CN100558776C - A kind of preparation method of polymer modified styrene resin for energy saving - Google Patents
A kind of preparation method of polymer modified styrene resin for energy saving Download PDFInfo
- Publication number
- CN100558776C CN100558776C CNB2005101152375A CN200510115237A CN100558776C CN 100558776 C CN100558776 C CN 100558776C CN B2005101152375 A CNB2005101152375 A CN B2005101152375A CN 200510115237 A CN200510115237 A CN 200510115237A CN 100558776 C CN100558776 C CN 100558776C
- Authority
- CN
- China
- Prior art keywords
- weight
- monomer
- vinyl
- polymerization
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a kind of preparation method of polymer modified styrene resin for energy saving, its feature is in the nonpolar mixed solvent of lower boiling, cause conjugated diene or conjugated diene and vinyl aromatic (co) polymerized hydrocarbon with lithium or hydrocarbyl lithium, form the base polymer of different structure, adopt the in-situ polymerization transforming methods of structural system then, transfer radical polymerization to by living anion polymerization, promptly add vinyl-arene again, monomer and catalyzer and thinners etc. such as acrylic and (methyl) alkyl acrylate, in temperature is under 80～170 ℃, carry out graft copolymerization, and in the graft polymerization process, get rid of low boiling point solvent by controlled polymerization system pressure and temperature section, under high temperature and vacuum condition, remove a small amount of unreacted monomer and thinner then, prepare method at last with the polymer graft modification phenylethylene resin series.
Description
Technical field
The present invention relates to the graftomer field, particularly relate to a kind of base polymer solution, the preparation method that the capable free radical grafting copolymerization of in-situ transesterification swap-in closes modified styrene resin with living anion polymerization.
Technical background
In the past, in order to see the content in plastic containers and the dish etc., though most biaxial stretch-formed sheet container that uses polystyrene system, these containers exist because poor impact resistance, the damage of very easily breaking, the edge of container produce the problem to people's cutting wound etc.
Shock resistance transparent polystyrene resin is because of its shock strength height, transmittance is good, formability might as well, and be widely used at packaging field, and cup, dish, pipe and outside very useful in the purposes such as shell product, cause that countries in the world extensively note, dropped into a large amount of man power and materials and developed research, many patented technology documents have been reported, wherein
China publication CN 1172120A and U.S. Pat 2005070663 have been reported: the styrene-butadiene-styrene block copolymer [styrene content is approximately composition part cumulative (tapered) segmented copolymer of 70%] that the anionic solution polymerization method is made is dissolved in the vinylbenzene, use the radical initiator initiated polymerization, obtain transparent impact-resistant polystyrene resin, in this method, the resin of preparation need dissolve by the process of complexity separately, obtain being dissolved in the resin solution in the vinylbenzene, this solution must remove by filter gel particle before polymerization, increased flow process and equipment and energy expenditure.Butadiene-styrene block copolymer is in dry and storage process, and is crosslinked rotten in order to prevent it, must add phenols or phosphoric acid ester oxidation inhibitor, and these oxidation inhibitor tends to have influence on later graft polymerization reaction.In addition, therefore butadiene content low (being less than 50%) in their the used butadiene-styrene block copolymer, need use more butadiene-styrene block copolymer as reaching certain shock strength, so cost is higher.
English Patent 1,013,205 carry out anionoid polymerization by divinyl in non-polar solvent such as hexanaphthene, make it inactivation, add vinylbenzene subsequently and the catalyzer grafting makes HIPS.Yet this method is limited to polybutadiene rubber shape thing graft phenylethene, what obtain is opaque polystyrene graft thing, and need be before graft reaction, with big weight phenylethylene displacement low boiling point solvent, remove boiling point with the subduction distillation then and be lower than cinnamic solvent, thereby increased flow process and equipment and energy expenditure.
China granted patent 89101618.X has described a kind of: carry out polymerizing butadiene in the inert solvent of q.s, be tangible liquid form to keep final polyhutadiene, with a kind of anionic initiator initiated polymerization of preferably lithium.The ethylbenzene consumption is generally between 20～50% (weight) of divinyl total amount.The polymerizing butadiene temperature can be between 20～130 ℃ changes on a large scale.Consider the control of temperature of reaction, regulate polymerization temperature automatically by feeding divinyl continuously in the medium.Polymerizing butadiene is finished, and after destroying initiator, then adds vinyl monomer in the medium in the past and carries out polymerization.
This method has avoided removing low boiling point solvent, directly makes solvent with ethylbenzene, but the system viscosity height is unfavorable for the reaction heat derivation, the difficult control of polymerization temperature.When ethylbenzene recycles, be difficult to separating phenylethylene homologue impurity, industrial production proves, 0.2% vinylbenzene homologue impurity will make the product quality fluctuation, and make BuLi consume increase, thereby cost rises.This patent adopts continuous processing to produce polyhutadiene, gained polyhutadiene molecular weight distribution wide (greater than 2), thereby obtain the relatively poor grafted products of rerum natura.In addition, this method also is difficult to make the base polymer of complex construction, as the needed bimodal phenylethylene/butadiene block thing of preparation high gloss polymer graft modification phenylethylene resin series product.
In addition, polyhutadiene is used for styrene-grafted and can only obtains opaque high-impact polystyrene.Because in order to keep the mechanical property of impact-resistant polystyrene, it is enough big that the molecular weight of polyhutadiene is wanted, as: 120,000～220,000, in polystyrene, formed the rubber grain of cohesive size like this greater than wavelength of visible light (greater than 200nm), thereby can reflect or refracted light, make the finished product opaque.
United States Patent (USP) 3,264,374,4311819 described a kind of method for preparing polyhutadiene in vinylbenzene: with lithium compound is initiator, in the presence of vinyl aromatic monomer, carry out divinyl anionoid polymerization by halves, obtain a kind of divinyl-vinyl aromatic monomer multipolymer of low vinyl aromatic monomer content, in above-mentioned monomer mixture, add terminator and stop polymerization and remove divinylic monomer, add or do not add monovinylarene family monomer therein in addition with afterreaction formation anti-impact styrene polymer.This technology has been simplified the method for making of polyhutadiene and anti-impact polymkeric substance effectively, and this is that it has been cancelled on the one hand and desolventizes and polyhutadiene exsiccant step, has cancelled on the other hand pulverizing and making polyhutadiene be dissolved in the step of vinyl aromatic monomer.
It has two great shortcomings at present at least.Do not add the retarding agent list and cause polymerizing butadiene with butyllithium, because polymerization rate is very fast, difficulty is controlled the transformation efficiency of polyhutadiene or is made transformation efficiency keep stable, (the promptly difficult molecular weight of controlling polyhutadiene); Simultaneously, be difficult to control and enter cinnamic amount in the polymeric chain, if these two amounts are unstable, grafts character also can not be stablized, so this is the industrial method that is difficult to carry out.Although saved solvent, adopt the part method for polymerizing butadiene, need to increase divinyl reuse and rectification flow.In addition and since anti-should the back divinyl autohemagglutination very easily, industrially be difficult to carry out recovery, increased divinyl consumption, cost up has also lost the monomer conversion that the butyllithium system had and can reach 99%, does not need to reclaim monomeric advantage.
United States Patent (USP) 6143833, described: a kind of method for preparing HIPS with polyhutadiene, this method may further comprise the steps: add enough divinyl earlier 1., approximate content is about the 1-15 weight part, preferably can make the polyhutadiene that contains 12 weight parts after the polymerization, again that preheating is good varsol and suitable polymerizing catalyst are added in the continuously stirring jar shape reactor; 2. these components of polymerization move on to them in the plug flow reactor from continuously stirring jar shape reactor, make the complete polymerization of divinyl; 3. styrene monomer is added wherein, mix, heat, remove through the vacuum devolatilization flash distillation of two steps and desolvate and unreacted divinylic monomer, to produce the solution of polyhutadiene at styrene monomer; 4. this formulations prepared from solutions of polymerization contains dispersion rubber particulate polystyrene then.Yet this method polyhutadiene graft phenylethene, what obtain is opaque polystyrene graft thing, also needs to replace low boiling point solvent, and carries out graft reaction after two steps, vacuum devolatilization flash distillation desolventized, thereby has increased flow process and equipment and energy expenditure.
United States Patent (USP) 6437043 has been described: carry out the negatively charged ion successive polymerization by Butadiene in non-polar solvent (as: hexanaphthene or pentamethylene), the segmented copolymer of preparation random styrene-butadiene rubber and polystyrene, add vinylbenzene subsequently, after hexanaphthene or pentamethylene solvent are finished by styrene monomer " exchange ", graft polymerization takes place in the presence of peroxide initiator, obtains transparent impact-resistant polystyrene resin.Yet therefore butadiene content low (being less than 50%) in their the used butadiene-styrene block copolymer, need use more butadiene-styrene block copolymer as reaching certain shock strength, so cost is higher; And need the displacement low boiling point solvent, thereby flow process and equipment and energy expenditure have been increased.In addition, at the lithium initiator system, use vinylbenzene to cross metering method, be difficult to control ratio of components strict in the multipolymer, this will cause the end product quality fluctuation.
Simultaneously, above-mentioned two pieces of patents all adopt continuous processing production basis polymkeric substance, gained base polymer molecular weight distribution wide (greater than 2), this method is difficult to make the base polymer of complex construction, disorderly arrange segmented copolymer, form part cumulative segmented copolymer, segmented copolymer, segmented copolymer and a bimodal distribution segmented copolymer etc. as the block part, therefore have the prepared few shortcoming of the impact-resistant polystyrene trade mark.
Summary of the invention
The objective of the invention is to overcome the deficiency that above-mentioned prior art exists, be engaged in anionic polymerization and free radical grafting copolymerization development research and suitability for industrialized production practice for a long time through the contriver, exploitation provides a kind of method of the capable free yl graft polymerization modified styrene resin of base polymer solution in-situ transesterification swap-in of energy-efficient living anion polymerization.
The preparation method of polymer modified styrene resin for energy saving provided by the invention, its feature comprises the following steps:
1) mixes in the type stirring tank complete, with respect to the whole monomer weight 50-90% that use, the boiling point of preferred 65-85% is 30-100 ℃, in preferred 40-90 ℃ the nonpolar mixed solvent of lower boiling, at 10-120 ℃, under the preferred 20-100 ℃ of temperature, with lithium or hydrocarbyl lithium is initiator, adopt interrupter method to cause conjugated diolefine or conjugated diolefine and vinyl-arene and carry out living anion polymerization, or add coupling agent behind the living anion polymerization again and carry out coupling, form the base polymer solution of various structures;
2) in the successive polymerization system of a plurality of no back-mixed reactors, in the base polymer solution of step 1), add and comprise monomer component, initiator (catalyzer) and thinner etc., at temperature 60-180 ℃, under preferred 80-170 ℃, close by the capable free radical grafting copolymerization of living anion polymerization system in-situ transesterification swap-in, and each reactor pressure of controlled polymerization system and temperature automatic segmentation get rid of the nonpolar mixed solvent of lower boiling, form the polymer modified styrene resin of various structures;
3) with step 2) polymer modified styrene resin that forms removes the polymer modified styrene resin that a small amount of unreacted monomer and thinner obtain various structures under 160-220 ℃ of high temperature and 5-10Kpa vacuum condition.
Among the preparation method according to energy-efficient polymer modified styrene resin provided by the invention, described polymerization and polymkeric substance comprise homopolymerization and homopolymer and copolymerization and multipolymer, as various segmented copolymers and various graft copolymer.Described step 2) the monomer component is meant step 2 in) in monomers such as related monomer such as vinyl-arene, alkyl acrylate, maleic anhydride, (N-phenyl) maleimide, acrylic, unsaturated carboxylic acid anhydrides.Described thinner is an ethylbenzene, the common 2-20% of its consumption.
The base polymer solution that the living anion polymerization of conjugated diolefine or conjugated diolefine and vinyl-arene forms various structures in described step 1) comprises:
1. add conjugated diene and prepare homopolymer;
2. after adding conjugate diene polymerization, add with respect to per 100 molar part polymkeric substance, 5～60 molar part, the coupling agent of preferred 10～50 molar part carries out coupling or part linked reaction, prepares star-like or multimodal homopolymer again;
3. add conjugated diene and vinyl-arene prepares multipolymer, wherein the mol ratio of conjugated diene and vinyl-arene is 20: 80～95: 5, preferred 40: 60～80: 20;
4. add after conjugated diene and vinyl-arene prepare copolymer polymerization, adding is with respect to per 100 molar part polymkeric substance, 5～60 molar part, the coupling agent of preferred 10～50 molar part carries out coupling or part linked reaction, prepare star-like or multimodal multipolymer, wherein the mol ratio of conjugated diene and vinyl-arene is 20: 80～90: 10, preferred 40: 60～80: 20;
5. after adding conjugate diene polymerization, add with respect to per 100 parts by weight polymer, 10～120 weight parts, the vinyl-arene of preferred 15～100 weight parts continues polymerization and prepares segmented copolymer again;
6. after adding conjugate diene polymerization, add again, after the vinyl-arene of preferred 15～100 weight parts continues polymerization, add with respect to per 100 molar part polymkeric substance with respect to per 100 parts by weight polymer, 10～120 weight parts
5～60 molar part, the coupling agent of preferred 10-50 molar part carries out coupling or the part linked reaction prepares star-like or the multimodal segmented copolymer;
7. after adding conjugated diene and vinyl aromatic (co) polymerized hydrocarbon, wherein the mol ratio of conjugated diene and vinyl-arene is 20: 80～90: 10, preferred 40: 60～80: 20, add with respect to per 100 parts by weight polymer 10-120 weight parts, the vinyl-arene of preferred 15-100 weight part continues the segmented copolymer that polymerization prepares multipolymer again;
Or [wherein the mol ratio of conjugated diene and vinyl-arene is 20: 80～90: 10 after 8. adding conjugated diene and vinyl aromatic (co) polymerized hydrocarbon, preferred 40: 60～80: 20, add again with respect to per 100 parts by weight polymer, 1～100 weight part, after the vinyl-arene of preferred 15-100 weight part continues polymerization, adding is with respect to per 100 molar part polymkeric substance 5～60, and the coupling agent of preferred 10-50 molar part carries out coupling or the part linked reaction prepares segmented copolymer star-like or the multimodal multipolymer;
In described step 2) in the monomer component be following monomer mixture:
1. add with respect to every weight part base polymer 2～35 weight parts preferred 4～20 parts by weight of ethylene base aromatic monomers;
2. add with respect to every weight part base polymer 2～35 weight parts the monomeric mixture that preferred 4～20 weight parts are made up of following ratio:
20～80, the vinyl aromatic monomer of preferred 30～70 weight parts and
20～80, preferred 30～70 weight parts (methyl) alkyl acrylate monomer;
3. add with respect to every weight part base polymer 2～35 weight parts the monomeric mixture that preferred 4～20 weight parts are made up of following ratio:
60～90, the vinyl aromatic monomer of preferred 70～80 weight parts and
10～40, preferred 20～30 weight part α-Jia Jibenyixidantis;
4. add with respect to every weight part base polymer 2～35 weight parts the monomeric mixture that preferred 4～20 weight parts are made up of following ratio:
40～90, the vinyl aromatic monomer of preferred 50～80 weight parts and
10～60, preferred 20～50 weight part unsaturated carboxylic acid anhydrides class monomers;
5. add with respect to every weight part base polymer 2～35 weight parts the monomeric mixture that preferred 4～20 weight parts are made up of following ratio:
40～90, the vinyl aromatic monomer of preferred 50～80 weight parts and
10～60, preferred 20～50 weight part maleimide monomers;
6. add with respect to every weight part base polymer 2～35 weight parts the monomeric mixture that preferred 4～20 weight parts are made up of following ratio:
60～98, the vinyl aromatic monomer of preferred 70～90 weight parts and
2～40, preferred 10～30 parts by weight of acrylonitrile are monomer.
7. add with respect to every weight part base polymer 2～35 weight parts the monomeric mixture that preferred 4～20 weight parts are made up of following ratio:
8～80, the vinyl aromatic monomer of preferred 12～70 weight parts and
10～90, preferred 20～80 weight parts (methyl) alkyl acrylate monomer and
2～40, preferred 5～30 parts by weight of acrylonitrile are monomer.
8. add with respect to every weight part base polymer 2～35 weight parts the monomeric mixture that preferred 4～20 weight parts are made up of following ratio:
30～90, the vinyl aromatic monomer of preferred 40～78 weight parts and
10～40, preferred 20～30 weight part α-Jia Jibenyixidantis and
2～40, preferred 5～30 parts by weight of acrylonitrile are monomer.
9. add with respect to every weight part base polymer 2～35 weight parts the monomeric mixture that preferred 4～20 weight parts are made up of following ratio:
45～90, the vinyl aromatic monomer of preferred 55～80 weight parts and
2～30, preferred 5～15 weight part unsaturated carboxylic acid anhydrides class monomers and
2～40, preferred 3～30 parts by weight of acrylonitrile are monomer.
Or 10. add with respect to every weight part base polymer 2～35 weight parts the monomeric mixture that preferred 4～20 weight parts are made up of following ratio:
20～93, the vinyl aromatic monomer of preferred 30～80 weight parts and
5～60, preferred 10～50 weight part maleimide monomers and
2～50, preferred 10～40 parts by weight of acrylonitrile are monomer.
In above-mentioned steps 1) in, described conjugated diene is divinyl, isoprene, pentadiene or its mixture, preferred divinyl.When synthesizing transparent resin, the molecular weight of soft section block part of base polymer is 20000～50000, preferred 30000～40000, when the molecular weight of soft section of base polymer is lower than 20000, the impact strength decreased that will cause resin, opposite, greater than 50000, the transparency difference of resin can't be reached the transparency required for the present invention and shock strength rerum natura equilibrated purpose as if molecular weight.
The nonpolar mixed solvent of described lower boiling, its boiling point be at 30～100 ℃, the mixture of preferred 40～90 ℃ alkane, naphthenic hydrocarbon, aromatic hydrocarbons.For example: the mixture of butane, pentane, hexane, heptane, octane, pentamethylene, hexanaphthene, suberane and benzene etc., be preferably the mixture of hexanaphthene, butane, hexane, pentane or pentamethylene, more preferably the mixture of hexane and hexanaphthene, butane or pentane and hexanaphthene.
When under enough big pressure, reacting, select the lower boiling non-polar solvent for use so that be in liquid phase during its reaction.Its consumption is for using 60～90%, preferred 65～85% of whole monomer weights.When the basic multipolymer of preparation, use lower boiling mixing stable hydrocarbon as solvent, can be by changing the ratio of mixing stable hydrocarbon, look the composition difference of basic multipolymer and regulate mixed solvent system easily, up to system viscosity low and with polymer dissolution is in optimum balance, to improve monomer content, characteristics as 25～30%.Such as: when hexanaphthene/hexane=7～9/3～1 during, can well dissolve polyhutadiene and vinylbenzene, and the viscosity of system is little as solvent.Contain 25% polyhutadiene in segmented copolymer, under 40 ℃, as solvent, the viscosity of system is 9000cp with hexane, but its solvability is bad; With cyclohexane give is solvent, and the viscosity of system is 38000cp; When hexanaphthene/hexane=7/3 as solvent, the viscosity of system is approximately 12000cp, its solvability might as well.
In the presence of mixed solvent, the reaction of conjugated diolefine or conjugated diene and vinyl-arene and lithium or hydrocarbyl lithium initiator is usually at 10～120 ℃, preferred 40～80 ℃.Can make reaction mixture be in liquid phase adding to depress.
Described lithium or hydrocarbyl lithium initiator, wherein alkyl is a 1-10 carbon atom, optional self-contained lithium alkylide, the thiazolinyl lithium, lithium aryl, the cycloalkyl lithium, ring lithium aryl isofamily, lithium methide for example, lithium ethide, the isopentyl lithium, butyllithium, the amyl group lithium, hexyl lithium, 2-ethylhexyl lithium, the allyl group lithium, the methacrylic lithium, phenyl lithium, the benzyl lithium, the tolyl lithium, 4-butyl phenyl lithium, 4-phenyl butyl lithium, the cyclohexyl lithium, 4-butyl cyclohexyl lithium, 4-cyclohexyl butyllithium, trimethylene two lithiums, tetramethylene two lithiums, one or more mix use two lithiums of divinyl and the two lithiums of isoprene etc., are preferably butyllithium or tert-butyl lithium.In order to obtain narrow molecular weight distribution but be the base polymer that multimodal distributes, present method is divided 1～4 adding with lithium or hydrocarbyl lithium.
The add-on of lithium or hydrocarbyl lithium initiator depends on the molecular weight of required base polymer.The initiator of high density content causes low molecular weight.Add 1*10 in common every gram monomer
-6～3*10
-5The mol initiator.By with the levigate dispersion of initiator, or initiator is dissolved in the suitable non-polar solvent,, in aromatic hydrocarbons or the Vaseline, can promotion closely contacts with vinyl-arene with conjugated diene as alkane.
The preparation of base polymer solution of the present invention can be finished in turn by two batch stills, its rate of polymerization, 1 when polymerization, the 2-contents of ethylene, monomeric reaction ratio of conjugated diene monomer and vinyl-arene (polystyrene) and disorganized form, can be adjusted by polar additive (compound) or irregular agent (random), above-mentioned polar compound or irregular agent are selected from: the potassium or the sodium salt of ethers, amine, thioether amine, alkylbenzene, sulfonic acid class, trialkylphosphine oxide.Ether additive such as glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, triethylene glycol dme, triethylene glycol diethyl ether, tetraethyleneglycol dimethyl ether, tetrahydrofuran (THF), 2-methoxyl group tetrahydrofuran (THF), 2-methoxymethyl tetrahydrofuran (THF), 2,5-dimethoxy-methyl tetrahydrofuran (THF) is Ji diox etc.Amine additive such as N, N, N ', N ' ,-Tetramethyl Ethylene Diamine, N, N, N ', N ' ,-tetraethylethylenediamine, triethylenediamine, N-methylmorpholine, N-ethylmorpholine and HMPA etc.Preferred polar additive is tetrahydrofuran (THF), glycol dimethyl ether, diethylene glycol dimethyl ether or N, N, N ', N ' ,-Tetramethyl Ethylene Diamine etc.Above-mentioned polar additive can use separately, also can two kinds or multiple mixing use.The mol ratio of polar additive and organic lithium initiator is 0.05 ~ 500.
Described vinyl-arene be vinylbenzene, alpha-methyl styrene, o-vinyl toluene, p-vinyl toluene, m-vinyl toluene, ethyl styrene, Vinylstyrene, i-butylstyrene or t-butylstyrene or and composition thereof, be preferably vinylbenzene.Its content is 5～55 weight % of total monomer weight, preferred 10～35 weight %, under the usual conditions, when the content of polystyrene block is lower than 5 weight %, the transparency of resin is poor, and is opposite, and if this content is greater than 35 weight %, the impact strength decreased that will cause resin can't be reached the transparency required for the present invention and shock strength rerum natura equilibrated purpose.But some special property kinds are arranged,, can improve in the base polymer vinyl-arene total amount to greater than 35% as multimodal section unregulated polymer.
In step 2) in vinyl-arene except that with above-mentioned steps 1) in identical, also can use halogenated styrenes, as o-bromstyrol, p-bromstyrol, m-bromstyrol, o-chloro-styrene, p-chloro-styrene or m-chloro-styrene.
In above-mentioned steps 1) described in coupling agent be two or many vinyl aromatic compounds; Two or polyepoxide; Two or polyisocyanates; Two or many imines; Two or many aldehyde; Two or many ketone; Two or polyhalogenide; Single, two or the polyacid acid anhydride; Single, two or polyester; The epoxidized polybutadiene that has three or four epoxy-functionals, epoxidised soybean oil, nonmetal trihalid such as METHYL TRICHLORO SILANE, nonmetal tetrahalide such as SiCl
4
General formula is expressed as: R-X-(OR ')
3, wherein R is the saturated fatty alkyl that contains 1～6 carbon atom, is preferably methyl; R ' is preferably the saturated fatty alkyl that contains 1～2 carbon atom for containing the aliphatic saturated hydrocarbon of 1～4 carbon atom; X=Si, Sn are preferably the Sn atom, as ethyl three oxygen base tin.
General formula Si-(OR)
4Organoalkoxysilane, R is selected from the alkyl group of line style and side chain in the formula.Alkyl group preferably has 1～12 carbon atom, more preferably has 1～4 carbon atom.Tetraalkoxysilane is tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes and four (2-ethyl hexyl oxy) silane.Be preferably epoxidised soybean oil, epoxidation (three or four epoxy-functionals) polyhutadiene, SiCl
4, ethyl triethoxy tin, tetraethoxysilane.
The consumption of coupling agent is decided according to the amount of initiator, is generally 0.05～0.6 (mol ratio) of initiator amount, preferred 0.1～0.5 (mol ratio).By batchwise polymerization technology, carry out linked reaction or part linked reaction complete mixing in the type stirring tank, prepare star-like basic multipolymer and multimodal distributed basis multipolymer.
The structure of the base polymer that the present invention is prepared can be: homopolymer, random copolymers, pure segmented copolymer, part statistic copolymer, a composition part cumulative segmented copolymer, segmented copolymer, star block copolymer and multimodal distribution block copolymer etc., and these various architecture basics polymkeric substance are applicable to various trade mark polymer graft modification phenylethylene resin series resins such as preparing transparent, opaque, heat-resisting and high gloss, therefore, to have a covering device multiple product be the characteristics of product diversification in the present invention.
Described (methyl) alkyl acrylate monomer is methyl methacrylate, Jia Jibingxisuanyizhi, n-butyl methyl acrylate, 2-methyl ethylhexyl acrylate or 2-ethylhexyl acrylate, preferable methyl methyl acrylate or n-butyl methyl acrylate or its mixture.
Described acrylic monomer comprises one or more in vinyl cyanide, methacrylonitrile, ethyl acrylonitrile and the derivative thereof, preferred vinyl cyanide, its content preferred 5～20%.If its content is less than 5%, chemical resistant properties is poor; If its content is greater than 20%, color of resin becomes yellow, thereby can not satisfy the requirement of human consumer to natural color, and produces a large amount of solid inclusions (coagulum) thereby be difficult to production.
Described unsaturated carboxylic acid anhydrides class monomer is selected from one or more in cis-1, propylenedicarboxylic acid acid anhydride, citraconic anhydride and the derivative thereof, is preferably cis-1.
Described maleimide monomer be selected from comprise maleimide, N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide, N-octyl group maleimide, N-sec.-propyl maleimide, N-phenylmaleimide, N-right-bromo-phenyl maleimide, N-neighbour-chloro-phenyl maleimide, N-encircle one or more in several alkyl maleimides etc. and the derivative thereof, preferred maleimide or N-phenylmaleimide.
Described graft copolymerization catalyzer is an organo-peroxide, as 1, and 1-two (t-butyl peroxy)-3,3,5-trimethyl-cyclohexane; Dialkyl peroxide, as peroxidation two-t-butyl or 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane; Diacyl peroxide is as dibenzoyl peroxide; Peroxyester is as t-butyl peroxy sec.-propyl carbonic ether; Ketone peroxide is as the pimelinketone superoxide; And azo-compound, as 2, the family of 2 '-Diisopropyl azodicarboxylate.Preferred organo-peroxide is to increase percentage of grafting and to reduce the mean size of rubber grain.
Provided by the invention with among the preparation method of polymer modified styrene resin, also can add the solvent such as ethylbenzene or the butanone that use in the conventional polymerization, chain-transfer agent, softening agent, antioxidant, releasing agent, lubricant or ultraviolet absorbers etc.
Described chain-transfer agent is used to adjust the molecular-weight average of rubber modified styrene series resin, and it is selected from and comprises n-octyl mercaptan, n-lauryl mercaptan, t-lauryl mercaptan, the dimeric family of alpha-methyl styrene, preferred t-lauryl mercaptan.
Compare with the present the whole bag of tricks of reporting, method provided by the invention has following advantage:
1. adopt intermittence-continuous process to prepare polymer modified styrene resin, preceding half section prepares base polymer in the full type stirring tank discontinuous of mixing, adopt the polymerization system conversion method, graft polymerization is finished in the successive polymerization system of a plurality of no back-mixed reactors, this method has energy-conservation characteristics, can save from the polymers soln desolventizing and become solid and be dissolved into two processes of solution again, and the high quality of the base polymer that provides has been provided by solid.
2. have in preparation during basic multipolymer, use lower boiling mixings stable hydrocarbon as solvent, by changing the ratio of mixing stable hydrocarbon, can make system viscosity low/with to the polymer dissolution sexual balance, with raising polymer content, characteristics as 25～30%.
3. have by controlling graft polymerization system pressure and temperature section eliminating low boiling point solvent the special process that vacuum decompression distillation separately removes solvent or passes through solvent exchange, therefore make the inventive method have energy-efficient characteristics.
4. adopt batchwise polymerization prepared base polymer, various complex constructions such as homopolymer, random copolymers, pure segmented copolymer, part statistic copolymer be can prepare, a part cumulative segmented copolymer, segmented copolymer, star block copolymer and multimodal distribution block copolymer etc. formed, and these complex construction basis multipolymers are applicable to various trade mark polymer graft modification phenylethylene resin series such as preparing transparent, opaque, heat-resisting and high gloss, and having a covering device multiple product is the characteristics of product diversification.
Embodiment
The present invention further specifies the present invention with the following example, but protection scope of the present invention is not limited to the following example.
Embodiment 1 usefulness polyhutadiene formulations prepared from solutions graft phenylethene anti-impact resin
Steps A: under the high pure nitrogen protection; by following prescription batching; with hexanaphthene (1350g), hexane (3150g), divinyl (796g); tetrahydrofuran (THF) (1g) joins in the stainless steel polymeric kettle of 10 liter bands stirring; after mixing; be warming up to 50 ℃; behind the impurity in a spot of butyllithium elimination system; add the butyllithium of 5.1 mmoles in the still fast; feed 50～90 ℃ of the polymerization temperatures that hot water guarantees required control with the still chuck; behind the polymerization 60min, obtain dienite, its molecular weight 15.6 ten thousand and molecular weight distribution 1.05.
Step B: using by one group of cubic capacity is the successive polymerization system synthesis modification phenylethylene resin series that 5 reactors of 25 liters constitute.1st, 2 stills are two prepolymerization kettles in parallel, and the 3rd is anti-phase still.4th, 5 stills are polymeric kettle, and still top is provided with the solvent relief outlet.According to the reaction different steps, control the temperature of each reactor with chuck and inner cool tube.Monomer is need and to change according to the different trades mark with reinforced position of auxiliary agent and feeding quantity, to adapt to the needs of many kinds.Base polymer solution is under refrigerative situation not, the solution that contains 15 weight part base polymers that will obtain by steps A with the speed of 2-3L/hr with volumetric pump, with corresponding 75 parts by weight of styrene, 10 weight part ethylbenzenes, 0.2 the polymer raw that weight part uncle dodecyl mercaptans and 0.05 weight part polymerization starter constitute, add reactive system continuously and carry out graft polymerization reaction, carry out in the graft copolymerization process, in 80～170 ℃ of polymerization temperature scopes, the low boiling point solvent segmentation is got rid of by the pressure and temperature of controlled polymerization system.Then reactant is moved into and be equipped with in the system that can make the viscous substance homogenizing, reached 180 ℃ and 0.5 hour temperature program(me) of 200 ℃ by 1 hour therein, heat the transformation efficiency that finally reaches regulation with mass transfer.Under vacuum, remove residual monomer and organic solvent etc. again.After this, generate resin and pass through twin-screw set, under non-engagement mitigation condition, further under reduced pressure remove residual monomer, make that monomer content reaches the 300ppm level in the product, under clear screw acting, carry out extruding pelletization at height again and become formal product, adopt standard method specimen performance at last, its tensile strength is 27.8MPa, and flexural strength is 35.6MPa, the Izod shock strength is 89.6J/m, and heat-drawn wire is 81 ℃.
The random butylbenzene block polymer of embodiment 2 usefulness formulations prepared from solutions binary graft modification styrene resin
Embodiment 2 repeats the polymerization process of embodiment 1 steps A, the solution of preparation base polymer in solvent, different is, by following prescription batching, with hexanaphthene (3150g), hexane (1550g), divinyl (600g), vinylbenzene (60g), N, N, N ', N ',-Tetramethyl Ethylene Diamine (106mmol), behind the tert-butyl lithium initiated polymerization 90min with 10.6 mmoles, add the vinylbenzene (300g) of removing impurity, behind the polyase 13 0min, obtain random butylbenzene-styrene block copolymer, its molecular weight 10.1 ten thousand and molecular weight distribution 1.15.
Repeat the polymerization process of embodiment 1 step B, the preparation phenylethylene resin series, different is, by following prescription batching, the solution that contains 10 weight part base polymers, 60 parts by weight of styrene, 25 parts by weight of acrylonitrile, 10 weight part ethylbenzenes, 0.1 weight part alpha-methyl styrene dimer and 0.03 weight part polymerization starter, obtain modified styrene resin after the graft polymerization, adopt standard method specimen performance, its tensile strength is 42.1MPa, and flexural strength is 61.2MPa, the Izod shock strength is 201.3J/m, and heat-drawn wire is 85 ℃.
Embodiment 3 usefulness butadiene-styrene block copolymers prepare three-component grafted transparent styrene resin
Embodiment 3 repeats the polymerization process of embodiment 1 steps A, the solution of preparation base polymer in solvent, different is, by following prescription batching, hexanaphthene (2350g), pentane (2350g), add vinylbenzene (400g), tetrahydrofuran (THF) (1.60g) at twice, behind the butyllithium-initiated polymerization 30min with 11.2 mmoles, add the divinyl of adding at twice (600g) of removing impurity, behind the polymerization 90min, obtain styrene-butadiene-styrene-butadiene block copolymer, its molecular weight be 10.8 ten thousand and molecular weight distribution be 1.12.
Repeat the polymerization process of embodiment 1 step B, the preparation phenylethylene resin series, different is by following prescription batching, to contain the solution of 7 weight part base polymers, 35 parts by weight of styrene, 30 parts by weight of methylmethacrylate, 3 weight part n-butylacrylic acid esters, 20 weight part ethylbenzenes, 0.05 weight part uncle dodecyl mercaptans and 0.03 weight part polymerization starter obtain modified styrene resin after the graft polymerization.Adopt standard method specimen performance, its transmittance is (3mm) 85%, and its tensile strength is 38.4MPa, and flexural strength is 41.2MPa, and the Izod shock strength is 187.2J/m, and heat-drawn wire is 84 ℃.
Embodiment 4 usefulness multimodal long-chain cladodification polyhutadiene prepare binary grafting thermal resistant styrene resin
Embodiment 4 repeats the polymerization process of embodiment 1 steps A, the solution of preparation base polymer in solvent, different is, by following prescription batching, pentamethylene (2350g), hexane (2350g), divinyl (996g), tetrahydrofuran (THF) (1.60g), behind the butyllithium-initiated polymerization 60min with 21.2 mmoles, add the vinylbenzene (204g) of removing impurity, behind the polyase 13 0min, adding coupling agent epoxy soybean oil (3.1mmol) carries out the part coupling and obtains the multimodal butadiene-styrene block copolymer, the molecular weight at first peak be 5.6 ten thousand and molecular weight distribution be 1.03, its weight content 26.8%; The molecular weight at second peak be 11.3 ten thousand and molecular weight distribution be 1.05, its weight content 44.3%; The molecular weight at the 3rd peak be 20.1 ten thousand and molecular weight distribution be 1.11, its weight content 28.9%.
Repeat the polymerization process of embodiment 1 step B, the preparation phenylethylene resin series, different is, by following prescription batching, the solution that contains 15 weight part base polymers, 60 parts by weight of styrene, 25 parts by weight of acrylonitrile, 10 weight part ethylbenzenes, 0.1 weight part alpha-methyl styrene dimer and 0.03 weight part polymerization starter, obtain modified styrene resin after the graft polymerization, with standard method specimen performance, its tensile strength is 38.7MPa, and flexural strength is 31.8MPa, the Izod shock strength is 142.3J/m, and heat-drawn wire is 99 ℃.
Embodiment 5 has the star-like butylbenzene copolymer of tapering transition section and prepares binary graft modification styrene resin
Embodiment 5 repeats the polymerization process of embodiment 1 steps A, the solution of preparation base polymer in solvent, different is, by following prescription batching, hexanaphthene (3290g), hexane (1410g), divinyl (900g), vinylbenzene (300g), tetrahydrofuran (THF) (1.02g), behind the butyllithium-initiated polymerization 90min with 16.8 mmoles, adding epoxidized polybutadiene (5.5mmol) carries out coupling and obtains star-like styrene butadiene part statistic copolymer, and the part content of its molecular weight 28.6 ten thousand and molecular weight distribution 1.16 is 68.9%.
40 parts by weight of styrene, 8 weight part base polymers and 30 weight part butanone are mixed down at 85 ℃, butanone solution with 12 weight part cis-butenedioic anhydrides and 0.07 weight part Diisopropyl azodicarboxylate, in 10 hours, add with the speed that falls progressively gradually, in reactor, stay for some time (90 ℃, 1.5hr), enter the two-stage flash devolatilization system at last, obtain modified styrene resin after removing solvent and unreacted monomer.Adopt standard method specimen performance, its Izod shock strength is 127.3J/m, and heat-drawn wire is 103 ℃.
Embodiment 6 usefulness butadiene-styrene block copolymers prepare binary graft modification high gloss styrene resin
Embodiment 6 repeats the polymerization process of embodiment 1 steps A, the solution of preparation base polymer in solvent, different is, by following prescription batching, hexanaphthene (3290g), hexane (1410g), vinylbenzene (220g), diethylene glycol dimethyl ether (1.5mmol) are behind the butyllithium-initiated polymerization 30min with 15.2 mmoles, add the divinyl (980g) of removing impurity, behind the polymerization 90min, obtain styrene-butadiene block copolymer, its molecular weight be 8.1 ten thousand and molecular weight distribution be 1.12.
Repeat the polymerization process of embodiment 1 step B, the preparation phenylethylene resin series, different is, by following prescription batching, contain the solution of 12.8 weight part base polymers, 63.6 parts by weight of styrene, 22.6 parts by weight of acrylonitrile, 10 weight part ethylbenzenes, 0.1 weight part uncle dodecyl mercaptans and 0.03 weight part polymerization starter obtain modified styrene resin after the graft polymerization.Adopt standard method specimen performance, its tensile strength is 41.3MPa, and flexural strength is 58.2MPa, and heat-drawn wire is 82 ℃, gloss (60 ° of reflection incident lights) 93%.
Embodiment 7 branched polybutadiene prepare three-component grafted modified heat resistant styrene resin
Embodiment 7 repeats the polymerization process of embodiment 1 steps A, the solution of preparation base polymer in solvent, different is, by following prescription batching, hexanaphthene (1350g), hexane (3150g), divinyl (1000g), tetrahydrofuran (THF) (1.8g) behind the butyllithium-initiated polymerization 90min with 8.2 mmoles, adds coupling agent SiCl
4(1.2mmol) carry out the part coupling and obtain the multimodal dienite, the molecular weight at first peak be 13.2 ten thousand and molecular weight distribution be 1.08, its weight content 36.2%; The molecular weight at second peak be 47.3 ten thousand and molecular weight distribution be 1.12, its weight content 63.8%.
Repeat the polymerization process of embodiment 1 step B, the preparation phenylethylene resin series, different is, by following prescription batching, the solution that contains 20 weight part base polymers, 40 parts by weight of styrene, 10 parts by weight of acrylonitrile, 30 weight part N-phenylmaleimides, 10 weight part ethylbenzenes, 0.1 weight part uncle dodecyl mercaptans and 0.2 weight part polymerization starter obtain modified styrene resin after the graft polymerization, its Izod shock strength is 147.4J/m, and heat-drawn wire is 108 ℃.
Embodiment 8 bimodal distribution polyhutadiene prepare modification sheet material styrene resin
Embodiment 8 repeats the polymerization process of embodiment 1 steps A, the solution of preparation base polymer in solvent, different is, by following prescription batching, hexanaphthene (1350g), hexane (3150g), divinyl (1000g), tetrahydrofuran (THF) (1.8g) behind the butyllithium-initiated polymerization 90min with 16.2 mmoles, adds coupling agent SiCl
4(3.5mmol) carry out the part coupling and obtain the multimodal dienite, the molecular weight at first peak be 7.2 ten thousand and molecular weight distribution be 1.07, its weight content 11.2%; The molecular weight at second peak be 23.3 ten thousand and molecular weight distribution be 1.12, its weight content 88.8%.
Repeat the polymerization process of embodiment 1 step B, the preparation phenylethylene resin series, different is, by following prescription batching, contain the solution of 20 weight part base polymers, 60 parts by weight of styrene, 20 parts by weight of acrylonitrile, 5 weight part ethylbenzenes, 0.02 weight part uncle dodecyl mercaptans and 0.03 weight part polymerization starter obtain modified styrene resin after the graft polymerization.Adopt standard method specimen performance, its tensile strength is 38.5MPa, and flexural strength is 55.3MPa, and the Izod shock strength is 301.1J/m, and heat-drawn wire is 82 ℃.
Embodiment 9 random styrene-butadiene polymers prepare the transparent styrene resin of modification
Embodiment 9 repeats the polymerization process of embodiment 1 steps A, the solution of preparation base polymer in solvent, different is, by following prescription batching, with hexanaphthene (1350g), hexane (3150g), divinyl (950g), vinylbenzene (50g), glycol dimethyl ether (10.8mmol) and uncle's fourth oxygen potassium (0.54mmol) are behind the tert-butyl lithium initiated polymerization 90min with 10.8 mmoles, obtain random butylbenzene copolymer, its molecular weight 10.2 ten thousand and molecular weight distribution 1.05.
Repeat the polymerization process of embodiment 1 step B, the preparation phenylethylene resin series, different is, by following prescription batching, contain the solution of 30 weight part base polymers, 50 parts by weight of styrene, 20 parts by weight of acrylonitrile, 5 weight part ethylbenzenes, 0.1 weight part n-octyl mercaptan and 0.2 weight part polymerization starter obtain modified styrene resin after the graft polymerization.
Repeat the polymerization process of embodiment 1 step B, the preparation acrylonitrile methyl meth acrylat copolymer, different is, by following prescription batching, 9 parts by weight of acrylonitrile, 91 parts by weight of methylmethacrylate, 20 weight part ethylbenzenes, 0.1 weight part n-octyl mercaptan and 0.03 weight part polymerization starter obtain acrylonitrile methyl meth acrylat copolymer
The resin that the mixture that above-mentioned two kinds of modified resin are formed with 54: 46 ratio is made adopts standard method specimen performance, and its transmittance is (3.2mm) 87%, and the Izod shock strength is 238.5J/m, and heat-drawn wire is 88 ℃.
Claims (5)
1, a kind of preparation method with polymer modified styrene resin, its feature comprises the following steps:
1) mixes in the type stirring tank complete, with respect to the boiling point of the whole monomer weight 50-90% that use as in the nonpolar mixed solvent of 30-100 ℃ lower boiling, under 10-120 ℃ of temperature, with lithium or hydrocarbyl lithium is initiator, adopt interrupter method to cause conjugated diolefine or conjugated diolefine and vinyl-arene and carry out living anion polymerization, or behind living anion polymerization, add coupling agent again and carry out the base polymer solution that coupling forms various structures, the molecular weight of soft section block part of base polymer is 20000 to 50000;
2) in the successive polymerization system of a plurality of no back-mixed reactors, in the base polymer solution of step 1), add monomer component, graft copolymerization evocating agent and thinner, under temperature 60-180 ℃, close by the capable free radical grafting copolymerization of living anion polymerization system in-situ transesterification swap-in, and each reactor pressure of controlled polymerization system and temperature automatic segmentation get rid of the nonpolar mixed solvent of lower boiling, forms the polymer modified styrene resin of various structures;
3) with step 2) polymer modified styrene resin that forms removes the polymer modified styrene resin that a small amount of unreacted monomer and thinner obtain various structures under 160-220 ℃ and 5-50Kpa vacuum condition.
2, according to the preparation method with polymer modified styrene resin of claim 1, it is characterized in that the preparation of the base polymer of various structures in the described step 1) comprises:
1. add conjugated diene and prepare homopolymer;
Or after 2. adding conjugate diene polymerization, the coupling agent that adds again with respect to per 100 molar part polymkeric substance, 5～60 molar part carries out coupling or part linked reaction, prepares star-like or multimodal homopolymer;
Or 3. add conjugated diene and vinyl-arene prepares multipolymer, wherein the mol ratio of conjugated diene and vinyl-arene is 20: 80～95: 5;
Or 4. add after conjugated diene and vinyl-arene prepare copolymer polymerization, the coupling agent that adds again with respect to per 100 molar part polymkeric substance, 5～60 molar part carries out coupling or part linked reaction, prepare star-like or multimodal multipolymer, wherein the mol ratio of conjugated diene and vinyl-arene is 20: 80～90: 10;
Or after 5. adding conjugate diene polymerization, the vinyl-arene continuation polymerization that adds again with respect to per 100 parts by weight polymer, 10～120 weight parts prepares segmented copolymer;
Or after 6. adding conjugate diene polymerization, add again continue polymerization with respect to the vinyl-arene of per 100 parts by weight polymer, 10～120 weight parts after, add that coupling agent with respect to per 100 molar part polymkeric substance, 5～60 molar part carries out coupling or the part linked reaction prepares star block copolymer or multimodal segmented copolymer;
Or after 7. adding conjugated diene and vinyl aromatic (co) polymerized hydrocarbon, wherein the mol ratio of conjugated diene and vinyl-arene is 20: 80～90: 10, add vinyl-arene again, continue polymerization, the preparation segmented copolymer with respect to per 100 parts by weight polymer, 10～120 weight parts;
Or after 8. adding conjugated diene and vinyl aromatic (co) polymerized hydrocarbon, wherein the mol ratio of conjugated diene and vinyl-arene is 20: 80～90: 10, add again continue polymerization with respect to the vinyl-arene of per 100 parts by weight polymer, 1～100 weight part after, add that coupling agent with respect to per 100 molar part polymkeric substance, 5～60 molar part carries out coupling or the part linked reaction prepares segmented copolymer star-like or the multimodal multipolymer;
In described step 2) in, adding described monomer component is following monomer or monomer mixture:
1. with respect to every weight part base polymer 2～35 parts by weight of ethylene base aromatic monomers;
Or the monomeric mixture of 2. forming by following ratio with respect to every weight part base polymer 2～35 weight parts:
The vinyl aromatic monomer of 20～80 weight parts and
20～80 weight parts (methyl) alkyl acrylate monomer;
Or the monomeric mixture of 3. forming by following ratio with respect to every weight part base polymer 2～35 weight parts:
The vinyl aromatic monomer of 60～90 weight parts and
10～40 weight part α-Jia Jibenyixidantis;
Or the monomeric mixture of 4. forming by following ratio with respect to every weight part base polymer 2～35 weight parts:
The vinyl aromatic monomer of 40～90 weight parts and
10～60 weight part maleic anhydride monomers;
Or the monomeric mixture of 5. forming by following ratio with respect to every weight part base polymer 2～35 weight parts:
The vinyl aromatic monomer of 40～90 weight parts and
10～60 weight part N-phenylmaleimide monomers;
Or the monomeric mixture of 6. forming by following ratio with respect to every weight part base polymer 2～35 weight parts:
The vinyl aromatic monomer of 60～98 weight parts and
2～40 parts by weight of acrylonitrile are monomer;
Or the monomeric mixture of 7. forming by following ratio with respect to every weight part base polymer 2～35 weight parts:
The vinyl aromatic monomer of 8～80 weight parts and
10～90 weight parts (methyl) alkyl acrylate monomer and
2～40 parts by weight of acrylonitrile are monomer;
Or the monomeric mixture of 8. forming by following ratio with respect to every weight part base polymer 2～35 weight parts:
The vinyl aromatic monomer of 30～90 weight parts and
10～40 weight part α-Jia Jibenyixidantis and
2～40 parts by weight of acrylonitrile are monomer;
Or the monomeric mixture of 9. forming by following ratio with respect to every weight part base polymer 2～35 weight parts:
The vinyl aromatic monomer of 45～90 weight parts and
2～30 weight part unsaturated carboxylic acid anhydride monomers and
2～40 parts by weight of acrylonitrile are monomer;
Or the monomeric mixture of 10. forming by following ratio with respect to every weight part base polymer 2～35 weight parts:
The vinyl aromatic monomer of 20～93 weight parts and
5～60 weight part maleimide monomers and
2～50 parts by weight of acrylonitrile are monomer.
3, according to the preparation method with polymer modified styrene resin of claim 1, it is characterized in that the mixture that described lower boiling nonpolar mixed solvent is hexanaphthene, hexane, pentane, butane or pentamethylene:
Described lithium or hydrocarbyl lithium initiator are selected from the family of lithium alkylide, thiazolinyl lithium, lithium aryl, cycloalkyl lithium, ring lithium aryl, and wherein carbonatoms is 1-10 in the alkyl;
Described conjugated diene is divinyl, isoprene, 1,3-pentadiene or its mixture;
Described vinyl-arene be vinylbenzene, alpha-methyl styrene, neighbour-vinyl toluene, p-methylstyrene ,-vinyl toluene, ethyl styrene, different-butylstyrene, tert-butyl vinylbenzene or its mixture;
Described coupling agent is two or many vinyl aromatic compounds; Two or polyepoxide; Two or polyisocyanates; Two or many imines; Two or many aldehyde; Two or many ketone; Two or polyhalogenide; Single, two or the polyacid acid anhydride; Single, two or polyester;
Described graft copolymerization evocating agent is organo-peroxide or azo-compound;
Described (methyl) alkyl acrylate monomer be methyl methacrylate, Jia Jibingxisuanyizhi, just-butyl methyl acrylate, 2-methyl ethylhexyl acrylate, 2-ethylhexyl acrylate or its mixture;
Described acrylic monomer is one or more in vinyl cyanide, methacrylonitrile, the ethyl acrylonitrile;
Described unsaturated carboxylic acid anhydride monomer is one or more in cis-1, propylenedicarboxylic acid acid anhydride, the citraconic anhydride;
Described maleimide monomer be maleimide, N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide, N-octyl group maleimide, N-sec.-propyl maleimide, N-phenylmaleimide, N-right-in the bromo-phenyl maleimide, N-neighbour-chloro-phenyl maleimide one or more;
Described thinner is ethylbenzene, toluene or butanone.
4, according to the preparation method with polymer modified styrene resin of claim 3, it is characterized in that described conjugated diolefine is divinyl or isoprene; Described hydrocarbyl lithium initiator is a butyllithium; Described vinyl-arene is vinylbenzene or a-vinyl toluene; Described organo-peroxide is 1,1-two (tert-butyl peroxide)-3,3,5-trimethyl-cyclohexane, peroxidation two-tert-butyl, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane, dibenzoyl peroxide, tert-butyl peroxidation sec.-propyl carbonic ether or pimelinketone superoxide; Described azo-compound is 2,2 '-Diisopropyl azodicarboxylate; Described coupling agent is epoxidised soybean oil, epoxidized polybutadiene, Vinylstyrene or SiCl
4Described acrylic monomer is a vinyl cyanide; Described (methyl) alkyl acrylate monomer is methyl methacrylate or n-BMA; Described unsaturated carboxylic acid anhydride monomer is a MALEIC ANHYDRIDE.
5, according to claim 1 with the preparation method of polymer modified styrene resin, it is characterized in that base polymer comprises: homopolymer, random copolymers, pure segmented copolymer, part statistic copolymer, form cumulative segmented copolymer, segmented copolymer, star-type polymer and multimodal distribution polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101152375A CN100558776C (en) | 2005-11-11 | 2005-11-11 | A kind of preparation method of polymer modified styrene resin for energy saving |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101152375A CN100558776C (en) | 2005-11-11 | 2005-11-11 | A kind of preparation method of polymer modified styrene resin for energy saving |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1772783A CN1772783A (en) | 2006-05-17 |
| CN100558776C true CN100558776C (en) | 2009-11-11 |
Family
ID=36759936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101152375A Active CN100558776C (en) | 2005-11-11 | 2005-11-11 | A kind of preparation method of polymer modified styrene resin for energy saving |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100558776C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628952A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Monovinylarene-conjugated diene copolymer, preparation method and application thereof |
| TWI504661B (en) * | 2013-11-19 | 2015-10-21 | Chi Mei Corp | Block copolymer composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804615B (en) * | 2012-11-06 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of polarity diene polymer and preparation method thereof |
| CN114075431B (en) * | 2020-08-17 | 2023-10-13 | 中石化石油工程技术服务有限公司 | Weak cross-linked polymer for plugging oil-based drilling fluid and preparation method thereof |
| CN113416288A (en) * | 2021-06-01 | 2021-09-21 | 广东众和化塑股份公司 | Preparation method of environment-friendly gel-free grafted diene polymer |
-
2005
- 2005-11-11 CN CNB2005101152375A patent/CN100558776C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628952A (en) * | 2013-11-12 | 2015-05-20 | 中国石油化工股份有限公司 | Monovinylarene-conjugated diene copolymer, preparation method and application thereof |
| CN104628952B (en) * | 2013-11-12 | 2017-06-06 | 中国石油化工股份有限公司 | Monovinylarene and conjugated diene copolymer and its preparation method and application |
| TWI504661B (en) * | 2013-11-19 | 2015-10-21 | Chi Mei Corp | Block copolymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1772783A (en) | 2006-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100558776C (en) | A kind of preparation method of polymer modified styrene resin for energy saving | |
| US8378026B2 (en) | Transparent rubber modified styrene resin and method for preparing the same by continuous bulk polymerization | |
| JP2012505960A (en) | Ethylene copolymer with excellent impact resistance | |
| WO2013069077A1 (en) | Method for producing styrene-based resin composition comprising highly branched ultra-high-molecular-weight polymer, and composition | |
| US4242469A (en) | Controlling grafted elastomers in blends with resinous copolymers | |
| JPS5840970B2 (en) | Styrenic copolymer and its manufacturing method | |
| US6506846B1 (en) | Method for producing impact-resistant modified thermoplastic moulding materials | |
| KR100604087B1 (en) | Continuous Process of Preparing High-Flow and High-Gloss Rubber-Modified Styrenic Resin | |
| KR100751020B1 (en) | Continuous Polymerization Process of High Impact Polystyrene Resin with High Heat Resistance and High Gloss and High Falling Dart Impact | |
| KR101250229B1 (en) | High impact polystyrene resin with high heat resistance and method for preparing the same | |
| Scheirs | Historical overview of styrenic polymers | |
| CN101838379A (en) | High-impact polystyrene and preparation method thereof | |
| KR100543926B1 (en) | Continuous Process for Preparing High Impact Polystyrene Resin | |
| KR100650915B1 (en) | Continuous polymerization process for high impact polystyrene resin | |
| CN102482443A (en) | High impact polymers and methods of making and using same | |
| KR100829850B1 (en) | Continuous bulk polymerization process of rubber-modified transparent styrenic resin having uniform composition, good transparency and high impact strength | |
| JPH09143322A (en) | Styrene resin composition | |
| JPH08269142A (en) | Transparent rubber-modified styrene-based resin composition | |
| CN1325527C (en) | Heat-proof impact-resistant thermoplastic resin continuous preparation method | |
| CN102558466B (en) | Synthesis method of transparent block copolymer | |
| JP2006249446A (en) | Method for producing transparent, impact-resistant styrene-based resin composition | |
| CN106543341B (en) | A method of preparing EVA elastomer | |
| KR100587650B1 (en) | Continous Polymerization Process of Rubber-Modified Styrenic Resin with Good Falling Dart Impact | |
| KR20240027601A (en) | Process for manufacturing vinyl aromatic polymer | |
| KR100587648B1 (en) | Continous Polymerization Process of High Impact Polystyrene Resin with Good High Gloss and Falling Dart Impact |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 210005 No. 9, Tianquan Road, Qilin street, Jiangning District, Nanjing City, Jiangsu Province Patentee after: JIANGSU SHENGJIE INDUSTRY Co.,Ltd. Address before: 211135, Jiangsu, Nanjing province Jiangning District, Tangshan Road, Kirin Road, No. 60, science and technology innovation center, South first floor Patentee before: JIANGSU SHENGJIE INDUSTRY Co.,Ltd. |