CN101503555B - Heat resisting resin composition and preparation thereof - Google Patents
Heat resisting resin composition and preparation thereof Download PDFInfo
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- CN101503555B CN101503555B CN2008100576275A CN200810057627A CN101503555B CN 101503555 B CN101503555 B CN 101503555B CN 2008100576275 A CN2008100576275 A CN 2008100576275A CN 200810057627 A CN200810057627 A CN 200810057627A CN 101503555 B CN101503555 B CN 101503555B
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Abstract
The invention relates to a heat-resistant resin composition and a preparation method thereof. The resin composition comprises the following: 10 to 65 portions of maleimide heat-resistant resin, 30 to 55 portions of graft polymer of conjugated diene rubber grafted aryl ethylene unit body and nitrile vinyl unit, and 5 to 35 portions of biopolymer of aryl ethylene monomer and nitrile vinyl monomer. The heat-resistant resin composition prepared by the method for preparing the maleimide heat-resistant resin composition has the advantages of good appearance and high heat resistance, and is a heat-resistant material with good performance. The prepared heat-resistant resin can be widely used for heat-resistant modification of materials, such as ABS, PC, PBT and the like. As a material with excellent heat-resistant performancs, the resin composition can be independently used, and can also be used for preparing high heat-resistant parts of automobiles and home appliances.
Description
Technical field
The present invention relates to a kind of heat resistant resin composition and preparation method, particularly a kind of heat-resistant resin in maleimide class composition and method of making the same that contains.
Background technology
The monomeric free-radical polymerized thing of maleimide because of containing the plane five-membered ring structure on its molecular chain, can effectively suppress the rotation of chain, thereby have very high structure rigidity and thermostability, thereby be subjected to extensive concern.Wherein also a lot of about the research of maleimide monomer and the monomeric multipolymer of aryl ethylene class.
The preparation of superelevation heat-resisting ABS resin comprises two kinds of alloyage and modification by copolymerization methods, and wherein the modification by copolymerization method is a kind of reasonable technological line.Alloyage mainly is meant the PC/ABS alloy.The modification by copolymerization method mainly is made up of two portions technology, what a part was a maleimide (IMID) with the monomeric terpolymer of maleimide (SMIA) of aryl ethylene class monomer (AEM) itrile group vinyl monomer (NEM) is synthetic, and another part is the synthetic of ABS graft copolymer.The synthetic of the monomeric terpolymer of maleimide is the stable on heating assurance of superelevation heat-resisting ABS resin, and the ABS graft copolymer is determining the balance of its over-all properties.
The patented technology of production heat-resisting ABS resin the earliest is mainly, produce earlier alpha-methyl styrene (α-MS)-vinyl cyanide (AN) multipolymer (α-MSAN) and with itself and the blending of graft rubber matrix, adjust ratio, the kind of blend components, design is produced and is had different temperature classifications, flowability, shock strength and inflexible ABS product respectively.SUMITOMO CHEMICAL patent US 4294946 for example, developed a kind of letex polymerization production technique of heat stable resin: α-MS and AN join in the reactor free radical polymerization in 65: 35～80: 20 ratio.Polymerization at first takes place in whole α-MS and 10～99% AN in the reaction, treats that polymerization adds remaining AN after finishing again, takes place fully until reaction; The heat-resisting SAN of Sheng Chenging obtains heat-resisting level ABS resin with the blending of grafting rubbers matrix more thus.
As the stable on heating method that improves the ABS thermoplastic resin, known have one by introduce alpha-methyl styrene or other similar monomer methods in copolyreaction.For example, US 4874829 generates multipolymer or trimeric method with alpha-methyl styrene, vinyl cyanide and maleimide monomer continuous polymerization, in order to break through the low-conversion of alpha-methyl styrene, uses a large amount of highly active vinyl cyanide in the feed composition.Adopt the final easy variable color of resin that generates of aforesaid method and generate gel, this will cause the mechanical property of materials of heat-resisting ABS resin significantly to descend.
The open NO.1983-206657 of US 4757109 and Japanese Patent proposes a kind of heat stable resin and ABS resin to be mixed and improves the stable on heating method of ABS resin.Above-mentioned heat stable resin is by the maleimide monomer, and vinyl nitrilation thing monomer and aromatic ethylene base generate with emulsion polymerization, and the maleimide monomer content is high more in the resin, and thermotolerance is good more.Yet because this heat-resisting monomer reaction speed is fast, heat release two is big, and content is limited in resin.In order to break through this restriction, it is very complicated that polymerization process becomes; The maleimide monomer content is high more in the polymer resin, and is poor more with the ABS resin consistency, thereby causes the product resistance to impact shock to descend.Commercial emulsion method heat-resisting ABS resin is the grafting rubbers copolymerization component that vinylbenzene, vinyl cyanide and rubber generation letex polymerization is obtained high glue content at present, the multipolymer that olefinic monomers such as heat-resisting monomer such as maleimide or maleic anhydride and vinyl cyanide, vinylbenzene are made is by being obtained two kinds of components by the twin screw extruder blending.In order to improve resistance toheat, adding graft copolymer has certain limitation, thereby rubber content can not be too high in the product, therefore generally is difficult to obtain have the high-impact performance when product has the high heat resistance energy.
When needs are used for the higher thermotolerance of industrial application, mix multipolymer that imines replaces with the preparation heat-resisting ABS resin.By adopting the N-phenylmaleimide (NPMI) (US 4567233) in the preparation of thermotolerance toughener or adopting N-Chloro-O-Phenyl maleimide or allyl group, alkyl or ring-type substituent, and preparing this heat-proof ABS (US 3652726 and US 5726265), these methods have characteristics such as manufacturing cost height.
CN1126734A discloses and has adopted the maleimide modification to prepare the method for ABS resin.This method comprises mediates a kind of maleimide copolymer, a kind of ABS graft copolymer and optional a kind of vinylbenzene (ST)-acrylonitrile copolymer (SAN) multipolymer, thereby it is obtain heat-stable master batch resin, and further that a kind of ABS graft copolymer and a kind of san copolymer is kneaded together in heat-stable masterbatch.Although but the maleimide copolymer in the component has high heat-stable characteristics, compare in common SAN resin, low in the molten state current downflow, thereby molding performance is poor.Be injection molded into the mould processing characteristics in order to improve, use this method to have to add softening agent, lubricant etc., must use additive homodisperse in resin in the course of processing, but additive will be penetrated into and cause the outward appearance generation defective that is damaged on the product surface in links such as injection molding, processing, tends to reduce resistance toheat.
For the continuous bulk production technique, at high temperature, the NPMI of high density easily forms oligopolymer, thereby causes the thermal distortion contribution of per unit NPMI to descend, be exactly that NPMI and ST reaction forms in the process of alternating copolymer more in addition, a spot of AN will cause serious component migration.
Patent US 5270387 points out that body NPMI-SAN and the blend of emulsion graft polymerization rubbery copolymer can be used for producing the product of high gloss.For the automobile Application Areas, need the outward appearance of low gloss usually, contain the ABS product of body NPMI-SAN and emulsion or mass polymerization, can be so that product has good balance rigidity, thermotolerance and tensile property.Use for automobile, the another one advantage be mass polymerization owing to do not contain emulsifying agent and corresponding treatment process, its ABS resin that contains NPMI does not haze, can not discharge irritating smell.Heat-proof ABS mold thing can directly obtain pellet or utilize general ABS and maleimide blend, colour batch blend or the heat-proof ABS masterbatch.
The patented technology CA 1185737 that Mitsubishi-Monsanto Company uses, GB 2102815 is: a kind of production technique with heat-resisting ABS resin of fabulous high-temperature stability, constituting component is: A.10～and 90%:15～50 part N substituted aromatic base maleimide, 40～85 parts of vinyl aromatic monomers, 0～30 part of vinyl monomer; B.10～and 90%:15～30 part vinyl cyanide, 65～85 parts of ST, 0～30 part of vinyl monomer.This invents prepared excellent heat resisting and high high-temp stability, mold and processing flowability.But the shock strength of product is lower.
The patented technology US5532317 that the NEC chemistry uses, JP10036614 is: maleimide modified heat resistant ABS resin masterbatch production technique, mediate the modified master that forms for two kinds or three kinds of three kinds of multipolymers, the second-order transition temperature of the masterbatch of acquisition is above 140 ℃.This kind masterbatch makes heat-resisting ABS resin with the ABS resin blending and modifying again.
The patent US4808661 of MTC shows, the compatibility problem of considering in its patent is at first considered in the reaction to add part NPMI, adds remaining NPMI monomer again after treating to change mutually.All contain NPMI in external phase and the disperse phase like this, guaranteed the biphase consistency.The ABS composition for preparing the maleimide modification with continuous bulk is disclosed among the US4808661.
CN200710099316.0 relates to chemical field, specifically, relate to a kind of preparation method of heat-resistant ABS polymer of continuous bulk, comprising: the grafting of main feed step, inferior feed step, main charging and the grafting of conversion step, inferior charging mutually and the mixing step of conversion step and main charging and inferior charging mutually.The polymkeric substance of preparation has 9～15 swelling index, 14～16% rubber contents, and 1～2 micron particle diameter, and present the heat-resisting level ABS product of two or multimodal size distribution, the product that obtains has 10～28kJ/m
2Shock strength and 1～2.5g/10min melt index and 108～125 ℃ of vicat softening temperatures, product are applicable to heat resistance modified and accessory manufacturing automotive field.
DOW chemical company is again on the basis of MTC production technique, a kind of shock-resistant monovinylidene aromatic copolymer composition of maleimide modification of graft copolymerization is disclosed in patent US5412036, when its swelling index more than 12, and the difference of the maleimide monomer content in its graft copolymer and matrix multipolymer two portions is when being no more than 9 percentage points, and the shock strength and the fatigue resistance of said composition significantly improve.This composition can pass through body, solution or body/suspension grafting copolymerization process preparation easily, the rubber polymer component that at least 20% maleimide monomer component is postponed till dissolved improvement impact property in the polymerization process changes adding afterwards mutually, but because preparation technology's complexity, cause maleimide monomer not transform fully, cause the yellowness index of product higher, outward appearance is relatively poor.
Patent KR 9605078 cases of CHEIL, in order to improve the resistance toheat of resin, with three kinds of copolymer blended making, wherein three kinds of blends are respectively (A) NPMI, ST, AN emulsion polymer, account for 35～60%, (B) NPMI, ST, three kinds of monomer emulsion polymkeric substance of AN, but molecular weight is higher, accounting for 5～30% of final heat resistant product, (C) is the emulsion graft copolymer of NPMI, ST and rubber, accounts for 20～50% of final heat resistant product.Under the situation that does not reduce SAN resin mechanical property, improve its resistance toheat, and can significantly improve the heat-drawn wire of the finished product, but the processing characteristics of product is relatively poor.
Core technology is the blending consistency between synthesizing of heat stable resin and heat stable resin and the ABS graft copolymer two-phase in the heat-resisting ABS resin technology of preparing.Heat stable resin is the key ingredient of decision heat-proof ABS composition resistance toheat, processing characteristics and strength and extension property.The performance of ABS graft copolymer and determined the shock resistance of heat-resistant composition and processing characteristics, strength and extension property and the outward appearance of composition had certain influence with the consistency of heat stable resin.
The synthetic of SMIA (the monomeric terpolymer of maleimide of aryl ethylene class monomer itrile group vinyl monomer) then can be adopted various polymerization processs such as body, suspension, emulsion and solution polymerization.Adopt the synthetic heat stable resin of body and solution polymerization process, monomer maleimide residual in equipment requirements height, complex technical process, the reaction process is difficult for removing, when the preparation heat-resistant composition, can influence the outward appearance of heat-resistant composition, and the maleimide monomer has and the general different characteristics of copolyreaction with AEM and NEM and three's copolyreaction, polymerization rate is very fast, and reaction is difficult to control.Though high temperature suspension polymerization also may address this problem, its to the requirement of equipment than higher.The molecular weight of the monomeric terpolymer of emulsion polymerisation process synthetic maleimide is with respect to various polymerization processs such as body, suspension and solution polymerizations, the molecular weight of polymerisate is bigger, helps improving the physical strength and the resistance toheat (especially heat-drawn wire performance) of product.
GB1026912 has described the multipolymer for preparing maleimide and MMA with the method for mass polymerization, and the initiator of employing is an organo-peroxide.GB1062872 has described the multipolymer for preparing vinylchlorid and maleimide with method of emulsion polymerization, adopts redox initiation system.CA2078337 etc. have reported the method for its solution polymerization, and its solvent generally uses organic solvents such as benzene, and initiator adopts oil-soluble initiator, as azo-initiator.What GB1086673 and GB1213061 introduced is that what it adopted is water soluble starter with the method for the multipolymer of emulsion polymerization prepared maleimide and vinylbenzene etc.In " polymer material science and engineering " 2001 (17) .1, reported in " second-order transition temperature of St-AN-NPMI emulsion copolymers and the rheological " that people such as Liu Guodong deliver and described its general emulsion polymerisation process, promptly adopt emulsifying agent, and be the polymerization process of initiator with the persulphate.
US4757109 has described a kind of technology with emulsion polymerisation process synthesizing styrene, vinyl cyanide, maleimide terpolymer, employing has the anionic emulsifier of well emulsify ability in the pH value is 3～9 scopes, initiator adopts redox system or Diisopropyl azodicarboxylate initiator, when this patent is pointed out with the Diisopropyl azodicarboxylate initiator, speed of response is slower, its polymerization technique is fairly simple, does not discuss in view of polymerization process.KR9510550 has also introduced a kind of technology that adopts method of emulsion polymerization synthesizing styrene, vinyl cyanide, maleimide terpolymer, what adopt is used water soluble starter of typical letex polymerization or redox initiation system, does not also discuss in view of polymerization process.
In order to obtain the good heat-resistant composition of over-all properties, need the conjugated diene rubber grafting aryl ethylene class monomer of the suitable glue content of preparation and the grafting powder of itrile group vinyl monomer, and particle diameter and gel to the graft base latex of the grafting powder of preparation conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer have higher requirement, and factors such as grafted monomer proportioning, molecular weight also all can produce considerable influence to the final performance of heat-resistant composition.
The contriver attempts to seek a kind of comparatively convenient, under the situation of easy handling, synthesize and in the monomer ratio scope of broad, can obtain forming the relatively emulsion polymerisation process of the SMIA multipolymer of homogeneous that distributes, and by the synthetic conjugated diene rubber grafting aryl ethylene class monomer that is complementary with it and the graft latex of itrile group vinyl monomer, graft latex and latex of heatresistant resin condense respectively or carry out common cohesion then, the method that the multipolymer of dry back and aryl ethylene class monomer and itrile group vinyl monomer carries out blend obtains the good heat resistant resin composition of over-all properties.
Summary of the invention
At the problems referred to above, the object of the present invention is to provide a kind of heat resistant resin composition and preparation method.
Heat resistant resin composition of the present invention, in heat resistant resin composition is 100 mass parts, contain: 10～65 parts of A. heat-resistant resin in maleimide class, the maleimide unit accounts for 10～45 quality % in the heat-resistant resin in maleimide class, aryl ethylene class unit accounts for 30～65 quality %, and the itrile group vinyl units accounts for 0～30 quality %; B. the graftomer of conjugated diene rubber grafting aryl ethylene class cell cube and itrile group vinyl units is 30～55 parts, conjugated diene rubber accounts for 35～60 quality % in the graftomer, aryl ethylene class unit accounts for 27～53 quality %, and the itrile group vinyl units accounts for 5～22.5 quality %; C. the copolymer of aryl ethylene class monomer and itrile group vinyl monomer is 5～35 parts, and aryl ethylene class unit accounts for 65～78 quality % in the copolymer, and the itrile group vinyl units accounts for 22～35 quality %; Wherein the emulsion of heat-resistant resin in maleimide class is to obtain (being 100 mass parts in its polymerization single polymerization monomer total amount, as follows) by the following method:
(a) preparation of monomer mixed solution
25～35 ℃ with 10～45 parts of maleimide monomers, 30～65 parts of aryl ethylene class monomers, 0～30 part of itrile group vinyl monomer, 0.1～0.6 part of oil soluble thermal decomposition initiating, 0.01～0.65 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (a).
Optimum condition is: 25～35 ℃ with 15～45 parts of maleimide monomers, 35～60 parts of aryl ethylene class monomers, 0.2～0.5 part of oil soluble thermal decomposition initiating, 0～25 part of itrile group vinyl monomer, 0.05～0.45 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (a).
(b) preparation of monomer emulsion
25～35 ℃ with 80～150 parts of de-salted waters, and 2.0～8.5 parts of emulsifying agents join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 20～75 minutes monomer emulsion (b).
Optimum condition is: 25～35 ℃ with 100～130 parts of de-salted waters, and 2.5～2.7 parts of emulsifying agents join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b);
(c) preparation of latex of heatresistant resin
Add 10～50 parts of de-salted waters in the reactor of whipping appts is housed, temperature is raised to after 60～80 ℃, divided more than 3 batches with (b) within 3～8 hours or join continuously in the reactor, and the temperature of maintenance system is carried out polyreaction under 60～90 ℃.(b) add after, polyreaction was carried out 0.5～2.0 hour again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.
Optimum condition is: add 20～40 parts of de-salted waters in the reactor of whipping appts is housed, temperature is raised to after 65～80 ℃, within 4～6 hours (b) joined in the reactor continuously, and the temperature of maintenance system is carried out polyreaction under 70～85 ℃.(b) add after, polyreaction was carried out 0.5～1.5 hour again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.
In (b) step, monomer emulsion (b) can divide to be added to more than 3 batches in the reactor in 3～8 hours and mix with (a) in the present invention, as adding 2～35% (b) every 5～100 minutes.
Also can add common agent such as softening agent, thermo-stabilizer etc. among the present invention after polymerization finishes, they can be mixed with the emulsion of auxiliary agent with emulsifying agent and de-salted water in emulsifying tank, and the mode with emulsion after copolyreaction finishes adds.The emulsion of described auxiliary agent, be meant the emulsion that softening agent, thermo-stabilizer, emulsifying agent and de-salted water is mixed with auxiliary agent in emulsifying tank, mode that can emulsion after copolyreaction finishes adds, and makes their degrees of scatter in polymkeric substance more even, thus better effects if.Used auxiliary agent can be softening agent, thermo-stabilizer etc. in emulsion, be employed softening agent such as DOP, DCP, Magnesium Stearate etc. in the general plastic working process, thermo-stabilizer is as 1076,1010,2246, emulsifying agent such as potassium stearate, potassium oleate, synthetic fatty acid potassium etc., proportioning also is to adopt general proportioning in the prior art, as softening agent: thermo-stabilizer: the weight ratio of emulsifying agent is (1～5): (1～5): (3～10), the consumption of emulsifying agent, water, softening agent, thermo-stabilizer is identical with general letex polymerization, be conventional amount used, no longer describe in detail.Certainly the present invention also can not add the emulsion of auxiliary agent, and use directly is provided after the polymerization.
Because the solubleness of RMI (alkyl substituted maleimide amine) in the ST/AN mixed solution is limited, after the RMI formula ratio reaches certain umber, temperature is lower than 25 ℃, RMI will separate out with solid-state from solution, so the starting temperature of emulsion polymerization should be more than 25 ℃, and temperature is higher than 35 ℃, the part initiator will begin to decompose, thereby the configuration temperature condition of emulsion polymerization chemical generally fixes within 25～35 ℃ the scope.
Obtaining resin by resin emulsion (comprise copolymer emulsion, graft copolymer emulsion or claim copolymer emulsion, graft copolymer latex) is very sophisticated prior art, all be by cohesion, the dry acquisition, the present invention is no exception, adopts universal method to be about to resin emulsion and is dried to resin by cohesion.
Among the present invention, when describing the monomer link configuration on the polymer chain structure, adopt " unit of the same name " to be used as its title, be called styrene units as the corresponding with it macromolecule chain section structure of styrene monomer, other same appellation with monomeric compound.
Maleimide unit or maleimide monomer have following structural formula among the present invention:
(R in the formula
nFor hydrogen or contain the alkyl of 1-15 carbon, cycloalkyl, substituted alkyl, aryl, substituted aryl)
Concrete example has: N-methyl maleimide, maleimide, N-ethyl maleimide, N-tertiary butyl maleimide, N-isobutyl-maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-aminomethyl phenyl maleimide, N-p-methoxy-phenyl maleimide, N-carboxyl phenyl maleimide, N-nitrophenyl maleimide, N-naphthyl maleimides etc., these maleimide monomers can be used alone or in combination.Wherein preferred N-cyclohexyl maleimide and N-phenylmaleimide.
Aryl ethylene class unit or aryl ethylene class monomer are the compounds that contains aryl hydrocarbon or substituted arene in the vinyl monomer.Mainly contain: vinylbenzene, right/adjacent/-vinyl toluene (being also referred to as Vinyl toluene), 1, the 3-dimethyl styrene, 2, the 4-dimethyl styrene, ethyl styrene is to tert-butylbenzene ethene, alpha-methyl styrene, α-ethyl styrene, Alpha-Methyl p-methylstyrene, halogenated styrenes, haloalkyl vinylbenzene, vinyl naphthalene or the like.The combination of one or more in these monomers all can be used.Optimization styrene wherein, Vinyl toluene.
Itrile group vinyl units or itrile group vinyl monomer are the compounds of nitrile group-containing in the vinyl monomer, mainly contain: vinyl cyanide, methacrylonitrile etc.
Among the present invention in the heat-resistant resin in maleimide class polymerization process used initiator be the used oil soluble thermal decomposition initiating of general radical polymerization, usually oil dissolubility thermal decomposition initiating is meant at the initiator of the half life of decomposition below 100 ℃ less than 4 hours, comprises azo class, organo-peroxide class.The object lesson of initiator has: Diisopropyl azodicarboxylate, and 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxides etc. can be one or more.Since be general general type, just no longer for example many.Wherein preferred Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).Initiator once adds, and oil-soluble conditioning agent also must add in (a), and emulsifying agent then must add aqueous phase.
The emulsifying agent that the present invention uses, mainly contain anion surfactant, nonionogenic tenside or their compound system, for example: sodium lauryl sulphate, dodecyl sulphate potassium, Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate, potassium stearate, synthetic fatty acid potassium, disproportionated rosin acid soap, anion surfactants such as sodium oleate, OP (alkylphenol polyoxyethylene), Tween, polyoxyethylene nonionogenic tensides such as Span, wherein preferably sodium dodecyl sulfate, disproportionated rosin acid soap, Sodium dodecylbenzene sulfonate or synthetic fatty acid potassium or their compound system.
The molecular weight regulator that the present invention uses is not particularly limited, as being general tert-dodecyl mercaptan, dodecyl mercaptan carbon etc.
The copolymer of the graftomer of the aryl ethylene of conjugated diene rubber grafting in the present invention class monomer and itrile group vinyl monomer (or claiming multipolymer), aryl ethylene class monomer and itrile group vinyl monomer all can adopt commercially available product or utilize mature industrial technology to obtain, can take methods such as CN1555398, CN1394216 to obtain as the graftomer of conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer, perhaps use present commercially available prod have GE 338, the high branch powder that glueds joint of ABS of Daqing petrochemical, Lanzhou petrochemical industry.Conjugated diene rubber latex, mainly be the homopolymer of conjugated diolefine and the multipolymer that can form with the monomer that it reacts, as polybutadiene latex, polyisoprene latex, polychloroprene latex, butadiene-styrene (wherein styrene content 3～10%) copolymer emulsion, butadiene-acrylonitrile (wherein acrylonitrile content 3～8%) copolymer emulsion, butadiene-acrylic acid butyl ester (wherein Butyl acrylate content 3～10%) copolymer emulsion etc., preferably polybutadiene latex.Among the present invention, used graft rubber latex is existing Industrial products on ripe production technology or the market, and preferably structural gel is 70～90%.The present invention is not limited the preparation method of conjugated diene rubber (as polybutadiene latex), the preparation method of common polybutadiene latex all can, but particle diameter is preferably between 260～400nm; The graft copolymer of conjugated diene rubber grafting aryl ethylene class monomer, itrile group vinyl monomer is Polybutadiene-acrylonitrile-vinylbenzene, butadiene-styrene copolymer-vinyl cyanide, polyisoprene-acrylonitrile-styrene graftomer (AIS), sovprene-acrylonitrile-styrene graftomer (ACS) etc. preferably, preferably Polybutadiene-acrylonitrile-styrene-grafted polymer A BS.
The copolymer of aryl ethylene class monomer and itrile group vinyl monomer can take methods such as CN1455786, CN85101103 to obtain, BHF, the CHF etc. that perhaps use present commercially available prod to have Lanzhou Petrochemical Company to produce.The copolymer of aryl ethylene class monomer and itrile group vinyl monomer is SAN, α-MSAN, styrene methacrylonitrile copolymer (SMAN) etc. preferably, its nitrile content is preferably in 22～35% (preferred 26～30%), and molecular weight is preferably in 60000～120000 (preferred 80000～100000).
The present invention also provides a kind of conjugated diene rubber grafting aryl ethylene class unit and the graft copolymer latex of itrile group vinyl units or preparation method of title emulsion of the suitable especially preparation present composition: the summation in conjugated diene rubber, aryl ethylene class monomer and itrile group vinyl monomer is 100 mass parts:
Under 25～35 ℃ with 35～60 parts particle diameter conjugated diene rubber latex at 260～400nm, 0.2～0.8 part of emulsifying agent, 0.1～0.6 part of pH buffer reagent, 0.1～0.5 part of complexing agent, 0.1～0.6 part is helped reductive agent, 120～200 parts of de-salted waters join in the reactor, begin to stir, the itrile group vinyl monomer that adds 2～6 parts then, 0.1～0.3 part oxygenant, 6～14 parts aryl ethylene class monomer and 0.1～0.5 part of molecular weight regulator join in the reactor, heat up after 5～15 minutes, be warmed up to 60～70 ℃ and add 0.01～0.05 part of reductive agent, begin reaction, 0.5 add 3～16.5 parts of itrile group vinyl monomers after～2.5 hours, 21～39 parts aryl ethylene class monomer and 0.1～0.3 part oxygenant.Record the graft latex transformation efficiency by the method for surveying dry-matter and finish reaction more than 95%, finish the copolymer emulsion of conjugated diene rubber grafting aryl ethylene class unit and itrile group vinyl units or the preparation of title emulsion.
Optimum condition:
Under 25～35 ℃ with 40～55 parts particle diameter conjugated diene rubber latex (in butt) at 300～350nm, 0.4～0.6 part of emulsifying agent, 0.2～0.5 part of pH buffer reagent, 0.2～0.4 part of complexing agent, 0.2～0.4 part is helped reductive agent, 150～180 parts of de-salted waters join in the reactor, begin to stir, the itrile group vinyl monomer that adds 3.0～6.0 parts then, 0.2～0.3 part oxygenant, 9～13.5 parts aryl ethylene class monomer and 0.2～0.5 part of molecular weight regulator join in the reactor, heat up after 5～15 minutes, be warmed up to 60 ℃ and add 0.01～0.03 part of reductive agent, begin reaction, 0.5 add 7.0～13.5 parts of itrile group vinyl monomers after～2.0 hours, 21～32 parts aryl ethylene class monomer and 0.2～0.3 part oxygenant.Record the graft latex transformation efficiency by the method for surveying dry-matter and finish reaction more than 95%, finish the copolymer emulsion of conjugated diene rubber grafting aryl ethylene class unit and itrile group vinyl units or the preparation of title emulsion.
Promptly can provide use with emulsion form among the present invention, also the graftomer emulsion of conjugated diene rubber grafting aryl ethylene class unit and itrile group vinyl units can be condensed, provide use after the drying the graftomer emulsion that generates conjugated diene rubber grafting aryl ethylene class unit and itrile group vinyl units.Dry auxiliary agent that uses of cohesion and usage quantity, condition are prior art, universal method.
Flocculation agent is the conventional flocculation agent that uses.Flocculation agent described in the present invention mainly contains sulfuric acid, calcium chloride, sal epsom, sodium-chlor, potassium aluminium sulfate, polymeric flocculant etc., preferably sulfuric acid magnesium.
Used oxygenant is the general oxygenant of redox system in the emulsion synthesis method of the conjugated diene rubber grafting aryl ethylene class monomer that provides among the present invention, the graft copolymer of itrile group vinyl monomer, as being hydrogen peroxide, hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide, tertbutyl peroxide, isopropyl benzene hydroperoxide, peroxidation 2,4 dichloro benzene formyl, 1,1-two (tert-butyl peroxy base) hexanaphthene etc., preferred hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide.Employed reductive agent in the invention, help reductive agent to be the general reductive agent of redox system, to help reductive agent, as using ferrous sulfate, sodium sulfoxylate formaldehyde, glucose, S-WAT, organism such as alcohol, amine, oxalic acid, preferably sulfuric acid is ferrous, glucose, sodium sulfoxylate formaldehyde.
Complexing agent also is the general complexing agent of redox system, as being sodium ethylene diamine tetracetate (EDTA), trisodium phosphate etc.; The pH buffer reagent also is general pH buffer reagent, as being yellow soda ash or sodium bicarbonate etc.
The present invention is not specially limited the preparation method of heat resistant resin composition, as adopting the most frequently used mixing method: each is formed blending, extruding pelletization and obtain.Certainly each is formed also and can the blending cohesion of partial tree fat liquor form elder generation dryly to obtain with the mode of other component mixing moulding again.Can adopt specifically and in latex of heat-resistant resin in maleimide class, add common agent such as softening agent, thermo-stabilizer etc., they can be mixed with the emulsion of auxiliary agent with emulsifying agent, de-salted water in emulsifying tank, the mode with emulsion after copolyreaction finishes adds.This emulsion can be carried out blend through the multipolymer of cohesion, dry back and graft copolymer, aryl ethylene class monomer and the itrile group vinyl monomer of conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer and be prepared heat resistant resin composition; Also the latex of heat-resistant resin in maleimide class that obtains directly can be mixed with the graft latex of conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer and carry out blend with the multipolymer of aryl ethylene class monomer and itrile group vinyl monomer again after condense altogether the back and prepare heat resistant resin composition.
The present invention also provides a kind of preparation method of this heat resistant resin composition, be specifically a kind of maleimide monomer and aryl ethylene class monomer or and the latex of heatresistant resin of itrile group vinyl monomer and the graftomer emulsion of conjugated diene rubber grafting aryl ethylene class monomer and the itrile group vinyl monomer copolymer that carries out common cohesion, dry back and aryl ethylene class monomer and itrile group vinyl monomer carry out the method that blend prepares heat resistant resin composition:
Latex of heat-resistant resin in maleimide class is mixed with the graftomer emulsion of conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer and the emulsion of 0.8～1.2 part of auxiliary agent, 100 parts of these mixed emulsions are under agitation joined temperature continuously under 25～35 ℃ be in 60～70 ℃ 100～500 part 2～8 ‰ the aqueous solution that contains flocculation agent, added in 30～45 minutes.After emulsion adds mixed solution is warming up to 90～100 ℃ and keeps and to lower the temperature in 1～1.5 hour, finish agglomeration process.Condense the slurry that and wash after drying with de-salted water after filtration, standby.With heat-resistant resin in maleimide class after 65～95 parts of oven dry and conjugated diolefine graft polymer mixture, with 5～35 parts aryl ethylene class monomer and the blend of itrile group vinyl monomer copolymer, blend can obtain the heat resistant resin composition product through twin screw extruder.
Among the present invention, do not get rid of during the composition blending and add other common agent, as oxidation inhibitor, softening agent, lubricant, fire retardant or the like.Oxidation inhibitor can be 1010,1076,2246 etc., and softening agent can be Magnesium Stearate, DOP, DDP etc., and lubricant can be silicone oil, EBS etc., and its consumption and ratio are all same as the prior art, to kind, add-on the present invention of auxiliary agent and have no special requirements.The consumption of various common agents is generally about 0.1～0.5 part, is 0.2～0.5 part as oxidation inhibitor, and 0.2～0.5 part in softening agent, lubricant are 0.2～0.5 part.Be preferably in during blend and mix 3～5min in the high speed mixing machine (1300～1500 rev/mins, as follows).
Heat resistant resin composition of the present invention and preparation method's characteristics are as follows:
1. the synthetic method of latex of heat-resistant resin in maleimide class of the present invention has thoroughly solved the instability of emulsion, problems such as pH reduces and emulsion variable color, precipitate be more.Polyreaction is very easily controlled, and reaction process is highly stable, and polymerization finishes not have substantially precipitate and produces.The polymerization reaction monomer transformation efficiency is more than 95%, and the solids that emulsion filtered out after reaction finished and the ratio of total monomer charging capacity are lower than 1.0%.The second-order transition temperature test result of product only shows a second-order transition temperature value, illustrates that its structural homogeneity is good.
2. the method that heat resistant resin composition of the present invention adopts latex of heatresistant resin and conjugated diene rubber graft copolymer emulsion to condense has altogether solved the difficult problem that latex of heatresistant resin particle in agglomeration process is thin, yield is low.
3. the conjugated diene rubber graft copolymer of the present invention's preparation has been adjusted the particle diameter of graft base latex, the nitrile content in the graftomer, the structural parameter such as glue content of graftomer according to the structure and the performance characteristics of heat stable resin, and making it has good consistency with heat stable resin.
4. with the preparation method of heat resistant resin composition of the present invention, it is good that the heat resistant resin composition that makes has outward appearance, and the advantage that thermal stability is high is the good heat-stable material of a kind of performance.The heat stable resin of preparation can be widely used in the heat resistance modified aspect to materials such as ABS, PC, PBT.As a kind of material of fine heat-resisting performance, its independent use also can be used for preparing automobile, the high heat-stable component of household electrical appliances.
Embodiment
Following examples are to specify of the present invention, and wherein reactor reacts in water-bath for three mouthfuls of glass flask of band stirring, condenser, thermometer; The end opening glass flask that tempering tank stirs for band.Hereinafter " % ", " part " all refers to weight percentage or parts by weight, molecular weight refers to weight-average molecular weight.
Second-order transition temperature Tg:DSC-differential thermal differential method
Vicat softening temperature: GB/T 1633-2000
GPC：W-150C
Nitrile content: GB/T 4486-84
Melt flow rate (MFR) (g/10min): 3682-2000
Cantilever beam impact strength (KJ/m
2): GB/T 1843-1996
Resin emulsion whether weighed by variable color after certain hour is weighed and placed to the solids that emulsion filtered out after resin emulsion stability finished with reaction and the ratio magnitude of total monomer charging capacity.
The preparation of the emulsion of auxiliary agent: the emulsion that under 75 ℃, 5.0% oleic acid potash soap, 10% antioxidant 1076,5% plasticizer phthalic acid dibutylester and 80% de-salted water is mixed with auxiliary agent in emulsifying tank.
Blending auxiliary agent: lubricant EBS: antioxidant 1010: the weight ratio of softening agent Magnesium Stearate is 1: 2: 1.
Embodiment:
The preparation of A1:
A) preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B) preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 3.0 parts of sodium lauryl sulphate join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).Measuring its pH is 9～10.
C) preparation of latex of heatresistant resin
Add 30 parts of water in the reactor, treat that its temperature rises to after 79 ℃, immediately (b) joined continuously equably in the reactor also the temperature of maintenance system and under 80 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9.
In (c), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion (≤1.5% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.2%, and is qualified.
Calculated yield 95.3% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=140 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 147 ℃.
The preparation of A2:
A) preparation of monomer mixed solution
30 ℃ with 45 parts of N-phenylmaleimides, 55 parts of alpha-methyl styrenes, and 0.45 part of 2,2'-Azobis(2,4-dimethylvaleronitrile), 0.15 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B) preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 3.4 parts of Sodium dodecylbenzene sulfonatees join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).Measuring its pH is 9～10.
C) preparation of latex of heatresistant resin
Add 30 parts of water in the reactor, treat that its temperature rises to after 80 ℃, immediately (b) joined continuously equably in the reactor also the temperature of maintenance system and under 90 ℃, carry out polyreaction.The feed rate of control (b) added it within 3.5～4.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.2%, and is qualified.
Calculated yield 95.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=177 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 157 ℃.
The preparation of A3:
A) preparation of monomer mixed solution
32 ℃ with 10 parts of N-cyclohexyl maleimides, 65 parts of vinylbenzene, and 25 parts of methacrylonitriles, 0.35 part of Diisopropyl azodicarboxylate, 0.2 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B) preparation of monomer emulsion
32 ℃ with 130 parts of de-salted waters, and 1.7 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).Measuring its pH is 9～10.
C) preparation of latex of heatresistant resin
Add 30 parts of water in the reactor, treat that its temperature rises to after 73 ℃, (b) divided 4 times, add 25% at every turn, join in the reactor and to mix also the temperature of maintenance system with (a) and under 75 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.1%, and is qualified.
Calculated yield 95.3% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=117 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 108 ℃.
The preparation of A4:
A) preparation of monomer mixed solution
25 ℃ with 25 parts of N-phenylmaleimides, 50 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Diisopropyl azodicarboxylate, 0.22 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B) preparation of monomer emulsion
25 ℃ with 130 parts of de-salted waters, and 2.3 parts of sodium lauryl sulphate and 1.0 parts of synthetic fatty acid potassium join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).Measuring its pH is 9～10.
C) preparation of latex of heatresistant resin
Add 30 parts of water in the reactor, treat that its temperature rises to after 79 ℃, immediately (b) joined continuously equably in the reactor and to mix also the temperature of maintenance system with (a) and under 80 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9, adds the emulsion of auxiliary agent at last, is all processes of finishing preparation (c).
Emulsion in the reactor, after filtration, filtrate latex of heatresistant resin, this emulsion is placed nondiscoloration in 120 hours.The solids that filters out is weighed after the drying, as the criterion of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.3%, and is qualified.
Calculated yield 95.3% after the product that emulsion makes after cohesion, filtration, drying is weighed.Get second-order transition temperature Tg=133 ℃ with differential differential thermal instrumentation.Record its vicat softening temperature: 124 ℃.
The preparation of B1
Under 30 ℃ with the polybutadiene latex of 35 parts particle diameter 330nm, 0.7 part sodium lauryl sulphate, 0.1 part yellow soda ash, 0.1 part EDTA, 0.5 part glucose, 190 parts of de-salted waters join in the reactor, begin to stir, and add 6 parts vinyl cyanide then, 0.30 the hydrogen phosphide cumene of part, 13.5 vinylbenzene and 0.45 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 10 minutes, are warmed up to 60 ℃ and add 0.041 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 13.5 parts of vinyl cyanide after 1.5 hours in the system, the hydrogen phosphide cumene of 32 parts vinylbenzene and 0.25 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABS graft copolymer.The grafting efficiency 50% of the ABS graft copolymer that obtains, the molecular weight 6.2 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B2
Under 28 ℃ with styrene-butadiene copolymer (styrene content 5%) latex of 45 parts particle diameter 290nm, 0.5 part Sodium dodecylbenzene sulfonate, 0.4 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.4 part sodium sulfoxylate formaldehyde, 190 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 4.4 parts then, 0.30 the di-isopropylbenzene hydroperoxide of part, 13.5 vinylbenzene and 0.45 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 5 minutes, are warmed up to 60 ℃ and add 0.028 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, treat to add after 1.5 hours 11 parts of vinyl cyanide in the system, the di-isopropylbenzene hydroperoxide of 26.1 parts vinylbenzene and 0.25 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABS graft copolymer.The grafting efficiency 49% of the ABS graft copolymer that obtains, the molecular weight 7.1 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B3
Under 35 ℃ with styrene-butadiene copolymer (styrene content 10%) latex of 50 parts particle diameter 380nm, 0.2 part Sodium dodecylbenzene sulfonate and 0.3 part of disproportionated rosin acid soap, 0.5 part sodium bicarbonate, 0.6 part trisodium phosphate, 0.2 part glucose, 120 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 4.1 parts then, 0.10 the di-isopropylbenzene hydroperoxide of part, 12.4 vinylbenzene and 0.50 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 10 minutes, are warmed up to 60 ℃ and add 0.05 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 9.7 parts of vinyl cyanide after 2.5 hours in the system, the di-isopropylbenzene hydroperoxide of 23.8 parts vinylbenzene and 0.30 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABS graft copolymer.The grafting efficiency 51% of the ABS graft copolymer that obtains, the molecular weight 7.3 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B4
Under 28 ℃ with the polybutadiene latex of 45 parts particle diameter 330nm, 0.3 part Sodium dodecylbenzene sulfonate and 0.5 part of synthetic fatty acid potassium, 0.6 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.3 part glucose, 200 parts of de-salted waters join in the reactor, begin to stir, and add 3.3 parts vinyl cyanide then, 0.15 the di-isopropylbenzene hydroperoxide of part, 13.2 vinylbenzene and 0.40 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 15 minutes, are warmed up to 60 ℃ and add 0.012 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 7.7 parts of vinyl cyanide after 1.5 hours in the system, the di-isopropylbenzene hydroperoxide of 30.8 parts vinylbenzene and 0.25 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABS graft copolymer.The grafting efficiency 52% of the ABS graft copolymer that obtains, the molecular weight 7.9 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B5
Under 25 ℃ with acrylonitrile butadiene copolymer (the containing vinyl cyanide 5%) latex of 45 parts particle diameter 360nm, 0.5 part Sodium dodecylbenzene sulfonate, 0.4 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.4 part sodium sulfoxylate formaldehyde, 160 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 4.4 parts then, 0.15 the di-isopropylbenzene hydroperoxide of part, 13.5 vinylbenzene and 0.20 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 7 minutes, are warmed up to 60 ℃ and add 0.045 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 11 parts of vinyl cyanide after 1.5 hours in the system, the di-isopropylbenzene hydroperoxide of 26.1 parts vinylbenzene and 0.24 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABS graft copolymer.The grafting efficiency 50% of the ABS graft copolymer that obtains, the molecular weight 10.5 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B6
Under 30 ℃ with butyl acrylate-butadienecopolymer (containing butyl acrylate 5%) latex of 45 parts particle diameter 350nm, 0.6 part Sodium dodecylbenzene sulfonate, 0.35 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.5 part glucose, 160 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 4.1 parts then, 0.18 the di-isopropylbenzene hydroperoxide of part, 12.4 vinylbenzene and 0.35 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 13 minutes, are warmed up to 60 ℃ and add 0.022 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 9.7 parts of vinyl cyanide after 1.0 hours in the system, the di-isopropylbenzene hydroperoxide of 28.8 parts vinylbenzene and 0.25 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABS graft copolymer.The grafting efficiency 54% of the ABS graft copolymer that obtains, the molecular weight 8.3 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B7
Under 30 ℃ with the polybutadiene latex of 55 parts particle diameter 340nm, 0.6 part Sodium dodecylbenzene sulfonate, 0.4 part sodium bicarbonate, 0.24 part trisodium phosphate, 0.34 part glucose, 140 parts of de-salted waters join in the reactor, begin to stir, and add 4.0 parts vinyl cyanide then, 0.15 the di-isopropylbenzene hydroperoxide of part, 9.6 vinylbenzene and 0.22 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 6 minutes, are warmed up to 60 ℃ and add 0.040 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 9.0 parts of vinyl cyanide after 0.5 hour in the system, the di-isopropylbenzene hydroperoxide of 22.4 parts vinylbenzene and 0.26 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABS graft copolymer.The grafting efficiency 53% of the ABS graft copolymer that obtains, the molecular weight 10.4 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B8
Under 35 ℃ with the polybutadiene latex of 60 parts particle diameter 320nm, 0.3 part Sodium dodecylbenzene sulfonate, 0.3 part sodium bicarbonate, 0.21 part trisodium phosphate, 0.20 part glucose, 145 parts of de-salted waters join in the reactor, begin to stir, and add 3.0 parts vinyl cyanide then, 0.13 the di-isopropylbenzene hydroperoxide of part, 9.0 vinylbenzene and 0.39 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 14 minutes, are warmed up to 60 ℃ and add 0.020 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 7.0 parts of vinyl cyanide after 1.5 hours in the system, the di-isopropylbenzene hydroperoxide of 21 parts vinylbenzene and 0.18 part.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of ABS graft copolymer.The grafting efficiency 59% of the ABS graft copolymer that obtains, the molecular weight 7.1 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
B9: the Ge338 that commercially available GE company produces
C1: commercially available SAN, the trade mark: BHF, index: in conjunction with nitrile content 25.3%
C2: commercially available SAN, the trade mark: HH, index: in conjunction with nitrile content 28.1%
C3: commercially available SAN, the trade mark: HH-C300, index: in conjunction with nitrile content 30.2%
Embodiment 1:
Latex of heatresistant resin A1 is mixed according to 10: 55: 0.82 ratio with the emulsion of ABS emulsion B1 and auxiliary agent, with 100 parts of these mixed emulsions under 25 ℃, under agitation join temperature continuously and be in 65 ℃ the aqueous solution of 300 part 5 ‰ sal epsom, keep uniform feed rate and in 30～35 minutes, add.After emulsion adds mixed solution is warming up to 95 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, promptly become A1 and B1 mixture.With A1 after 65 parts of oven dry and B1 mixture, with 35 parts C3,0.80 part blending auxiliary agent the high speed mixing machine (1400 rev/mins, mixing machine 3 minutes, down with) in mix.Blend can obtain the heat resistant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 2:
Latex of heatresistant resin A2 is mixed according to 25: 50: 0.80 ratio with the emulsion of ABS emulsion B1 and auxiliary agent, 100 parts of these mixed emulsions are under agitation joined temperature continuously under 30 ℃ be in 60 ℃ the aqueous solution of 100 part 2 ‰ sal epsom, keeps uniform feed rate and added in 30～35 minutes.After emulsion adds mixed solution is warming up to 97 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.With A1 after 75 parts of oven dry and B1 mixture, with 25 parts C1,0.80 part blending auxiliary agent mixes in the high speed mixing machine.Blend can obtain the heat resistant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 3:
Latex of heatresistant resin A3 is mixed according to 35: 40: 1.20 ratio with the emulsion of ABS emulsion B1 and auxiliary agent, 100 parts of these mixed emulsions are under agitation joined temperature continuously under 30 ℃ be in 70 ℃ the aqueous solution of 500 part 8 ‰ sal epsom, keeps uniform feed rate and added in 30～35 minutes.After emulsion adds mixed solution is warming up to 100 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.With A1 after 75 parts of oven dry and B1 mixture, with 25 parts C3,0.80 part blending auxiliary agent mixes in the high speed mixing machine.Blend can obtain the heat resistant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 4:
Latex of heatresistant resin A1 is mixed according to 45: 40: 1.20 ratio with the emulsion of ABS emulsion B2 and auxiliary agent, 100 parts of these mixed emulsions are under agitation joined temperature continuously under 35 ℃ be in 70 ℃ the aqueous solution of 300 part 8 ‰ sal epsom, keeps uniform feed rate and added in 30～35 minutes.After emulsion adds mixed solution is warming up to 100 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.With A1 after 85 parts of oven dry and B1 mixture, with 15 parts C3,0.80 part blending auxiliary agent mixes in the high speed mixing machine.Blend can obtain the heat resistant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 5～8, and just the kind of A, B, C and consumption see Table 2 listedly, and other are identical with embodiment 4.
Embodiment 9:
100 parts of latex of heatresistant resin A1 under 35 ℃, are under agitation joined temperature continuously and are in 70 ℃ the aqueous solution of 350 part 6 ‰ sal epsom, keep uniform feed rate and in 30～35 minutes, add.After emulsion adds mixed solution is warming up to 100 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.
With the A1 after 55 parts of oven dry and 30 parts of commercially available ABS height splicing branch part B9, C3 of 15 parts, 0.80 part blending auxiliary agent mixes in the high speed mixing machine.Blend can obtain the heat resistant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 10:
100 parts of latex of heatresistant resin A1 under 35 ℃, are under agitation joined temperature continuously and are in 70 ℃ the aqueous solution of 450 part 4 ‰ sal epsom, keep uniform feed rate and in 30～35 minutes, add.After emulsion adds mixed solution is warming up to 100 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.
100 parts of ABS emulsion B6 under 25 ℃, are under agitation joined temperature continuously and are in 63 ℃ the aqueous solution of 350 part 5 ‰ sal epsom, keep uniform feed rate and in 30～35 minutes, add.After emulsion adds mixed solution is warming up to 96 ℃ and keeps and to lower the temperature in 1 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.
With ABS grafting powder B6,5 parts C3 after the A1 after 65 parts of oven dry and the 30 parts of oven dry, 0.80 part blending auxiliary agent mixes in the high speed mixing machine.Blend can obtain the heat resistant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 11,12, and just the kind of A, B, C and consumption see Table 2 listedly, and other are identical with embodiment 10.
The performance perameter of table 1 C,
[0154]Table 2 embodiment heat resistant resin composition blend prescription and The performance test results
Comparative Examples:
A
01 preparation:
A) preparation of monomer mixed solution
30 ℃ with 30 parts of N-phenylmaleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.35 part of Potassium Persulphate, 0.1 part of tert-dodecyl mercaptan adds tempering tank, opens to stir and mixes, and forms homogeneous phase monomer mixed solution (a).
B) preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 3.0 parts of sodium lauryl sulphate join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).Measuring its pH is 9～10.
C) preparation of latex of heatresistant resin
Add 30 parts of water in the reactor, treat that its temperature rises to after 79 ℃, immediately (b) joined continuously equably in the reactor also the temperature of maintenance system and under 80 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9.
In (c), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (c).
A
02 preparation:
A) preparation of monomer emulsion
30 ℃ with 130 parts of de-salted waters, and 3.0 parts of sodium lauryl sulphate join in the emulsor, open to stir (a) joined and carry out emulsification in the emulsor.Emulsification 30～45 minutes monomer emulsion (b).Measuring its pH is 9～10.
B) preparation of latex of heatresistant resin
Add 30 parts of water in the reactor, treat that its temperature rises to after 79 ℃, immediately (b) joined continuously equably in the reactor also the temperature of maintenance system and under 80 ℃, carry out polyreaction.The feed rate of control (b) added it within 4.5～5.0 hours.(b) add after, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content promptly forms latex of heatresistant resin (c) after qualified.(c) after polymerization finished, measuring its pH was about 9.
In (c), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (c).
Comparative Examples B
0Synthetic:
B
01 preparation
Under 25 ℃ with the polybutadiene latex of 35 parts particle diameter 320nm, 0.8 part sodium lauryl sulphate, 0.1 part yellow soda ash, 0.1 part EDTA, 0.6 part glucose, 200 parts of de-salted waters join in the reactor, begin to stir, the hydrogen phosphide cumene that adds 0.30 part then, 19.4 parts vinylbenzene and 0.45 part of tert-dodecyl mercaptan join in the reactor, heat up after 10 minutes, be warmed up to 60 ℃ and add 0.041 part of ferrous sulfate, begin reaction, because exothermic heat of reaction begins to heat up, add 45.6 parts vinylbenzene and 0.25 part hydrogen phosphide cumene after 1.5 hours in the system.Constant temperature is 1 hour when treating that system temperature rises to 75 ℃, records the graft latex transformation efficiency by the method for surveying dry-matter and finishes 95% or more to react, and finishes the preparation of graft copolymer.The grafting efficiency 50% of the ABS graft copolymer that obtains.
Table 3 comparative example heat resistant resin composition blend prescription and The performance test results
Claims (16)
1. heat resistant resin composition, it is characterized in that: in heat resistant resin composition is 100 mass parts, contain: 10～65 parts of A. heat-resistant resin in maleimide class, the maleimide unit accounts for 10～45 quality % in the heat-resistant resin in maleimide class, aryl ethylene class unit accounts for 30～65 quality %, and the itrile group vinyl units accounts for 0～30 quality %; B. the graftomer of conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer is 30～55 parts, conjugated diene rubber accounts for 35～60 quality % in the graftomer, aryl ethylene class unit accounts for 27～53 quality %, and the itrile group vinyl units accounts for 5～22.5 quality %; C. the copolymer of aryl ethylene class monomer and itrile group vinyl monomer is 5～35 parts, and aryl ethylene class unit accounts for 65～78 quality % in the copolymer, and the itrile group vinyl units accounts for 22～35 quality %; Wherein the emulsion of heat-resistant resin in maleimide class is to obtain by the following method, is 100 mass parts in its polymerization single polymerization monomer total amount:
(a) preparation of monomer mixed solution
25～35 ℃ with 10～45 parts of maleimide monomers, 30～65 parts of aryl ethylene class monomers, 0～30 part of itrile group vinyl monomer, 0.1～0.6 part of oil soluble thermal decomposition initiating, 0.01～0.65 part of molecular weight regulator adds tempering tank, open to stir and mix, form homogeneous phase monomer mixed solution (a);
(b) preparation of monomer emulsion
25～35 ℃ with 80～150 parts of de-salted waters, and 2.0～8.5 parts of emulsifying agents join in the emulsor, open to stir monomer mixed solution (a) joined and carry out emulsification in the emulsor, emulsification 20～75 minutes monomer emulsion (b);
(c) preparation of latex of heatresistant resin
In being housed, the reactor of whipping appts adds 10～50 parts of de-salted waters, temperature is raised to after 60～80 ℃, within 3～8 hours, in batches or continuously join in reactor more than 3 batches monomer emulsion (b), and the temperature of maintenance system is carried out polyreaction under 60～90 ℃, after monomer emulsion (b) adds, polyreaction was carried out 0.5～2.0 hour again, promptly formed latex of heatresistant resin (c).
2. heat resistant resin composition according to claim 1, it is characterized in that aryl ethylene class unit or aryl ethylene class monomer are selected from vinylbenzene, Vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, in tert-butylbenzene ethene, alpha-methyl styrene, halogenated styrenes, haloalkyl vinylbenzene, the vinyl naphthalene one or more.
3. heat resistant resin composition according to claim 1 is characterized in that itrile group vinyl units or itrile group vinyl monomer are selected from one or more in vinyl cyanide, the methacrylonitrile.
4. heat resistant resin composition according to claim 1, it is characterized in that maleimide unit or maleimide monomer are selected from N-methyl maleimide, maleimide, the N-ethyl maleimide, N-tertiary butyl maleimide, N-isobutyl-maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-aminomethyl phenyl maleimide, N-p-methoxy-phenyl maleimide, N-carboxyl phenyl maleimide, N-nitrophenyl maleimide, one or more in the N-naphthyl maleimide.
5. heat resistant resin composition according to claim 1 is characterized in that emulsifying agent is anion surfactant, nonionogenic tenside or their compound system.
6. heat resistant resin composition according to claim 5, it is characterized in that emulsifying agent is selected from sodium lauryl sulphate, dodecyl sulphate potassium, Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate, potassium stearate, synthetic fatty acid potassium, disproportionated rosin acid soap, one or more in sodium oleate, the polyoxyethylene nonionogenic tenside.
7. heat resistant resin composition according to claim 1 is characterized in that molecular weight regulator is tert-dodecyl mercaptan or dodecyl mercaptan carbon.
8. heat resistant resin composition according to claim 1 is characterized in that the oil soluble thermal decomposition initiating is selected from one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the benzoyl peroxide.
9. heat resistant resin composition according to claim 1, the copolymer molecular weight that it is characterized in that aryl ethylene class monomer and itrile group vinyl monomer is 60000～120000.
10. heat resistant resin composition according to claim 1 is characterized in that conjugated diene rubber comes from polybutadiene latex, polyisoprene latex, polychloroprene latex, butadiene-styrene copolymer latex, perbutan latex or butadiene-acrylic acid butyl ester copolymer emulsion.
11. the preparation method of the described heat resistant resin composition of claim 1, it is characterized in that latex of heat-resistant resin in maleimide class is mixed with the graftomer emulsion of conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer and the emulsion of 0.8～1.2 part of auxiliary agent, 100 parts of these mixed emulsions are under agitation joined temperature continuously under 25～35 ℃ be in 60～70 ℃ 100～500 part 2～8 ‰ the aqueous solution that contains flocculation agent, in 30～45 minutes, add, after emulsion adds mixed solution being warming up to 90～100 ℃ keeps and can lower the temperature in 1～1.5 hour, finish agglomeration process, condense the slurry that and wash after drying with de-salted water after filtration; With 65～95 parts of heat-resistant resin in maleimide class and conjugated diolefine graft polymer mixture, with 5～35 parts aryl ethylene class monomer and the blend of itrile group vinyl monomer copolymer, blend can obtain the heat resistant resin composition product through twin screw extruder.
12. the preparation method of heat resistant resin composition according to claim 11, it is characterized in that conjugated diene rubber grafting aryl ethylene class monomer, the emulsion preparation method of the graft copolymer of itrile group vinyl monomer: use the redox system initiator, with conjugated diene rubber, the summation of aryl ethylene class monomer and itrile group vinyl monomer is 100 mass parts meters, under 25～35 ℃ with 35～60 parts particle diameter conjugated diene rubber latex at 260～400nm, 0.2～0.8 part of emulsifying agent, 0.1～0.6 part of pH buffer reagent, 0.1～0.5 part of complexing agent, 0.1～0.6 part is helped reductive agent, 120～200 parts of de-salted waters join in the reactor, begin to stir, the itrile group vinyl monomer that adds 2～6 parts then, 0.1～0.3 part oxygenant, 6～14 parts aryl ethylene class monomer and 0.1～0.5 part of molecular weight regulator are in reactor, heat up after 5～15 minutes, be warmed up to 60～70 ℃ and add 0.01～0.05 part of reductive agent, begin reaction, 0.5 add 3～16.5 parts of itrile group vinyl monomers after～2.5 hours, 21～39 parts aryl ethylene class monomer and 0.1～0.3 part oxygenant, graft latex transformation efficiency finish reaction more than 95%.
13. the preparation method of heat resistant resin composition according to claim 11, the emulsion that it is characterized in that described auxiliary agent is mixed with softening agent, thermo-stabilizer, emulsifying agent and de-salted water in emulsifying tank, softening agent in the emulsion of auxiliary agent: thermo-stabilizer: emulsifying agent: the weight ratio of water is (1～5): (1～5): (3～10): (80～200).
14., it is characterized in that emulsifying agent is one or more in potassium stearate, potassium oleate, the synthetic fatty acid potassium according to the preparation method of claim 12 or 13 described heat resistant resin compositions.
15. the preparation method of heat resistant resin composition according to claim 11 is characterized in that flocculation agent is selected from one or more in calcium sulfate, calcium chloride, sal epsom, sodium-chlor, potassium aluminium sulfate, the polymeric flocculant.
16. the preparation method of heat resistant resin composition according to claim 12 is characterized in that the pH buffer reagent is yellow soda ash or sodium bicarbonate.
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|---|---|---|---|---|
| US4381373A (en) * | 1980-12-11 | 1983-04-26 | Mitsubishi Monsanto Chemical Company | Heat resistant resin composition |
| US4757109A (en) * | 1985-05-16 | 1988-07-12 | Mitsubishi Rayon Co., Ltd. | Process for the preparation of maleimide copolymers and thermoplastic resin composition using the same |
| CN1126734A (en) * | 1994-05-27 | 1996-07-17 | 电气化学工业株式会社 | Process for producing a maleimide-modified heat-resistant ABS resin |
| CN1982346A (en) * | 2005-12-16 | 2007-06-20 | 中国石油天然气股份有限公司 | Production of maleimide resin emulsion |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4381373A (en) * | 1980-12-11 | 1983-04-26 | Mitsubishi Monsanto Chemical Company | Heat resistant resin composition |
| US4757109A (en) * | 1985-05-16 | 1988-07-12 | Mitsubishi Rayon Co., Ltd. | Process for the preparation of maleimide copolymers and thermoplastic resin composition using the same |
| CN1126734A (en) * | 1994-05-27 | 1996-07-17 | 电气化学工业株式会社 | Process for producing a maleimide-modified heat-resistant ABS resin |
| CN1982346A (en) * | 2005-12-16 | 2007-06-20 | 中国石油天然气股份有限公司 | Production of maleimide resin emulsion |
Non-Patent Citations (1)
| Title |
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| JP特开2003-327777A 2003.11.19 |
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