CN1116631A - Method for preparing thermoplastic styrene resin composition - Google Patents
Method for preparing thermoplastic styrene resin composition Download PDFInfo
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- CN1116631A CN1116631A CN 94109547 CN94109547A CN1116631A CN 1116631 A CN1116631 A CN 1116631A CN 94109547 CN94109547 CN 94109547 CN 94109547 A CN94109547 A CN 94109547A CN 1116631 A CN1116631 A CN 1116631A
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Abstract
The thermoplastic styrene resin composition which has excellent ball impact strength, high tensile strength, better shaping ability and high brightness is such prepared that during aggregation in rubber emulsion synthesis, high-molecular aggregating agent containing carboxyl is added to synthetic rubber emulsion in two or more stages.
Description
Acrylonitrile-butadiene-styrene Copolymer in the existing polystyrene (ABS) resin manufacture technology is usually by rubber latex and vinylbenzene (SM), and vinyl cyanide (AN) or methyl methacrylate monomers such as (MMA) carry out the emulsion polymerization reaction.And because of surface of good glossiness and high anti-ball falling impact are widely used in daily lifes such as auto parts, electrical appliance.Wherein the size of rubber latex is relevant to the working properties and the shock resistance of product, and promptly shock resistance intensity increases when particle diameter increases.And particle diameter is when increasing, and tensile strength and gloss but descend thereupon.But still can keep the important topic that high-tensile and high-luster are current polymer investigators so increase the rubber latex particle diameter with preparation shock resistance resin.
The present invention discloses a kind of manufacture method to prepare a kind of thermoplastic styrene resin composition, and it has the excellent high anti-ball falling impact and the good characteristics such as processing forming, high-tensile and high gloss of tool of the particle diameter speciality of gatheringization.The technology of rubber particles gatheringization is one of polymer investigator important topic of endeavouring to develop for many years, in the gathering preparation method of rubber particles, have: utilize acid anhydrides technology (U.S.Pat.3652721, Dalton etc.) or the technology (U.S.Pat.3944630, Fumio etc.) that contains carboxylic acid be applicable to that the aggregated particles particle diameter is in narrow distribution range; The technology (ISRC-U.K.Pat.976212,297213,976214 and 1039727) of using pressurization or shearing can be used for the continuity operation to get the aggregation grain diameter that wide scope distributes; (three examines " to the observation of polymer lattice gatheringization " of Wesslaw etc. as the elastomeric aggregating agent prepared therefrom of water repellency at the latex processing procedure to utilize hydrophilic polymer, " Inves-tigationsintotheAgglomerationofPolymerLatices ", Ange-wandteMakaromolekulareChemie, 2, No.20, Apr.30,1969, PP.1-25), reaching (U.S.Pat.3825621, Ford etc.) wherein must be allowed a choice to aggregating agent prepared therefrom and graft polymerization reaction condition according to product property.
In above-mentioned United States Patent (USP), add in the aggregation method of physical methods such as chemical processes such as acid, salt or solvent or pressurization, adding speed and stirring velocity all may influence size, and easily produce particle diameter super large or grumeleuse because of the production period condition is wayward, acid and salt also can partial destruction emulsive stabilitys.Especially the polymer coagulant (hereinafter to be referred as C.A.latex) that contains the carboxylic acid group is added when assembling rubber particles in (section) mode once, usually only obtain a particle diameter that distributes and be rather narrow, can make tensile strength and glossiness all descend because of particle diameter increases for the high impact-resistant resin of desire manufacturing.And when assembling rubber particles with existing continuous interpolation C.A.latex mode (the interpolation time is many above 5 minutes), can be wayward because of size distribution, make and when graft polymerization, can't do the grafting adjustment at the grafting structure of various different-grain diameters, cause the graft polymerization ratio uncontrollable, so that the rerum natura variation.This kind shortcoming is for the ABS resin that contains small particle size, because of its particle dispersion distance weak point of macroparticle rubber in resin than same weight, make in the machine-shaping process because of fusion and cut off the bad aggegation that causes rubber particles easily, the ball falling impact intensity of finished product is reduced.Especially when the high temperature ejection formation, make moulding product surface luster obviously descend because of the bad aggegation of rubber particles.
The present invention is for solving the above-mentioned tool shock resistance simultaneously that is difficult to obtain, the difficult problem of high-tensile and high-luster thermoplastic resin, develop through result of study with keen determination and a novelty manufacture method, be about to C.A.latex respectively with specified proportion, specified time interval is assembled rubber particles with addition manner more than two sections or two sections, the graft polymerization ratio is controlled easily, and obtained the thermoplastic styrene resin composition of excellent high ball falling impact, high-tensile, well processed formability and high-luster.
The weight part of the following stated and relevant synthetic rubber latex or C.A.latex all represents it is at the dry weight state unless otherwise indicated.This manufacture method is characterised in that:
(1) contain C.A.latex that the synthetic rubber latex of 100 weight parts adds 1.0～6.7 weight parts to implement gatheringizations, the gatheringization afterwards pH value of emulsion is not less than 6;
(2) C.A.latex adopts more than two sections or two sections addition manner to assemble rubber particles, and first period timed interval with second section C.A.latex interpolation is 10～60 minutes; Wherein: (a) to 100 parts by weight of rubber, first section C.A.latex addition is 0.2～0.8 weight part; (b) to 100 parts by weight of rubber, first section later C.A.latex addition summation is 0.8～5.9 weight part; (c) ratio of first section addition and first section later C.A.latex addition sum total is 1: 1 to 1: 20;
(3) rubber latex after the gatheringization is in the presence of 100 weight parts, can be that monomer, unsaturated nitrile are to select two or more monomer 10～150 weight parts monomer, the methacrylate ester monomer from aromatic vinyl, and can close monomer 0～50 weight part of base and carry out graft polymerization and form feature constituent of the present invention with the insatiable hunger that contains of aforementioned monomer copolymerization.
The present invention is specified in its characteristics the back for the manufacture method of this feature constituent respectively according to its reactions steps:
One. the preparation of synthetic rubber latex
Employed synthetic rubber latex comprises the homopolymer of polyhutadiene system, acrylic ester or multipolymer, trimer, the polymer rubber that can form with these monomers in the manufacture method of the present invention.For example single vinylation multipolymer of fatty compounds is closed in polyhutadiene, butyl polyacrylate and divinyl-insatiable hunger, as the multipolymer of butadiene-styrene, divinyl-alpha-methyl styrene etc.; Lonitrile copolymer is closed in divinyl-insatiable hunger, as the multipolymer of butadiene-acrylonitrile, divinyl-methacrylonitrile etc.; The butadiene-acrylic acid ester copolymer is as butadiene-acrylic acid methyl esters, the positive butyl ester multipolymer of butadiene-acrylic acid; The multipolymer of divinyl-methacrylic ester etc. is as divinyl-Jia Jibingxisuanyizhi.This rubber particles in synthetic rubber latex is usually between 0.04～0.18 μ m.
The preparation of two .C.A.latex
C.A.latex of the present invention comprises the multipolymer of carboxyl carboxylic acid monomer and alkyl acrylate monomer usually.The alkyl carboxylic acid monomer can be vinylformic acid, methacrylic acid, 2-methylene-succinic acid and butenoic acid etc.And alkyl acrylate monomer comprises: methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, Octyl acrylate, 2-EHA, dodecyl acrylate and similar.
Suitable emulsifying agent also can add in the reaction of this step, and this type of emulsifying agent comprises the sodium salt of anion surfactant such as lipid acid, sylvite, sodium alkyl benzene sulfonate, rosin acid sodium, phenyl ethoxy sulfonate and the similar compound of lipid acid.
When substrate rubbers latex of the present invention was assembled by C.A.latex, the substrate rubbers particle only need at room temperature mix above-mentioned both latex and stir and can reach congregational rate.
If the pH value of C.A.latex is less than 4, just there is not the effect of the gatheringization that is showing.When with after rubber latex mixes, the pH value then is not less than 6, is preferably between pH7 to 13.When the pH value less than 6 the time, can't obtain good congregational rate, be higher than the rubber latex instability after then making gatheringization at 13 o'clock.
Three. the gatheringization reaction
First section C.A.latex addition to 100 parts by weight of rubber is 0.2～0.8, and with 0.3～0.6 the best; When first section addition is less than 0.2, then similar to one section additive process, can't when high rubber content, obtain the high gloss resin, when being higher than 0.8, then have super aggregate particles and produce, make tensile strength reduce.To first section of 100 parts by weight of rubber later C.A.latex addition summation is 0.8～5.9, and with 1～3 the best; When first section later addition summation is less than 0.8, can't obtain the resin of high ball falling impact, when being higher than 5.9, will make the processing forming variation, cause the uneconomical of production cost on the contrary.
The present invention all needs to add in 3 minutes to finish to each section interpolation of C.A.latex, is preferably in 1.5 minutes, is more preferred from 30 seconds.And first period timed interval of adding with second section C.A.latex be 10～60 minutes, and with 20～40 minutes the bests; If pitch time is when being less than 10 minutes, can makes when the high-temperature molding surface luster extreme difference that becomes not exclusively on the contrary because of first section gathering, and glossiness and ball falling impact be there is no further improvement when being higher than 60 minutes.And through the rubber particles of the inventive method gatheringization, its median size is between 0.23～1.00 μ m.
Four. graft polymerization reaction
The preparation of graft copolymer normally utilizes existing graft polymerization technique to carry out graft polymerization reaction with monomer mixture in the presence of the elastomerics (rubber) of gatheringization, utilizes the combination of chemical or at least a polymkeric substance of grafting on elastomerics.In monomer and elastomeric ratio and polymeric condition, can obtain simultaneously to be grafted on and be the polymkeric substance of the required grafting degree of people on the elastomerics.Usually, in the graft polymerization reaction, the speed that polymeric condition, elastomeric chemical property and size of particles, monomer add, chain-transfer agent, catalyzer etc. are all influential.
Initiator or catalyzer in the scope of 0.01～5.0 weight part of polymerisable monomer, are preferably in 0.1～3.0 usually, press monomer and required polyreaction and decide.But the initiator increment adds the carrying out in order to graft polymerization reaction.
The molecular weight size of graftomer, temperature control in the time of can be by graft polymerization reaction, and/or cooperate quite a small amount of existing molecular weight regulator of ratio, regulated and control as (examples: basic mercaptan of n-dodecyl mercaptan, the 3rd (dodecane) and terpinolene) such as mercaptan, halogenide and terpenes.Graft polymerization reaction also can be controlled by changing polymkeric substance grafting amount of (rubber) on elastomerics.Usually, this effect can utilize monomer mixture to add polyreaction with continuous or increment ground, and preferably continuous simultaneously or increment ground adding initiator.Various existing emulsification radical polymerization initiators can be used in graft polymerization reaction, comprise existing superoxide and azo-compound, and its addition manner can be in graft polymerization reaction once adds or continuously or the adding of increment ground.Suitable peroxide initiator, for example alkali metal peroxide, persulphate, perborate, peracetate, percarbonate, hydrogen peroxide.In addition, oil-soluble initiator also can be included, as peroxidation two-tertiary butyl, benzoyl peroxide, the laurylperoxide base, the peroxidation oil base, the peroxidation toluoyl, two phthalandione acyl-tertiary butyl ester of crossing, the peroxyacetic acid tertiary butyl ester, t-butyl perbenzoate, the dicumyl peroxide base, tert-butyl peroxide, heavy carbonic sec.-propyl peroxy ester, 2,5-dimethyl-2,5-two (tributyl peroxy) hexane, 2,5-dimethyl-2,5-two (tributyl peroxy)-hexane-3, the tert-butylhydroperoxide, the cumic aldehyde hydroperoxy-, to the hydroperoxy-that methylates, the cyclopentyl hydroperoxy-, the diisopropyl benzene hydroperoxy-, to tertiary butyl isopropyl benzene hydroperoxy-, the pinane hydroperoxy-, 2,5-dimethyl hexyl-2,5-diperoxy hydrogen etc., or above mixture.Other has the free radical catalyst of other modes also to be used, for example actinic radiation.
Rubber latex after the gatheringization and monomer mixture stir to do polyreaction under the rare gas element of 20～100 ℃ of temperature ranges, also can be forced into 0～100p.s.i.g..Polyreaction continues at least 90% monomer and is aggregated, and this polymerization reaction time takes 2～10 hours usually, and is preferably 4～8 hours.At last, in residual monomer and other volatile compounds with dehydration, washing, and the exsiccant mode separate.Latex can spraying drying, condense or other modes are dewatered with salt.
When the rubber latex after the gatheringization is carried out graft polymerization reaction, in the presence of 100 weight parts (dry weight), can be that monomer, unsaturated nitrile are to select two or more monomer 10～150 weight parts monomer, the methacrylate ester monomer from aromatic vinyl, and can with the aforementioned monomer polymeric contain insatiable hunger close the base monomer 0～50 weight part carry out graft polymerization.
Aromatic vinyl is that monomer can be: vinylbenzene, alpha-methyl styrene, α-chloro-styrene, p-t-butylstyrene, p-vinyl toluene, o-chloro-styrene, p-chloro-styrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromo-benzene ethene, 2,5-Dowspray 9 etc., wherein preferable with vinylbenzene or alpha-methyl styrene.
Unsaturated nitrile is that monomer can be: vinyl cyanide, Alpha-Methyl vinyl cyanide, methacrylonitrile, propane dinitrile, anti-crotononitrile etc., and wherein preferable with vinyl cyanide.
The methacrylate ester monomer can be: methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid benzene methyl, N-Hexyl methacrylate, cyclohexyl methacrylate, methacrylic dodecyl gallate, methacrylic acid 2-hydroxyl ethyl ester, glycidyl methacrylate and dimethylaminoethyl methacrylate etc., and wherein preferable with methyl methacrylate.
Copolymerizable monomer such as maleimide are 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-or 4-tolyl maleimide, N-2,3-or 4-ethylbenzene base maleimide, N-2,3-or 4-butylbenzene base maleimide, N-2,6-tolyl maleimide, N-2,3-or 4-chloro-phenyl-maleimide, N-2,3-or 4-bromophenyl Malaysia imide.
Except that above-mentioned person, other copolymerizable monomer still have: acrylic monomer, Maleic Acid, Anhydrous, anhydrous methyne Succinic Acid, anhydrous methyl-maleic acid, anhydrous neocerotic acid, one and unsaturated carbonic acid such as dihydroxy ester and its ester be monomer, ethene, propylene, 1-butylene, the 1-amylene, 4-methyl-1-pentene, the ethylene chloride base, ethylene chloride fork tetrafluoroethylene, one chlorine three is fluoridized ethene, the hexafluoro propylene, divinyl, propenyl amine, isobutenyl amine, the vinyl acetate between to for plastic base, vinyl one nitrogen 5 circle ketone, vinyl one nitrogen triolefin land surround, vinyl two semicarbazides, vinyl ether, vinyl ketone, the benzo cyclopropylene, naphtho-ethene etc.
Five. the fusion of polymkeric substance
The final product of the graft polymerization reaction program in the processing procedure of the present invention often is the polymeric blends of higher rubber content.The multipolymer that graftomer often is mixed into aforementioned grafting monomer and is become is as styrene-acrylonitrile copolymer, styrene-methylmethacrylate copolymer etc., with the amount that increases matrix polymer and reduce rubber content.This type of resin copolymer that is used for diluting graft copolymer can be via emulsification, suspension or the manufacturing of mass polymerization technology.Usually, final adulterant contains the rubber elastomer composition of 2～50 weight percents, is preferably 7～35 weight percents, and best be 10～25 weight percents.
Following embodiment can describe superiority of the present invention in detail, but is not in order to restriction protection scope of the present invention, mentions that wherein composition is is benchmark with the weight part.
Embodiment 1～5
Five kinds of graftomer that get because of the different addition manners of C.A.latex, according to following step (A)-(D) preparation and get:
(A) do not assemble the manufacture method of rubber latex (A-1)
| Constituent | Weight part |
| 1,3-butadiene | ????150.00 |
| Potassium persulfate solution (1%) | ????15.00 |
| Sodium dodecyl sulfate solution (10%) | ????20.00 |
| Distilled water | ????190.00 |
| Ethylene glycol dimethacrylate | ????0.13 |
In the reaction 12 hours down of 65 ℃ of temperature of reaction, obtaining transformation efficiency is 94% according to above prescription, and solids content is about 40%, and the rubber latex (A-1) of the about 0.1 μ m of weight average particle diameter.
(B) manufacture method of C.A.latex (B-1)
| Constituent | Weight part |
| Ethyl propenoate | ????90.0 |
| Vinylformic acid | ????10.0 |
| Potassium persulfate solution (1%) | ????0.5 |
| Sodium dodecyl sulfate solution (10%) | ????0.5 |
| Distilled water | ????200.0 |
In the reaction 5 hours down of 75 ℃ of temperature of reaction, it is about 95% to obtain transformation efficiency, the C.A.latex of pH6.0 (B-1) according to above prescription.
(C) manufacture method of gatheringization rubber latex (C-1) will contain the rubber latex (A-1) of 100 weight parts (dry weight), assemble rubber particles, gathering rubber latex (C-1) the pH value about 8.5 of gained according to the C.A.latex in the table 1 (B-1) composition with two sections (or more than) addition manners.
(D) gathering rubber latex (C-1) is carried out graft polymerization reaction, to make graft copolymer (D-1)
| Constituent | Weight part |
| Polybutadiene latex after the gatheringization (dry weight) | ????100.0 |
| Vinylbenzene | ????75.0 |
| Vinyl cyanide | ????25.0 |
| The 3rd-lauryl mercaptan | ????2.0 |
| Two-hyperis benzene | ????3.0 |
| Copperas solution (0.2%) | ????3.0 |
| Formaldehyde sodium sulfoxylate solution (10%) | ????0.9 |
| Ethylene dinitrilotetra-acetic acid solution (0.25%) | ????3.0 |
As the experimental procedure of embodiment 1～5, and the addition manner of C.A.latex (B-1) is with embodiment 1 (table 1), except the graft polymerization monomer of (D) step changes into:
| Monomer | Weight part |
| Vinylbenzene | ????70.0 |
| Vinyl cyanide | ????20.0 |
| Methyl methacrylate | ????5.0 |
| N-phenylmaleimide | ????5.0 |
Under mix monomer added continuously, graft polymerization reaction carried out 8.5 hours, obtained the graft copolymer of transformation efficiency about 95%.
The C.A.latex of table 1: embodiment 1～6 (B-1) addition manner
| Embodiment | Addition manner | First section addition (#) | Second section addition (#) | The 3rd section addition (#) | Total addition level (#) | First and second section is added (branch) at interval | Ratio (*) |
| ????1 | Two sections | 0.3 | ?2.2 | ??0 | ????2.5 | ????20 | ?7.3 |
| ????2 | Two sections | 0.4 | ?2.4 | ??0 | ????2.8 | ????20 | ?6.0 |
| ????3 | Two sections | 0.4 | ?2.4 | ??0 | ????2.8 | ????40 | ?6.0 |
| ????4 | Two sections | 0.6 | ?2.2 | ??0 | ????2.8 | ????20 | ?3.7 |
| ????5 | Three sections | 0.6 | ?2.0 | ??0.4($) | ????3.0 | ????20 | ?4.0 |
| ????6 | Two sections | 0.3 | ?1.8 | ??0 | ????2.1 | ????20 | ?6.0 |
(#): unit is a weight part
(*): C.A.latex total amount after second section/first section C.A.latex amount
($): it is 10 minutes that second and third section adds pitch time
Comparative example 1～8
Do not assemble rubber latex (A-1), C.A.latex (B-1) and graft copolymer (D-1) according to embodiment 1～6 same prescription manufacturing.Only the addition manner of C.A.latex adopts as two sections (comparative examples 1～4) of table 2, one section or continuous (comparative example 5～8).
Table 2: the C.A.latex of comparative example 1～8 (B-1) addition manner
| Comparative example | Addition manner | First section addition (#) | Second section addition (#) | Total addition level (#) | First and second section is added (branch) at interval | Continous way is added the time (branch) | Ratio (*) |
| ????1 | Two sections | 0.1 | ?2.7 | ?2.8 | ????20 | ?—— | ?27 |
| ????2 | Two sections | 1.0 | ?1.8 | ?2.8 | ????20 | ?—— | |
| ????3 | Two sections | 2.5 | ?0.3 | ?2.8 | ????20 | ?—— | |
| ????4 | Two sections | 0.4 | ?2.4 | ?2.8 | ????5 | ?—— | |
| ????5 | One section | —— | ?—— | ?2.8 | ????— | ?—— | |
| ????6 | One section | —— | ?—— | ?4.0 | ????— | ?—— | |
| ????7 | Continuously | —— | ?—— | ?2.8 | ????— | ?10 | |
| ????8 | Continuously | —— | ?—— | ?2.8 | ????— | ?20 |
(#): unit is a weight part
(*): C.A.latex total amount after second section/first section C.A.latex amount
The physicals test
Aqueous sulfuric acid with 5% adds graft copolymer (D-1), can obtain the curding out thing in 90 ℃ of stirrings after 10 minutes, and this precipitate obtains the graft copolymer powder after dehydration, washing, drying.
In the AS resin, add 2,6-two-tertiary butyl-4-methyl azoles (0.1%), triphenylphosphate (0.1%), ethene bis-stearamides (2%) etc., mix into different rubber contents with above-mentioned graft copolymer powder, and obtain the particles product with the extrusion machine extruding after the mixed together.Glossiness and the test of tensile strength physical property, measuring method is as follows:
Ball falling impact intensity
Penetrate radius 50mm with Jet forming machine, the circular test board of thickness 3mm, down with the steel ball of the 5kg impact test plate center of falling, in the hope of the not ruined beta maximum energy of test board, its unit is kg.cm in room temperature (23 ℃).Surface gloss
Respectively under 230 ℃ and the 280 ℃ of mold temperatures, penetrate the tabular forming composition of 50mm (wide) * 90mm (length) * 3mm (thick) with Jet forming machine (shaking the SM-90 Jet forming machine of male Mechanology Inc. system).Molding plate uses glossmeter (Gardner system, Micro-TRI type equipment) with 60.Input angle is measured the mean values of five composing type flat boards, and its unit is %.
Tensile strength
According to the test of U.S. rule ASTMD-638 method, its unit is kg/cm.
Test result
(A) graft copolymer that gets according to the different addition manners of C.A.latex in embodiment 1～6 makes particles test of products sheet again and imposes above-mentioned physical property test, result such as table 3.
Table 3: through embodiment 1～6 and the plastic cement products test film, its ball falling impact intensity, surface gloss, tensile strength test result.
| Embodiment | Rubber content (weight part) | Ball falling impact intensity (kgcm) | Surface gloss | Tensile strength (kg/cm) | |
| Penetrate 230 ℃ of temperature | Penetrate 280 ℃ of temperature | ||||
| ????1 | ????20 | ????400 | ????92 | ????82 | ????402 |
| ????2 | ????20 | ????400 | ????93 | ????80 | ????406 |
| ????3 | ????20 | ????420 | ????90 | ????82 | ????395 |
| ????4 | ????20 | ????380 | ????91 | ????80 | ????390 |
| ????5 | ????20 | ????380 | ????88 | ????78 | ????386 |
| ????6 | ????20 | ????380 | ????90 | ????80 | ????390 |
Show, add C.A.latex with two sections or two sections with upper type by method of the present invention and can get excellent high ball falling impact intensity, and the tool high-tensile, high-luster through gatheringization rubber modified styrene series resin.
(B) the grafting polymers that gets according to the different addition manners of C.A.latex in comparative example 1～8 makes particles test of products sheet again and imposes above-mentioned physical testing,
Result such as table 4.
Table 4: through comparative example 1～8 and the plastic cement products test film, its ball falling impact intensity, surface gloss, tensile strength test result.
| Embodiment | Rubber content (weight part) | Ball falling impact intensity (kgcm) | Surface gloss | Tensile strength (kg/cm) | |
| Penetrate 230 ℃ of temperature | Penetrate 280 ℃ of temperature | ||||
| ????1 | ????20 | ????320 | ????90 | ????62 | ????398 |
| ????2 | ????20 | ????340 | ????86 | ????70 | ????362 |
| ????3 | ????20 | ????350 | ????88 | ????68 | ????358 |
| ????4 | ????20 | ????360 | ????88 | ????52 | ????392 |
| ????5 | ????20 | ????320 | ????92 | ????82 | ????408 |
| ????6 | ????20 | ????380 | ????76 | ????64 | ????352 |
| ????7 | ????20 | ????360 | ????89 | ????46 | ????386 |
| ????8 | ????20 | ????350 | ????90 | ????34 | ????378 |
As shown in table 4, when the addition deficiency of first section C.A.latex, as comparing
Example 1, then ball falling impact intensity and surface gloss are not good; And when the addition of first section C.A.latex too much, as comparative example 2 and 3, tensile strength variation then; If first period timed interval with second section interpolation is not enough, as comparative example 4, then high temperature process formability variation can't obtain the high gloss characteristics resin.And add C.A.latex with an existing segmented mode, and as comparative example 5 and 6, when desire obtains high ball falling impact intensity, but making the tensile strength variation, glossiness also decreases.If add C.A.latex,, when desire obtains high ball falling impact intensity, then cause high temperature process formability variation, and greatly reduced the glossiness of moulding product as comparative example 7 and 8 with existing continuous mode.
Claims (6)
1. the manufacture method through gatheringization rubber modified styrene series resin comprises: (1) is that the rubber latex of 0.04～0.18 μ m is added polymer coagulant (C.A.latex) gatheringizations contain the carboxylic acid group with median size, and making the formation median size is the gathering rubber latex of 0.23～1.0 μ m; (2) rubber latex after the gatheringization is in the presence of 100 weight parts (dry weight), can be monomer from aromatic vinyl, unsaturated nitrile is a monomer, select two or more monomer 10～150 weight parts in the methacrylate ester monomer, and can carry out graft polymerization with the monomer that contains unsaturated group 0～50 weight part of aforementioned monomer copolymerization, it is characterized in that: the C.A.latex addition manner that contains the carboxylic acid group in described (1) is the mode that is divided into more than two sections or two sections, and in the presence of the rubber latex of 100 weight parts (dry weight), first section addition of C.A.latex is 0.2～0.8 weight part; First section later addition summation is 0.8～5.9 weight part.
2. according to the manufacture method of claim 1, it is characterized in that in the presence of the rubber latex of 100 weight parts (dry weight) that first section addition the best of C.A.latex is 0.3～0.6 weight part; First section later addition summation the best is 1～3 weight part.
3. according to the manufacturing processed of claim 1, it is characterized in that C.A.latex is 10～60 minutes first period timed interval with second section interpolation.
4. according to the manufacturing processed of claim 1, it is characterized in that C.A.latex is 20～40 minutes first section timed interval the best with second section interpolation.
5. according to the manufacturing processed of claim 1, it is characterized in that C.A.latex first section with first section after the ratio 1: 1～1: 20 of addition summation.
6. manufacturing processed according to claim 1 when it is characterized in that the C.A.latex addition manner is divided into more than two sections or two sections, is in 3 minutes during every section interpolation.
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| CN115043994A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Emulsion polymerization preparation method of thermoplastic resin with improved heat resistance and thermoplastic resin obtained by emulsion polymerization preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043994A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Emulsion polymerization preparation method of thermoplastic resin with improved heat resistance and thermoplastic resin obtained by emulsion polymerization preparation method |
| CN115043994B (en) * | 2021-03-08 | 2023-07-25 | 中国石油天然气股份有限公司 | Emulsion polymerization preparation method of thermoplastic resin with improved heat resistance and thermoplastic resin obtained by emulsion polymerization preparation method |
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