimide be monomer etc.
Graft copolymer of the present invention (C) is that rubber is drawn multipolymer (A) 0.1～10 weight part, propenyl based copolymer (B) 0.1～10 weight part, and gross weight is that the following monomeric mixture of 100 weight parts obtains with body and/or solution polymerization process polymerization.Described monomer mixture comprises: styrenic monomers 45～80 weight parts, acrylic monomer 15～50 weight parts and optional copolymerizable monomer 0～40 weight part.
Specifically, the present invention system is aforementioned monomer and graft rubber polymer (A), propenyl based copolymer (B), reaches according to need and the material solution that the optional solvent mixed dissolution is become is sent into polymerization in the reactor; Perhaps with part aforementioned monomer, rubber graft copolymer (A), propenyl based copolymer (B), and optionally and the optional solvent mixed dissolution becomes a material solution independently, make remaining monomer form another material solution again, two material solutions are sent into respectively carried out polymerization 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 time enough, above-mentioned rubber graft copolymer (A) and propenyl based copolymer (B) can be dissolved into fully the state of solution, carry out to make things convenient for pump delivery to the operation in the reactor.Graft copolymer of the present invention (C) can be finished by continous way body or solution polymerization.Described reactor comprises: column flow reactor, hybrid fully (CSTR) reactor perhaps contain the tubular reactor of silent oscillation hybrid element.Described reactor quantity can be one, also can use two or more, and reacts under cooperation interpolation chain transfer agent and the initiator.
Through the reaction of previous reaction device, its transformation efficiency is reached till 40～90% (weight), more reacted reaction mixture is delivered to volatilization device at last to remove unreacted monomer and solvent, can make graft copolymer (C).When making graft copolymer of the present invention (C), the polymerization initiator can be added in the reaction, this polymerization initiator comprises the acyl peroxide class, peroxyesters, ketal peroxide class, peroxycarbonates class, and have azo-compound of nitro and cyclohexane ring etc.The addition of this polymerization initiator is 100 weight parts in the gross weight of described monomer mixture, is 0.01～1.0 weight part.
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-controlling of reactor is at 1～5 kilogram/cm
2Between, and the residence time of material solution in reactor is preferably between 1～5 hour.
In the composition of the present invention, the content of graft copolymer (C) is 5～90% (weight).When its content was lower than 5% (weight), resin can't obtain superior vacuum formability, and the gloss homogeneity of resin is not good yet; If its consumption greater than 90% (weight), then makes its shock strength poor because of rubber content is not enough.
Employed rubber graft copolymer (A) is 0.1～10 weight part in the material solution of graft copolymer (C).If the usage quantity of rubber graft copolymer (A) is higher than 10 weight parts, can cause disappearances such as feedstock solution viscosity is too high, dissolving difficulties in dispersion, pumpdown difficulty.Propenyl based copolymer used in the present invention (B) accounts for 0.1～10 weight part in graft copolymer (C) material solution.When its consumption is lower than 0.1 weight part, rubber graft copolymer (A) is agglomerated together easily, and can't be fully by dispersing and dissolving in solution, cause the pump delivery operational difficulty, the reaction prepared graft copolymer in back (C) can contain coarse particles, the resin combination finished product then can produce the surface spots of flake (fish eye), and is not good in appearance, and the gloss homogeneity is improved the effect minimizing; If the addition of propenyl based polymer (B) is higher than 10 weight parts, feedstock solution viscosity is too high, operation is difficult for, and excessive propenyl based polymer (B) repeated polymerization reprocessing is not inconsistent economic benefit yet.
When the usage quantity of the rubber graft copolymer (A) in graft copolymer (C) material solution is lower than 0.1 weight part, can't obtain when in aftermentioned, carrying out fusion that vacuum formability is good, the resin combination of glossiness homogeneous.
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 can obtain the resin combination of preferable vacuum formability between 40,000～120,000 the time.The alleged percentage of grafting of the present invention means the hard multipolymer that grafts on the rubber and the ratio (%) of rubber.
Graft copolymer of the present invention (D) is by body or solution polymerization process polymerization and get, it constitutes: diene series rubber 5～25 weight parts, styrenic monomers 50～80 weight parts, acrylic monomer 20～50 weight parts, and other optional copolymerizable monomer 0～40 weight parts are formed; Its manufacture method is that diene series rubber is dissolved in monomer and/or the solvent in advance, pumps into reactive tank again and carries out graft polymerization reaction, and reactive tank can be combined by a plurality of, the general still type reactive tank that preferably utilizes with machine,massing.Monomer and diene series rubber are mixed into uniform state, carry out polymerization more in a continuous manner, also can use the piston-type reactive tank of tower during polymerization, certainly, also can add suitable chain transfer agent during reaction.(for example: uncle's lauryl mercaptan), to control its molecular weight.
Be applicable to that diene series rubber of the present invention has conjugated diene rubber, for example divinyl rubber, isoprene rubber, neoprene etc. are preferably arranged; Wherein, divinyl rubber has the branch of high-cis (Hi-Cis) content and low cis (Low-Cis) content; In the high-cis rubber, the typical weight of its cis (Cis)/vinyl (Vinyl) consists of 94～98%/1～5%, and all the other compositions then are trans (Trans) structure; Its Mooney viscosity is between 20～120, and molecular weight ranges is with 100,000～800, and 000 is good; In the low cis rubber, the typical weight compositing range of cis/vinyl is 20～40%/1～20%, and all the other are transconfiguration, and wherein Mooney viscosity is between 20～120.Other elastomeric materials that are fit to also have: acrylic-nitrile rubber, styrene/butadiene rubbers, the perhaps 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) copolymerization, syllogic (tri-block) copolymerization, random copolymerization (random) or star copolymerization (startype).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, and 000.Above-mentionedly be applicable to that rubber of the present invention is good with divinyl rubber and styrene/butadiene rubbers, wherein better with divinyl rubber again.
As for employed styrenic monomers, acrylic monomer, (methyl) acrylic monomer in the graft copolymer (D), and the kind of other copolymerizable monomer is to be same as rubber to connect employed those monomers of multipolymer (A), do not repeat them here.
By body or solution polymerization process polymerization and graft copolymer (D), its rubber weight average particle diameter is between 0.5～10 μ m, preferably between 0.8～7.0 μ m.The mix proportions of aforementioned graft copolymer (D) in composition of the present invention also is restricted, and the usage quantity scope is preferably between 5～90% (weight).When its mix proportions was lower than 5% (weight), the resin vacuum formability was not good; If its consumption greater than 90% (weight), will cause the tensile strength of composition to descend.
The manufacture method of graft copolymer of the present invention (E) is identical with the manufacturing instructions of rubber graft copolymer (A), graft copolymer (E) can be same composition with rubber graft copolymer (A), also can be different compositions, but based on the balance between preferable vacuum formability, gloss homogeneity, rigidity and the flowability, the percentage of grafting of graft copolymer (E) is between 18～80%, and the molecular weight of its grafted hard multipolymer is preferably 40,000～200, between 000.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, rigidity are not good, and are higher than at 200,000 o'clock when percentage of grafting big 80% or molecular weight, resin flow is poor.The content of above-mentioned graft copolymer (E) in composition of the present invention is 5～90% (weight).When its content when 5% (weight) is following, the shock strength deficiency of resin combination, if its content is higher than 95% (weight), then mobile poor, vacuum formability is also not good.
Above-mentioned graft copolymer (C) 5～90% (weight), graft copolymer (D) 5～90% (weight) and graft copolymer (E) 5～90% (weight) according to the general device fusion of mixing, can be obtained the styrene resin composite that the present invention has excellent vacuum formability and gloss homogeneity.
The device that generally mixes comprises single screw rod and twin screw extruder, mix in mix cylinder and inside device etc., and also can comprise or not comprise various known additives in the styrene resin composite, for example: stablizer, lubricant, flow promotor, conglomeration releasing agent, antioxidant, static inhibitor, weighting agent, glass fibre, pigment and analogue thereof.
Following embodiment and physical property measurement are further elaborated to the present invention.Unless stated otherwise, in following embodiment and the comparative example consumption weight percentage of each component and and weight part represent.＜preparation example 1〉preparation of rubber graft copolymer (A-1): composition weight part 1,3-butadiene 150.00 potassium persulfate solutions (1%) 15.00 potassium oleate 2.00 distilled waters 190.00 Ethylene glycol dimethacrylate 0.13
Under 65 ℃ of temperature of reaction, reacted 12 hours according to above prescription, obtain transformation efficiency and be 94%, solids content is about 40%, flat particle diameter is the synthetic rubber latex of 0.1 μ m.
In addition, the polymer coagulant that contains the carboxylic acid group with following composition manufacturing: composition parts by weight of acrylic acid ethyl ester 90.0 methacrylic acids 10.0 potassium persulfate solutions (1%) 0.5 sodium dodecyl sulfate solution (10%) 0.5 just-lauryl mercaptan 1.0 distilled waters 200.0
Under 75 ℃ of temperature of reaction, reacted 5 hours according to above prescription, obtain that transformation efficiency is about 95%, pH be 6.0 contain carboxylic acid group's polymer coagulant.
Afterwards, utilize the synthetic rubber breast (dry weight) 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 weight average particle diameter is 0.31 μ m.
At last; Carry out graft polymerization reaction with the 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 uncles-lauryl mercaptan 2.0 cumene hydroperoxide hydrogen 3.0 copperas solutions (0.2%) 3.0 sodium hydrosulfide formalin (10%) 0.9 edta solution (0.25%) 3.0
Condense with calcium chloride according to the last table prepared grafting rubbers emulsion of filling a prescription, just can make the rubber graft copolymer of wanting required for the present invention (A-1) (rubber content is 75% (weight)), its weight average particle diameter is that 0.31 μ m, percentage of grafting are 30.5%, the molecular weight of grafted styrene-acrylonitrile copolymer is 63,000.＜preparation example 2〉preparation of rubber graft copolymer (A-2):
With＜preparation example 1〉prepared synthetic rubber latex (the rubber weight average particle diameter is 0.1 μ m); Direct and following table prescription carries out graft polymerization reaction, to make rubber graft copolymer (A-2). composition weight portion synthetic rubber latex (0.1 μ m) (dry weight) 100.0 styrene 32.4 acrylonitrile 12.6 uncles-lauryl mercaptan 2.0 cumene hydroperoxide hydrogen 3.0 copperas solutions (0.2%) 3.0 sodium hydrosulfide formalin (10%) 0.9 edta solution (0.25%) 3.0
Condense with calcium chloride according to the last table prepared grafting rubbers emulsion of filling a prescription, just can make the rubber graft copolymer of wanting required for the present invention (A-2) (rubber content 69% (weight)), its weight average particle diameter is 0.1 μ m, percentage of grafting is 42%, the molecular weight of grafted styrene-acrylonitrile copolymer is 70,000.＜preparation example 3-1〉preparation of propenyl based copolymer (B-1):
The raw material that will consist of vinylbenzene 75% (weight), methyl methacrylate 25% (weight) with 12 kilograms/hour speed is mixed, again ethylene distearyl acid amides being reclaimed liquid with 3.0 Grams Per Hours, benzoyl peroxide and uncle-lauryl mercaptan and aftermentioned merges as stock liquid, with supply with internal temperature remain on 108 ℃ and volume be 45 liters with in the continous way still type reactor of agitator, and make the toluene ratio in the reaction solution keep 15%, and percent polymerization remain on 55%.
After reaction solution is removed volatile component by volatilization device, can obtain the particle of the propenyl based copolymer of wanting required for the present invention.On the other hand, the volatile component of being removed with condenser condenses after as reclaiming liquid, and continuously itself and aforementioned base materials mixed solution are re-used.Adjust speed of response with this method by the amount of benzoyl peroxide, or adjust the amount of uncle-lauryl mercaptan; And make melt flow index with about 12 kilograms/hour speed is 1.2 styrene-methylmethacrylate copolymer (B-1).＜preparation example 3-2〉preparation of propenyl based copolymer (B-2):
The preparation method is with＜preparation example 3-1 〉, difference is that set of monomers becomes vinylbenzene 78% (weight), vinyl cyanide 22% (weight), can make styrene-acrylonitrile copolymer (B-2).＜preparation example 4〉preparation of graft copolymer (C):
Make earlier following composition mix to make material solution: composition parts by weight of styrene 71.90 acrylonitrile 28.10 ethylbenzene, 7.00 rubber graft copolymers (A-2) (such as preparation example 2) 4.90 styrene-methyl methacrylate (B-1) (such as preparation example 3) 1.00 uncles-lauryl mercaptan 0.09 benzoyl peroxide (initiator) 0.05
Above-mentioned raw materials solution is sent in first reactor continuously with 22 liters/hour speed, the volume of this first reactor is that 44 liters, temperature of reaction are 120 ℃, reactor pressure is 4 kilograms, the residence time of reactant is 2 hours, the stirring velocity of the spiral whipping appts that is provided with in it is 100 rev/mins, is 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, the structure of this second reactor assembly is same as first reactor, by the time the transformation efficiency of mixture reaches at 56% o'clock, again mixture is taken out and send into volatilization device to remove unreacted monomer and volatile component, with its extruding pelletization, can make graft copolymer (C-1) afterwards.
According to aforementioned preparation method and with the contained ratio of table 1, produce graft copolymer (C-2), (C-3), (C-4), (C-5), (C-7).＜preparation example 5〉preparation of graft copolymer (D):
(company of Asahi Chemical Industry produces to use the polyhutadiene of 6.4 weight parts, trade(brand)name--Asadene 55AS) benzoyl peroxide of being used as the uncle-lauryl mercaptan of diene series rubber, 0.1 weight part and 0.07 weight part is dissolved in fully as initiator in the ethylbenzene of the vinyl cyanide of vinylbenzene, 22 weight parts of 64 weight parts and 30 weight parts, and forms feedstock solution; Described feedstock solution is sent in first reactor continuously, and the volume of this first reactor is that 44 liters, temperature of reaction are 100 ℃, and the stirring velocity of the spiral whipping appts that is provided with in it is 300 rev/mins, is provided with the refrigeration cycle pipe in whipping appts.To take out continuously and send in second reactor through the mixture behind first reactor reaction, the structure of this second reactor assembly be same as first reactor.By the time the transformation efficiency of mixture reaches at 60% o'clock, mixture is taken out send into volatilization device to remove unreacted monomer and volatile matter again, afterwards with its extruding pelletization, can make the graft copolymer that weight average particle diameter is 1.1 μ m (D).＜preparation example 6〉preparation of graft copolymer (E):
Synthesizing of rubber latex with preparation example 1, but the agglomeration processing changes the synthetic rubber latex that comes agglomeration 100 weight parts with the polymer coagulant that contains the carboxylic acid group of 3.5 weight parts into, the pH value of resulting rubber latex is 8.5, its rubber size is about 0.28 μ m, and carry out graft polymerization reaction according to following prescription, to obtain graft copolymer (E). composition weight portion agglomeration rubber latex (dry weight) 100.0 styrene 40.4 acrylonitrile 13.4 uncles-lauryl mercaptan 2.0 cumene hydroperoxide hydrogen 3.0 copperas solutions (0.2%) 3.0 sodium hydrosulfide formalin (10%) 0.9 edta solution (0.25%) 3.0
The weight average particle diameter of graft copolymer (E) is 0.28 μ m, and percentage of grafting is 42%, and grafted styrene-acrylonitrile copolymer molecular weight is 80,000.
The rerum natura that following embodiment and comparative example are measured and the testing standard of molded appearance are as follows: the * tensile strength: according to ASTM D-683 standard testing, unit represents with kilogram/cm2.* Emhorn shock strength (IZOD): according to ASTM D-256 standard testing, unit represents with kilogram .cm/cm.* glossiness (gloss homogeneity): with Gardner (Gardner60 ° of Incidence angle) according to the ASTMD-523 standard testing, unit adopts %, testing plate is the ejaculation goods of the wide 25mm of a long 300mm, thick 3mm, its fan-shaped cast gate is surveyed its glossiness apart from cast gate 5cm, 15cm, 25cm three places apart from limit end 15mm, can be as the decision method of gloss homogeneity, three value differences are different littler, and expression gloss homogeneity is better.* outward appearance: aforementioned gloss test film is with visual detection, and the flat appearance person is with zero expression, and there are granular projection or flake person in the surface with * expression.* vacuum formability: with resin with single screw rod plate squeezing machine L/D=28, D=90m/m (U.S. Gloucester Engineering Co.), extruding thickness is 3.175m/m sheet material, this sheet material is cut into the test piece (300mm * 19mm) of above-mentioned tensile strength shape again, the one end clamped be suspended to 15mm in 180 ℃ of thermostat containers, long 50mm is partly about the length variations before and after the test in the middle of surveying it, comply with: length (50mm) * 100% is calculated before test back length (mm)/test, and represent with %, represent that when this value is bigger vacuum formability is poorer, represent that promptly this panel material is responsive to the change of temperature, in the vacuum forming process, easily cause the situation of moulding product uneven thickness.Embodiment＜embodiment 1 〉
Under drying regime, with the graft copolymer (C-1) (making) of 46.1% (weight), the graft copolymer (D) (making) of 31.3% (weight), graft copolymer (E) (making) fusion of 22.6% (weight) by preparation example 6 by preparation example 5 by preparation example 4; Above-mentioned adulterant then is blended into a kind of melt of homogeneous in blender, melt is extruded into thread again and cuts into the particulate state plastic cement, to make physical property measurement; Measured result is stated from the table 2.＜embodiment 2 〉
According to the prescription of table 2 raw material is mixed the back and handle according to the treatment process of embodiment 1, and be molded into test and use test piece, the rerum natura that records is stated from the table 2.＜embodiment 3 〉
According to the prescription of table 2 raw material is mixed the back and handle according to the treatment process of embodiment 1, and be molded into test and use test piece, the rerum natura that records also is stated from the table 2.＜embodiment 4 〉
According to the prescription of table 2 raw material is mixed the back and handle according to the treatment process of embodiment 1, and be molded into test and use test piece, the rerum natura that records also is stated from the table 2.＜embodiment 5 〉
According to the prescription of table 2 raw material is mixed the back and handle according to the treatment process of embodiment 1, and be molded into test and use test piece, the rerum natura that records also is stated from the table 2.＜comparative example 1 〉
Operational condition with embodiment 1, difference is: graft copolymer (C) is used instead as (C-6) in the table 1, that is to say, graft copolymer (C) does not contain rubber graft copolymer (A), prepared test film carries out the test of various rerum naturas equally, and its result is stated from the table 2.＜comparative example 2 〉
Operational condition with embodiment 1, but the consumption of graft copolymer (C-1) changes 72.4% (weight) into, the consumption that the consumption of graft copolymer (D) changes 2.0% (weight), graft copolymer (E) into changes 25.6% (weight) into, the testing plate of institute's moulding is also surveyed its rerum natura, and its result is stated from the table 2.＜comparative example 3 〉
With the operational condition of embodiment 1, but graft copolymer (C) changes into and connects multipolymer (C-7) shown in the table 1, promptly do not contain propenyl based copolymer (B) in the graft copolymer (C), and the test piece of institute's moulding is tested equally, and its result also is stated from the table 2.＜comparative example 4 〉
Resin combination by: the graft copolymer (E) of the graft copolymer of 81.0% (weight) (D) and 19.0% (weight) is formed, all the other processing modes are same as embodiment 1, that is, lack in the resin combination and connect multipolymer (C), the test piece of institute's moulding is tested equally, and test result also is stated from the table 2.
Thus as can be known than the test-results of example 1, in the graft copolymer of the present invention (C) if do not contain rubber graft copolymer (A), can't obtain having the resin combination of good vacuum formability and gloss homogeneity, test result by comparative example 2 shows, when graft copolymer (D) content is lower than 5% (weight), the vacuum formability of resin is not good, and when not containing thiazolinyl based copolymer (B) in the graft copolymer (C), not only glossiness is lower, also heterogeneity of gloss, the outward appearance of resin combination finished product is also not good, and this by the test result of comparative example 3 as can be known; When lacking graft copolymer (C) in the resin combination, can't obtain all good resin combinations of vacuum formability and gloss homogeneity again, the tensile strength of finished product is also relatively poor, and this test-results by comparative example 4 is provable.
See embodiment 1～5 again, the present invention is through aforementioned each composition and use quantitative limitation, can improve the vacuum formability and the gloss homogeneity of styrene resin composite really, to reduce the influence of processing conditions variation to the finished surface glossiness, and make composition be applied in day by day the sheet material that maximizes to add and more attain man-hour perfectly, and can supply the industry utilization.
The above only is that mode with preferred possible embodiments describes the present invention.It is evident that,, in spirit of the present invention and essential scope, can make amendment or change the present invention for those skilled in the art.
Table 1 (weight part)
| The numbering No. of graft copolymer (C) | ????(C-1) | ????(C-2) | ????(C-3) | ????(C-4) | ????(C-5) | ????(C-6) | ????(C-7) |
| Rubber graft copolymer (A) | ????(A-2) ????4.9 | ????(A-1) ????3.1 | ????(A-2) ????4.9 | ????(A-2) ????5.2 | ????(A-2) ????9.6 | ????- ????0 | ????(A-2) ????4.8 |
| Propenyl based copolymer (B) | ????(B-1) ????1.1 | ????(B-1) ????1.1 | ????(B-2) ????1.1 | ????(B-1) ????3.9 | ????(B-1) ????4.5 | ????(B-1) ????1.1 | ????- ????0 |
| Vinylbenzene | ????71.9 | ????71.9 | ????68.1 | ????71.9 | ????71.9 | ????71.9 | ????71.9 |
| Vinyl cyanide | ????28.1 | ????28.1 | ????26.6 | ????28.1 | ????28.1 | ????28.1 | ????28.1 |
| N-phenylmaleimide | ????0 | ????0 | ????5.3 | ????0 | ????0 | ????0 | ????0 |
Table 2
| Experiment numbers | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | ||
| Composition | Graft copolymers (C) weight % | ????(C-1) ????46.1 | ????(C-2) ????46.1 | ????(C-3) ????46.1 | ????(C-4) ????46.1 | ????(C-5) ????41.5 | ????(C-6) ????43.4 | ????(C-1) ????72.4 | ????(C-7) ????46.1 | ????- ????0 | |
| Graft copolymer (D) weight % | ????31.3 | ????31.3 | ????31.3 | ????31.3 | ????38.6 | ????28.6 | ????2.0 | ????31.3 | ????81.0 | ||
| Graft copolymer (E) weight % | ????22.6 | ????22.6 | ????22.6 | ????22.6 | ????19.9 | ????28.0 | ????25.6 | ????22.6 | ????19.0 | ||
| Test subject | Emhorn shock strength (kg-cm/cm) | ????29.6 | ????30.8 | ????29.0 | ????29.2 | ????29.4 | ????30.1 | ????29.5 | ????28.9 | ????26.6 | |
| Tensile strength (kg/cm2) | ????369 | ????371 | ????365 | ????367 | ????366 | ????358 | ????377 | ????366 | ????313 | ||
| Vacuum formability (%) (180 ℃, 15 minutes sagging length | ????5.3 | ????5.5 | ????5.9 | ????5.6 | ????6.1 | ????14.6 | ????17.4 | ????8.5 | ????30.1 | ||
| Glossiness | ????5cm | ????88.1 | ????85.7 | ????84.6 | ????85.9 | ????84.5 | ????84.1 | ????87.2 | ????82.3 | ????86.6 | |
| ????15cm | ????84.6 | ????82.4 | ????83.7 | ????84.1 | ????83.1 | ????80.7 | ????85.3 | ????79.2 | ????81.5 | ||
| ????25cm | ????83.5 | ????82.1 | ????81.7 | ????83.3 | ????81.8 | ????75.5 | ????83.1 | ????75.2 | ????76.2 | ||
| Homogeneity % (5cm-25cm) | ????2.6 | ????3.6 | ????2.9 | ????2.6 | ????2.1 | ????8.8 | ????4.1 | ????7.1 | ????10.4 | ||
| Outward appearance | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????○ | ????× | ????○ | ||
Claims (3)
1. composition of styrene resin comprises:
(1) 5～90% (weight) graft copolymer (C), this graft copolymer (C) be the weight average particle diameter by 0.1～10 weight part be the rubber graft copolymer (A) of 0.05～0.8 μ m and 0.1～10 weight part propenyl based copolymer (B) and 100 weight parts to comprise (a) 45～80 parts by weight of styrene be monomer, (b) the acrylic monomer of 15～50 weight parts and (c) monomer mixture of the optional copolymerizable monomer of 0～40 weight part carry out body and or solution polymerization obtain:
(2) 5～90% (weight) graft copolymer (D), this graft copolymer (D) are that the monomer mixture of the optional copolymerizable monomer of monomer and 0-40 weight part carries out body and/or solution polymerization obtains by styrenic monomers, the 20-50 parts by weight of acrylonitrile of the diene series rubber of 5～25 weight parts and 50～80 weight parts;
The multipolymer of (3) 5～90% (weight) (E), this multipolymer (E) are that the mixture of the styrenic monomers, acrylic monomer of the rubber latex of 0.05～0.8 μ m and 15～50 weight parts and optional copolymerizable monomer carries out the emulsification graft polymerization and obtains by the weight average particle diameter of 50～85 weight parts.
2, composition as claimed in claim 1, wherein, the graft copolymer that described rubber graft copolymer (A) obtains for emulsion polymerization.
3, composition as claimed in claim 1, wherein, the percentage of grafting of described rubber graft copolymer (A) is 10～40%, the molecular weight of grafted hard multipolymer is 40,000～120, between 000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95120407 CN1152006A (en) | 1995-12-15 | 1995-12-15 | Styrene resin composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95120407 CN1152006A (en) | 1995-12-15 | 1995-12-15 | Styrene resin composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1152006A true CN1152006A (en) | 1997-06-18 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95120407 Pending CN1152006A (en) | 1995-12-15 | 1995-12-15 | Styrene resin composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1152006A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366671C (en) * | 2005-03-15 | 2008-02-06 | 奇美实业股份有限公司 | Transparent rubber modified polystyrene resin |
-
1995
- 1995-12-15 CN CN 95120407 patent/CN1152006A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366671C (en) * | 2005-03-15 | 2008-02-06 | 奇美实业股份有限公司 | Transparent rubber modified polystyrene resin |
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