CN101503542B - Heat resisting flame retardant resin composition and preparation thereof - Google Patents
Heat resisting flame retardant resin composition and preparation thereof Download PDFInfo
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Abstract
The invention provides a halogen substituent maleimide heat-resistant flame-retardant resin composition and a preparation method thereof. Based on 100 parts by weight, the resin composition comprises 10-65 parts of halogen substituent maleimide heat-resistant flame-retardant resin, 30-55 parts of a graft polymer of a conjugated diene rubber graft aryl ethylene unit and a nitrile vinyl unit and 5-35 parts of a binary copolymer of aryl ethylene monomers and nitrile vinyl monomers. The halogen substituent maleimide heat-resistant flame-retardant resin composition prepared by the method has the advantages of flame retardation and high heat resistance, and the resin composition is a heat-resistant flame-retardant material with excellent properties. The prepared heat-resistant flame-retardant resin can be widely used for modifying heat resistance and flame retardance of such materials as ABS, PC, PBT and the like. As a material with excellent heat-resistant and flame-retardant properties, the resin composition can be used alone for preparing high heat-resistant and flame-retardant parts of automobiles and household electrical appliances.
Description
Technical field
The present invention relates to a kind of heat resisting flame retardant resin composition and preparation method's, particularly a kind of maleimide heat resisting composition containing halogen substituent preparation method.
Background technology
The monomeric free-radical polymerized thing of halogen substituent 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, simultaneously because of containing halogen on its molecular chain, on stable on heating basis, have good flame retardancy again, thereby be subjected to extensive concern.
The preparation of heat-proof combustion-resistant 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 halogen substituent maleimide (XMI) with the monomeric terpolymer of halogen substituent maleimide (XSMIA) 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 halogen substituent maleimide is the stable on heating assurance of heat-proof combustion-resistant ABS resin, and the ABS graft copolymer is determining the balance of its over-all properties.
The synthetic of XSMIA then can be adopted various polymerization processs such as body, suspension, emulsion and solution polymerization.Halogen substituent maleimide monomer and AEM and or NEM and three's copolyreaction have and the general different characteristics of copolyreaction, polymerization rate is very fast, 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 halogen substituent 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 (methyl methacrylate) 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-PMI 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 pH value is 3～9 scopes, initiator adopts redox system or Potassium Persulphate initiator, when this patent is pointed out with the Potassium Persulphate 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, employing be used water soluble starter of typical letex polymerization or redox initiation system.
CN101007894 " PBT and ABS fire retardant material " adopts fire retardant to prepare a kind of PBT and ABS fire retardant material; CN1962751 " a kind of heat-proof combustion-resistant ABS resin and preparation method thereof " discloses a kind of method that adopts fire retardant to prepare heat-proof combustion-resistant ABS resin; CN1412238 " fire-resisting ABS special-purpose material " prepares heat-proof combustion-resistant ABS resin by the method for polyvinyl chloride, decabromodiphenyl oxide, antimonous oxide, properties-correcting agent chlorinatedpolyethylene, stablizer, lubricant and ABS resin blend.
KR20040047992 has described a kind of preparation method of heat resistant resin composition, and wherein the fire retardant of Cai Yonging is the halogenated compound of weight-average molecular weight at 2000-10000; KR950002892B has described a kind of employing tetrabromo-bisphenol, and decabromodiphenyl oxide prepares the method for heat resisting flame retardant resin composition; KR930004282B has described a kind of bromostyrene and has done the method that comonomer prepares the ABS heat resisting and flame-retardant alloy; JP8108137 has described a kind of patented method of utilizing the blend of small molecules fire retardant to prepare maleimide modified styrene resin/PC/ABS flame-proof heat-resistant alloy; JP3146542 has described a kind of by carrying out the method that blend prepares the flame-proof heat-resistant resin combination with PVC; JP63039953 has described and has a kind ofly prepared fire-retardant by carrying out blend with PVC and bromo dihydroxyphenyl propane; JP62143960 has described a kind of CPVC of utilization and has carried out the method that blend prepares the heat-proof combustion-resistant heat-resistant composition; JP63081152 has described a kind of method by mass polymerization and has prepared bromo maleimide and cinnamic multipolymer, carries out blend with bromo aryl organic fire-retardant ABS then, preparation heat-proof combustion-resistant method for compositions.
More than these patented methods, adopt small molecules fire retardant or small molecules halogen containing flame-retardant, in various degree exist the auxiliary agent transport phenomena, the heat-proof combustion-resistant performance is not good, prepares the shortcoming that alloy exists poor heat stability again with PVC or CPVC.
In order to obtain the good heat-proof combustion-resistant composition of over-all properties, need the suitable glue content of preparation conjugated diene rubber grafting aryl ethylene class monomer and or the grafting powder of itrile group vinyl monomer, and to preparation conjugated diene rubber grafting aryl ethylene class monomer and or the particle diameter and the gel of the graft base latex of the grafting powder of itrile group vinyl monomer higher requirement is arranged, factors such as grafted monomer proportioning, molecular weight also all can produce considerable influence to the final performance of heat-proof combustion-resistant composition.
The contriver attempts to seek a kind of under the situation of comparatively convenient, easy handling, synthesize and in the monomer ratio scope of broad, can obtain forming the relatively heat-proof flame-proof resin XSMIA multipolymer of homogeneous that distributes, and by the synthetic conjugated diene rubber grafting aryl ethylene class monomer that is complementary with it and or the graft latex of itrile group vinyl monomer, then graft latex and heat-proof flame-proof resin emulsion carry out common cohesion, dry back and aryl ethylene class monomer and or the multipolymer of the itrile group vinyl monomer method of carrying out blend obtain the good heat resisting flame retardant 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 resisting flame retardant resin composition and preparation method.
Heat resisting flame retardant resin composition of the present invention, in heat resisting flame retardant resin composition is 100 mass parts, contain: 10～65 parts of A. halogen substituent maleimide heat-proof flame-proof resins, the halogen substituent maleimide unit accounts for 10～45 quality % in the halogen substituent maleimide heat-proof flame-proof resin, aryl ethylene class unit accounts for 30～65 quality %, and the itrile group vinyl units accounts for 1～25 quality %; B. the graftomer of conjugated diene rubber grafting aryl ethylene class unit 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 20～60 quality %, and the itrile group vinyl units accounts for 5～20 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 halogen substituent maleimide heat-proof resin 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
In 25～35 ℃ with 10～45 parts of halogen substituent maleimide monomers, 30～65 parts of aryl ethylene class monomers, 1～25 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: in 25～35 ℃ with 15～45 parts of halogen substituent maleimide monomers, 35～60 parts of aryl ethylene class monomers, 0.2～0.5 part of oil soluble thermal decomposition initiating, 1～25 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 heat-proof flame-proof resin emulsion
With 100～200 parts of de-salted waters, 2.0～10.0 parts of emulsifying agents join in the reactor that whipping appts is housed in 25～35 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.Emulsification can heat up and carry out polymerization in 20～75 minutes.The temperature of maintenance system was carried out polyreaction 3～8 hours under 55～95 ℃.System temperature is risen to 90～100 ℃ then, polyreaction was carried out 0.5～2.0 hour again, the sampling and measuring total solid content, and qualified back (〉=37%, as follows) promptly forms heat-proof flame-proof resin emulsion (b).
Optimum condition is: with 140～180 parts of de-salted waters, 2.5～8.5 parts of emulsifying agents join in the reactor in 25～35 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.Emulsification can heat up and carry out polymerization in 20～75 minutes.The temperature of maintenance system was carried out polyreaction 4～6 hours under 70～85 ℃.System temperature is risen to 90～100 ℃ then, polyreaction was carried out 0.5～1.5 hour again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified.
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 a softening agent in emulsion, thermo-stabilizer etc., be employed softening agent such as DOP in the general plastic working process, DCP, Magnesium Stearate etc., 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), emulsifying agent, water, softening agent, the consumption of 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 XMI in the ST/AN mixed solution is limited, after the XMI formula ratio reaches certain umber, temperature is lower than 25 ℃, XMI 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.
The maleimide monomer that the preparation method adopted of maleimide unit or halogen substituent maleimide heat-proof flame-proof resin emulsion has following structure among the present invention:
(Rn contains the halo-alkyl of 1～15 carbon in the formula, cycloalkyl, and substituted alkyl, aryl, substituted aryl, wherein, halogens is bromine, chlorine)
Concrete example has: N-halogenated methyl maleimide, N-halogenated ethyl maleimide, N-halo tertiary butyl maleimide, N-halo isobutyl-maleimide, N-halo cyclohexyl maleimide, N-halogenophenyl maleimide, N-halogenated methyl phenyl maleimide, N-halogenated methoxy phenyl maleimide, N-halo carboxyl phenyl maleimide, N-halogenated nitrobenzene base maleimide, N-halo naphthyl maleimide etc., these halo maleimide monomers can be used alone or in combination.Wherein preferred N-tribromo cyclohexyl maleimide and N-tribromo phenyl maleimide.
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), 1,3-dimethyl styrene, 2,4-dimethyl styrene, ethyl styrene, 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.Wherein optimization styrene, 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.
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, 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.
Used initiator is the oil soluble thermal decomposition initiating in the synthetic method of halogen substituent maleimide heat-proof flame-proof resin emulsion of the present invention, it is the general initiator of radical polymerization, at 100 ℃ half life of decompositions less than 4 hours, as azo class, organo-peroxide class etc.The most frequently used initiator has: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide 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).
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 is 3～10%) copolymer emulsion, butadiene-acrylonitrile (wherein acrylonitrile content is 3～8%) copolymer emulsion, butadiene-acrylic acid butyl ester (wherein Butyl acrylate content is 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 polyhutadiene-acrylonitrile-styrene graftomer ABS.
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 monomer and the graft copolymer latex of itrile group vinyl monomer 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 (in butt) 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 2～10 parts then, 0.1～0.3 part oxygenant, 5～15 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 3～18 parts of itrile group vinyl monomers after～2.5 hours, 15～45 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 preparation of the multipolymer of conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer.
Optimum condition:
Under 25～35 ℃ with 40～55 parts particle diameter conjugated diene rubber latex 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, are warmed up to 60 ℃ and add 0.01～0.03 part of reductive agent, begin reaction, because exothermic heat of reaction begins to heat up, add 7.0～13.5 parts of itrile group vinyl monomers after 0.5～2.0 hour, 21～32 parts aryl ethylene class monomer and 0.2～0.3 part oxygenant in the system.Record the graft latex transformation efficiency by the method for surveying dry-matter and finish reaction more than 95%, finish the preparation of the multipolymer of conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer.
Promptly can provide use with emulsion form among the present invention, also the graftomer emulsion of conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer can be condensed, provide use after the drying the graftomer emulsion that generates conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer.Dry auxiliary agent that uses of cohesion and usage quantity, condition are prior art, universal method.
Employed flocculation agent is general flocculation agent among the present invention, as being calcium sulfate, calcium chloride, sal epsom, sodium-chlor, potassium aluminium sulfate, polymeric flocculant etc., can be one or more, preferably sulfuric acid magnesium.
The used oxygenant of the present invention is the general oxygenant of redox system, as being hydrogen peroxide, hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide, tertbutyl peroxide, isopropyl benzene hydroperoxide, peroxidation 2, the 4-dichloro-benzoyl, 1,1-two (tert-butyl peroxy base) hexanaphthene etc. can be one or more, preferred hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide.Employed reduction is reductive agent mutually, helps reductive agent to be the general reductive agent of redox system, to help reductive agent, as using ferrous sulfate, sodium sulfoxylate formaldehyde in the invention, glucose, S-WAT, organism such as alcohol, amine, oxalic acid, preferably sulfuric acid is ferrous, 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 resisting flame retardant 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 halogen substituent maleimide heat-proof flame-proof resin emulsion, 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 resisting flame retardant resin composition; Also the halogen substituent maleimide heat-proof flame-proof resin emulsion 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 resisting flame retardant resin composition.
The present invention also provides a kind of preparation method of this heat resisting flame retardant resin composition, is that the copolymer that the graftomer emulsion of the heat-proof flame-proof resin emulsion of a kind of halogen substituent maleimide monomer and aryl ethylene class monomer and itrile group vinyl monomer and conjugated diene rubber grafting aryl ethylene class monomer and itrile group vinyl monomer is carried out common cohesion, dry back and aryl ethylene class monomer and itrile group vinyl monomer carries out the method that blend prepares heat resisting flame retardant resin composition specifically:
Halogen substituent maleimide heat-proof flame-proof resin emulsion 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.The mixture that will contain the graftomer of 65～95 parts halogen substituent maleimide heat-proof resin and conjugated diene rubber, with copolymer (as the SAN) blend of 5～35 parts aryl ethylene class monomer and itrile group vinyl monomer, blend can obtain the heat resisting flame retardant 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).
Owing in auxiliary agent, generally also add the small molecules fire retardant during the conventional flame retarded polymeric material of preparation, but there is problems such as add-on big (generally wanting more than 10 parts), cost height, and the small molecules fire retardant is easy to migration and runs off, and makes the fire-retardant stability of fire retardant material very poor.The present invention makes fire-retardant group directly link on the macromole, the fire retardant usage quantity is little just to reach the good flame effect, reduced cost, also solved the transport property problem of small molecules fire retardant to a great extent, the add-on of small molecules fire retardant in the auxiliary agent is reduced greatly, even can not add the small molecules fire retardant.The fire-retardant add-on of auxiliary agent is 0～2 part among the present invention.
The characteristics of heat resisting flame retardant resin composition of the present invention and preparation method thereof are as follows:
1. the synthetic method of halogen substituent maleimide heat-proof flame-proof resin emulsion 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 resisting flame retardant resin composition of the present invention adopts halogen substituent maleimide heat-proof flame-proof resin emulsion and conjugated diene rubber graft copolymer emulsion to condense has altogether solved the difficult problem that heat-proof flame-proof resin emulsion 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-proof flame-proof resin, and making it has good consistency with heat-proof flame-proof resin.
4. with the preparation method of maleimide heat resisting flame retardant resin composition containing halogen substituent of the present invention, it is good that the heat resisting flame retardant resin composition that makes has outward appearance, fire-retardant, and the advantage that thermal stability is high is the good heat-proof combustion-resistant material of a kind of performance.The heat-proof flame-proof resin of preparation can be widely used in the heat-proof combustion-resistant modification aspect to materials such as ABS, PC, PBT.As a kind of heat-proof combustion-resistant performance excellent material, its independent use also can be used for preparing automobile, the component of the high-temp resistant fire-retarding 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, emulsor stir for band.Hereinafter " % ", " part " all refers to mass percent or mass fraction.
Second-order transition temperature Tg:DSC-differential thermal differential method
Vicat softening temperature: GB/T 1633-2000
Flame retardant properties test: UL-94
GPC：W-150C
Nitrile content: GB/T 4486-84
Melt flow rate (MFR) (g/10min): 3682-2000
Socle girder notched Izod impact strength (J/m): GB/T 1843-1996
Resin emulsion stability with reaction finish the ratio magnitude (≤0.5%) of solids that the back emulsion filters out and total monomer charging capacity and emulsion placement more than 12 hours nondiscoloration weigh.
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.
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, emulsor stir for band.Hereinafter " % ", " part " all refers to mass percent or mass fraction.
Blending auxiliary agent 1: lubricant EBS: antioxidant 1010: softening agent Magnesium Stearate: decabromodiphenyl oxide: Sb
2O
3Weight ratio be 1: 2: 1: 10: 15
Blending auxiliary agent 2: lubricant EBS: antioxidant 1010: the weight ratio of softening agent Magnesium Stearate is 1: 2: 1.
Embodiment:
The preparation of halogen substituent maleimide resin emulsion
The preparation of A1:
The preparation of monomer mixed solution
Under 30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 parts of vinylbenzene, 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).
The preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, open and stir, and (a) joined carry out emulsification in the reactor.The pH value is surveyed in emulsification after 40～45 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.5～5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.
In (b), add 0.7 part of the emulsion of auxiliary agent at last, be all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying, as the criterion (＜3.0% is qualified) of emulsion reaction system stability through washing.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.8%.
Calculated yield 93.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=133 ℃ with the differential calorimeter.Record its vicat softening temperature: 133 ℃, flame retardant properties reaches the V-0 level.
The preparation of A2:
The preparation of monomer mixed solution
Under 32 ℃ with 40 parts of N-tribromo phenyl maleimides, 45 parts of alpha-methyl styrenes, 15 parts of vinyl cyanide, 0.35 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).
The preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.4 parts of Sodium dodecylbenzene sulfonatees join in the reactor under 32 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 32 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 5.5～6 hours under 78 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.(b) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 1.3%.
Calculated yield 91.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=155 ℃ with the differential calorimeter.Record its vicat softening temperature: 153 ℃, flame retardant properties reaches the V-0 level.
The preparation of A3:
The preparation of monomer mixed solution
Under 25 ℃ with 10 parts of N-tribromo cyclohexyl maleimides, 65 parts of vinylbenzene, 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).
The preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of Sodium dodecylbenzene sulfonatees and 2.0 parts of synthetic fatty acid potassium join in the reactor under 25 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 31 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 5.8 hours under 72 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.(b) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 2.7%.
Calculated yield 94.1% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=108 ℃ with the differential calorimeter.Record its vicat softening temperature: 108 ℃, flame retardant properties reaches the HB level.
The preparation of A4:
The preparation of monomer mixed solution
Under 26 ℃ with 25 parts of N-tribromo phenyl maleimides, 50 parts of vinylbenzene, 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).
The preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 28 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor.The pH value is surveyed in emulsification after 44 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.5～5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion (b) after qualified, and surveying the pH value is about 9.(b) polymerization finishes the emulsion that the back adds auxiliary agent, is all processes of finishing preparation (b).
Emulsion in the reactor, after filtration, filtrate white heat-proof flame-proof resin emulsion product, placed nondiscoloration 120 hours.The solids that filters out is weighed after the drying through washing, as the criterion of emulsion reaction system stability (＜3.0% is qualified 〉.Under this condition, the ratio of solids that filters out and monomeric charge amount is 2.0%.
Calculated yield 92.5% after the white product that emulsion makes after cohesion, filtration, drying is weighed.Record second-order transition temperature Tg=120 ℃ with the differential calorimeter.Record its vicat softening temperature: 121 ℃, flame retardant properties reaches the V-1 level.
The preparation of conjugated diene rubber graft copolymer emulsion
The preparation of B1
Under 28 ℃ with the polybutadiene latex of 36 parts particle diameter 340nm, 0.9 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, and add 5.8 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 12.7 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 48% of the ABS graft copolymer that obtains, the molecular weight 6.6 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B2
Under 30 ℃ with styrene butadiene (wherein cinnamic massfraction the is 8%) copolymer emulsion of 42 parts particle diameter 290nm, 0.5 part Sodium dodecylbenzene sulfonate, 0.3 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.3 part sodium sulfoxylate formaldehyde, 190 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 5.4 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 0.025 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 28.1 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 48% of the ABS graft copolymer that obtains, the molecular weight 5.1 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B3
Under 35 ℃ with styrene butadiene (wherein cinnamic massfraction the is 10%) copolymer emulsion of 48 parts particle diameter 360nm, 0.2 part Sodium dodecylbenzene sulfonate and 0.3 part of disproportionated rosin acid soap, 0.6 part sodium bicarbonate, 0.5 part trisodium phosphate, 0.1 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, 13.5 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 24.7 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 49% of the ABS graft copolymer that obtains, the molecular weight 5.9 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B4
Under 30 ℃ with the polybutadiene latex of 40 parts particle diameter 390nm, 0.2 part Sodium dodecylbenzene sulfonate and 0.6 part of synthetic fatty acid potassium, 0.5 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 12.7 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 53% of the ABS graft copolymer that obtains, the molecular weight 7.5 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B5
Under 30 ℃ with acrylonitrile-butadiene (wherein the massfraction of vinyl cyanide the is 5%) copolymer emulsion of 45 parts particle diameter 390nm, 0.6 part Sodium dodecylbenzene sulfonate, 0.5 part sodium bicarbonate, 0.1 part trisodium phosphate, 0.4 part sodium sulfoxylate formaldehyde, 170 parts of de-salted waters join in the reactor, begin to stir, the vinyl cyanide that adds 5.4 parts then, 0.15 the di-isopropylbenzene hydroperoxide of part, 13.5 vinylbenzene and 0.21 part of tert-dodecyl mercaptan of part join in the reactor, heat up after 7 minutes, are warmed up to 60 ℃ and add 0.043 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 25.1 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 9.5 * 10 of free styrene-acrylonitrile copolymer in the ABS graft copolymer
4
The preparation of B6
Under 30 ℃ with butyl acrylate-(wherein the massfraction of butyl acrylate is 5%) butadienecopolymer latex of 45 parts particle diameter 370nm, 0.6 part Sodium dodecylbenzene sulfonate, 0.35 part sodium bicarbonate, 0.2 part trisodium phosphate, 0.3 part glucose, 170 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 0.019 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 52% 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 25 ℃ with the polybutadiene latex of 55 parts particle diameter 360nm, 0.6 part Sodium dodecylbenzene sulfonate, 0.4 part sodium bicarbonate, 0.24 part trisodium phosphate, 0.30 part glucose, 150 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 0.038 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 52% 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 55 parts particle diameter 350nm, 0.2 part Sodium dodecylbenzene sulfonate, 0.4 part sodium bicarbonate, 0.21 part trisodium phosphate, 0.11 part glucose, 145 parts of de-salted waters join in the reactor, begin to stir, and add 4.0 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 0.016 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 25 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 52% 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: commercially available GE company produce 338
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:
Heat-proof flame-proof resin emulsion 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 30～45 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 HH, 5.80 parts blending auxiliary agent 1 mixes in the high speed mixing machine.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 2:
Heat-proof flame-proof resin emulsion 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 30～45 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 BHF, 5.30 parts blending auxiliary agent 1 mixes in the high speed mixing machine.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 3:
Heat-proof flame-proof resin emulsion 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 30～45 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 HH-C300,3.90 parts blending auxiliary agent 1 mixes in the high speed mixing machine.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 4:
Heat-proof flame-proof resin emulsion 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 30～45 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 HH, 4.80 parts blending auxiliary agent 1 mixes in the high speed mixing machine.Blend can obtain the heat resisting flame retardant 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:
Heat-proof flame-proof resin emulsion A1100 part under 35 ℃, is under agitation joined temperature continuously and is in 70 ℃ the aqueous solution of 350 part 6 ‰ sal epsom, keep uniform feed rate and in 30～45 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, HH of 15 parts, 3.50 parts blending auxiliary agent 1 mixes in the high speed mixing machine.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 2.
Embodiment 10:
Heat-proof flame-proof resin emulsion A1100 part under 35 ℃, is under agitation joined temperature continuously and is in 70 ℃ the aqueous solution of 450 part 4 ‰ sal epsom, keep uniform feed rate and in 30～45 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.
ABS emulsion B6100 part under 25 ℃, is under agitation joined temperature continuously and is in 63 ℃ the aqueous solution of 350 part 5 ‰ sal epsom, keep uniform feed rate and in 30～45 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 part B6,5 parts HH after the A1 after 65 parts of oven dry and the 30 parts of oven dry, 0.80 part blending auxiliary agent 2 mixes in the high speed mixing machine.Blend can obtain the heat resisting flame retardant 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
Table 2 embodiment heat-resistant composition blend prescription and The performance test results
Comparative example 1～8: on the basis of embodiment 1～8, during the preparation heat-proof flame-proof resin emulsion, adopt N-phenylmaleimide to test.
Comparative Examples
Heat-proof flame-proof resin emulsion (the A of Comparative Examples
0) preparation
A
01 preparation:
A) preparation of monomer mixed solution
30 ℃ with 30 parts of N-tribromo phenyl maleimides, 45 parts of vinylbenzene, and 25 parts of vinyl cyanide, 0.7 part of sodium lauryl sulphate, 0.2 part of Potassium Persulphate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms the emulsus monomer mixed solution.
B) preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, open and stir, and (a) joined carry out emulsification in the reactor.The pH value is surveyed in emulsification after 40～45 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.5～5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, the sampling and measuring total solid content, and qualified back (〉=37%, as follows) promptly forms heat-proof flame-proof resin emulsion, and surveying the pH value is about 9.
A
02 preparation
A) preparation of monomer mixed solution
30 ℃ with 45 parts of phenyl maleimides, 45 parts of vinyl cyanide, and 15 parts of vinyl cyanide, 0.7 part of sodium lauryl sulphate, 0.2 part of Potassium Persulphate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms the emulsus monomer mixed solution.
B) preparation of heat-proof flame-proof resin emulsion
With 160 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 30 ℃, open and stir, and (a) joined carry out emulsification in the reactor.The pH value is surveyed in emulsification after 40～45 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.5～5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion after qualified, and surveying the pH value is about 9.
A
03 preparation
A) preparation of monomer mixed solution
35 ℃ with 10 parts of N-tribromo phenyl maleimides, 65 parts of vinylbenzene, and 25 vinyl cyanide, 0.7 part of sodium lauryl sulphate, 0.3 part of Sodium Persulfate, 0.1 part of mercaptan adds tempering tank, opens to stir and mixes, and forms the emulsus monomer mixed solution.
B) preparation of heat-proof flame-proof resin emulsion
With 180 parts of de-salted waters, 3.5 parts of sodium lauryl sulphate join in the reactor under 35 ℃, open and stir, and (a) joined carry out emulsification in the reactor.The pH value is surveyed in emulsification after 40～45 minutes be 9～10, can heat up and carry out polymerization.The temperature of maintenance system was carried out polyreaction 4.5～5 hours under 75 ℃.System temperature is risen to 95 ℃ then, polyreaction was carried out 1.0 hours again, and the sampling and measuring total solid content promptly forms heat-proof flame-proof resin emulsion after qualified, and surveying the pH value is about 9.
Conjugated diene rubber graft copolymer emulsion (the B of Comparative Examples
0) preparation
B
01 preparation
Under 25 ℃ with the polybutadiene latex of 45 parts particle diameter 280nm, 0.2 part Sodium dodecylbenzene sulfonate and 0.6 part of synthetic fatty acid potassium, 0.5 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, 0.15 the di-isopropylbenzene hydroperoxide of part, 13.5 parts vinylbenzene and 0.40 part of tert-dodecyl mercaptan join in the reactor, heat up after 15 minutes, be warmed up to 60 ℃ and add 0.012 part of ferrous sulfate, begin reaction, in the system because exothermic heat of reaction begins to heat up the di-isopropylbenzene hydroperoxide of 41.5 parts vinylbenzene and 0.25 part after 1.5 hours.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
Comparative Examples 1:
With heat-proof flame-proof resin emulsion A
01 mixes 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 30～45 minutes, add.After emulsion adds mixed solution is warming up to 95 ℃ and keeps and to lower the temperature in 1～1.5 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, promptly become A
01 with the B1 mixture.With the A after 65 parts of oven dry
01 with the B1 mixture, with 35 parts HH, 5.80 parts blending auxiliary agent 1 mixes in the high speed mixing machine.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 3.
Comparative Examples 2:
With heat-proof flame-proof resin emulsion A
02 mix according to 25: 50: 0.80 ratio with the emulsion of ABS emulsion B2 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 30～45 minutes.After emulsion adds mixed solution is warming up to 97 ℃ and keeps and to lower the temperature in 1～1.5 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.With the A after 75 parts of oven dry
02 with the B2 mixture, with 25 parts BHF, 8.30 parts blending auxiliary agent 1 mixes in the high speed mixing machine.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 3.
Comparative Examples 3:
With heat-proof flame-proof resin emulsion A
03 mix according to 35: 40: 1.20 ratio with the emulsion of ABS emulsion B3 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 30～45 minutes.After emulsion adds mixed solution is warming up to 100 ℃ and keeps and to lower the temperature in 1～1.5 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.With the A after 75 parts of oven dry
03 with the B3 mixture, with 25 parts HH-C300,3.90 parts blending auxiliary agent 1 mixes in the high speed mixing machine.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 3.
Comparative Examples 4:
With heat-proof flame-proof resin emulsion A1 and ABS emulsion B
01 and the emulsion of auxiliary agent mix according to 45: 40: 1.20 ratio, 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 30～45 minutes.After emulsion adds mixed solution is warming up to 100 ℃ and keeps and to lower the temperature in 1～1.5 hour, finish agglomeration process.Condense the slurry that and dry with de-salted water washing back after filtration, standby.With A1 and the B after 75 parts of oven dry
01 mixture, with 15 parts HH, 4.80 parts blending auxiliary agent 1 mixes in the high speed mixing machine.Blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.The performance of product sees Table 3.
Table 3 comparative example heat-resistant composition blend prescription and The performance test results
Claims (16)
1. heat resisting flame retardant resin composition, it is characterized in that: in heat resisting flame retardant resin composition is 100 mass parts, contain: 10～65 parts of A. halogen substituent maleimide heat-proof flame-proof resins, the halogen substituent maleimide unit accounts for 10～45 quality % in the halogen substituent maleimide heat-proof flame-proof resin, aryl ethylene class unit accounts for 30～65 quality %, and the itrile group vinyl units accounts for 1～25 quality %; B. the graftomer of conjugated diene rubber grafting aryl ethylene class unit 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 20～60 quality %, and the itrile group vinyl units accounts for 5～20 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 halogen substituent maleimide heat-proof resin 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
In 25～35 ℃ with 10～45 parts of halogen substituent maleimide monomers, 30～65 parts of aryl ethylene class monomers, 1～25 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 heat-proof flame-proof resin emulsion
With 100～200 parts of de-salted waters, 2.0～10.0 parts of emulsifying agents join in the reactor that whipping appts is housed in 25～35 ℃, and the unlatching stirring joins (a) carries out emulsification in the reactor; Emulsification can heat up and carry out polymerization in 20～75 minutes, the temperature of maintenance system was carried out polyreaction 3～8 hours under 55～95 ℃, system temperature is risen to 90～100 ℃ then, polyreaction was carried out 0.5～2.0 hour again, promptly formed heat-proof flame-proof resin emulsion (b).
2. heat resisting flame retardant 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, Alpha-Methyl p-methylstyrene, halogenated styrenes, haloalkyl vinylbenzene, the vinyl naphthalene one or more.
3. heat resisting flame retardant 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 resisting flame retardant resin composition according to claim 1, it is characterized in that halogen substituent maleimide unit or halogen substituent maleimide monomer are selected from N-halogenated methyl maleimide, N-halogenated ethyl maleimide, N-halo tertiary butyl maleimide, N-halo isobutyl-maleimide, N-halo cyclohexyl maleimide, N-halogenophenyl maleimide, N-halogenated methyl phenyl maleimide, N-halogenated methoxy phenyl maleimide, N-halo carboxyl phenyl maleimide, N-halogenated nitrobenzene base maleimide, one or more in the N-halo naphthyl maleimide.
5. heat resisting flame retardant resin composition according to claim 1 is characterized in that emulsifying agent is anion surfactant, nonionogenic tenside or their compound system.
6. heat resisting flame retardant 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 resisting flame retardant resin composition according to claim 1 is characterized in that molecular weight regulator is tert-dodecyl mercaptan or dodecyl mercaptan carbon.
8. heat resisting flame retardant 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 resisting flame retardant resin composition according to claim 1 is characterized in that the copolymer nitrile content of aryl ethylene class monomer and itrile group vinyl monomer is 22～35%, and molecular weight is 60000～120000.
10. heat resisting flame retardant 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 resisting flame retardant resin composition of claim 1, it is characterized in that halogen substituent maleimide heat-proof flame-proof resin emulsion 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, the mixture that will contain the graftomer of 65～95 parts halogen substituent maleimide heat-proof resin and conjugated diene rubber, with the copolymer blend of 5～35 parts aryl ethylene class monomer and itrile group vinyl monomer, blend can obtain the heat resisting flame retardant resin composition product through twin screw extruder.
12. the preparation method of heat resisting flame retardant 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, down will be at 25～35 ℃ in the particle diameter of 35～60 parts of butts 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 2～10 parts then, 0.1～0.3 part oxygenant, 5～15 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 3～18 parts of itrile group vinyl monomers after～2.5 hours, 15～45 parts aryl ethylene class monomer and 0.1～0.3 part oxygenant record graft latex transformation efficiency 95% by the method for surveying dry-matter and finish to react when above.
13. the preparation method of heat resisting flame retardant resin composition according to claim 11 is characterized in that 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 resisting flame retardant resin compositions.
15. the preparation method of heat resisting flame retardant 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 resisting flame retardant 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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| CN1280147A (en) * | 1999-07-08 | 2001-01-17 | 奇美实业股份有限公司 | Rubber modified resin composition |
| CN1394216A (en) * | 2000-11-10 | 2003-01-29 | Lg化学株式会社 | Method for preparing acrylonitrile-butadiene-styrene latex having high total solid content |
| CN1455786A (en) * | 2001-01-08 | 2003-11-12 | Lg化学株式会社 | Method for preparing thermoplastic resin |
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