CN101851321B - Terpolymer resin and preparation method thereof - Google Patents
Terpolymer resin and preparation method thereof Download PDFInfo
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- CN101851321B CN101851321B CN2009100488531A CN200910048853A CN101851321B CN 101851321 B CN101851321 B CN 101851321B CN 2009100488531 A CN2009100488531 A CN 2009100488531A CN 200910048853 A CN200910048853 A CN 200910048853A CN 101851321 B CN101851321 B CN 101851321B
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- 229920001897 terpolymer Polymers 0.000 title claims abstract description 30
- 239000011347 resin Substances 0.000 title claims abstract description 28
- 229920005989 resin Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 157
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000001506 calcium phosphate Substances 0.000 claims description 13
- 235000011010 calcium phosphates Nutrition 0.000 claims description 13
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 20
- 238000006116 polymerization reaction Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 3
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- 125000000524 functional group Chemical group 0.000 abstract description 2
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- 238000003912 environmental pollution Methods 0.000 abstract 1
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- 239000004033 plastic Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 14
- 239000000126 substance Substances 0.000 description 10
- 150000002924 oxiranes Chemical group 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
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- 238000005516 engineering process Methods 0.000 description 6
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- 238000011160 research Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
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- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- 239000002351 wastewater Substances 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention relates to a terpolymer resin and a preparation method thereof. The terpolymer resin comprises the following components in percentage by weight: 50 to 85 percent of vinyl aromatic monomer, 10 to 40 percent of acrylonitrile monomer, and 0.5 to 30 percent of glycidyl methacrylate (GMA), and is prepared by suspension polymerization. Compared with the prior art, the terpolymer resin has the content of the glycidyl methacrylate close to the addition of the glycidyl methacrylate, direct polymerization is carried out, epoxy functional groups are introduced, the components of the copolymer are easy to control, the production cost is low, water is taken as a medium in the reaction, environmental pollution is reduced, and the copolymer can be used as a chain extender of plastics (such as PA, PC, PET, PBT and the like), a delustering agent of alloys (such as PC/ABS, PBT/ABS and the like) and a compatilizer of alloys (such as ABS/PBT, ABS/PET and the like). The terpolymer resin and the preparation method have the advantages of reasonable process, convenient use, low cost and the like.
Description
Technical field
The present invention relates to technical field of polymer materials; Relate in particular to a kind of terpolymer resin and preparation method thereof, be specifically related to a kind of terpolymer resin and preparation technology thereof who forms by aromatic vinyl monomer, acrylic monomer and SY-Monomer G copolymerization.
Background technology
As everyone knows, (Glycidyl Methacrylate was GMA) because its intramolecularly had both contained carbon-carbon double bond to the monomer SY-Monomer G; Contain epoxide group again; So both can carry out the free radical type reaction, can carry out the reaction of ionic type again, therefore have very high reactive behavior.Active epoxide group; As a kind of function monomer; Normal and other monomers carry out copolymerization, the polymeric microball material that preparation has various functions, or directly utilize the surperficial epoxide group of copolymer microsphere as functional group; Make further macromolecular reaction, preparation contains the micro-sphere material of other function monomers.
The polymer microballoon that contains GMA is of many uses in various fields, but traditional research and Application Areas mainly concentrate on:
1, synthesizes the aspect, mainly be used as the comonomer of reactive thermoplastic elastic and thermosetting acrylic coating resin.
2, modification aspect is mainly used in multiple coating, tackiness agent, the properties-correcting agent of polyblend.
Like the thermosetting acrylic coating of modification, polyvinyl chloride coating, these coating such as Synolac all have better water tolerance and film-forming properties.And the tackiness agent of modification and non-woven fabrics coating cementability, water tolerance and solvent resistance are better.In paint field, SY-Monomer G belongs to the bigger function monomer of oiliness, can be well and other acrylate monomer copolymerization, and such monomeric content and distribution are easy to control in polymkeric substance, can be made into various acrylic powder coating.
3, field of medicaments can be used as separating medium or caking agent.As can be used for separation and the drug release or the like of carrier, chromatographic stationary phase, polymeric adsorbent, the biomacromolecule of immobilization, the catalyzer of biologically active substance.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of preparation technology terpolymer resin reasonable, easy to use, with low cost and preparation method thereof to be provided.
The object of the invention can be realized through following technical scheme: a kind of terpolymer resin is characterized in that this terpolymer resin comprises following component and content:
Aromatic vinyl monomer 50wt%～85wt%;
Acrylic monomer 10wt%～40wt%;
SY-Monomer G (GMA) 0.5wt%～30wt%.
The number-average molecular weight of described terpolymer resin is that the melt index of 50000～90000,235 ℃/2.16kg is 5～15g/10min.
Described aromatic vinyl monomer comprises styrenic monomers, and described acrylic monomer comprises acrylonitrile monemer or Alpha-Methyl acrylonitrile monemer, and the consumption of described SY-Monomer G (GMA) is 2wt%～25wt%.
Described styrenic monomers comprises styrene monomer, α-Jia Jibenyixidanti, α-chloro-styrene monomer or p-vinyl toluene monomer; Described acrylic monomer is an acrylonitrile monemer, and the consumption of described SY-Monomer G (GMA) is 2wt%～20wt%.
Described styrenic monomers is a styrene monomer.
A kind of preparation method of terpolymer resin is characterized in that, this method adopts suspension polymerization process, may further comprise the steps:
(1) be 100% to do benchmark with total monomer weight; With the part of the part of aromatic vinyl monomer 50wt%～85wt%, acrylic monomer 10wt%～40wt%, molecular weight regulator 0.1wt%～1wt%, oil-soluble initiator 0.1wt%～1wt%, dispersion agent 0.1wt%～3wt%, dispersion aids 0.001wt%～0.1wt%, with the total monomer weight ratio be that 1～2.5: 1 deionized water is mixed in the reaction kettle; Under stirring, be warming up to 65～80 ℃, reacted 0.5～2 hour;
(2) remaining aromatic vinyl monomer, acrylic monomer and the SY-Monomer G (GMA) that accounts for monomer total amount 0.5wt%～30wt% are mixed, and in 0.5～2 hour, drip in aforesaid reaction vessel;
(3) continue reaction 0.5～3 hour again, be warming up to 95 ℃ of slakings 0.5～2 hour;
(4) discharging is in stock chest, filters and with washed with de-ionized water 1～5 time, the gained filter cake is dried to constant weight under 90 ℃, sieves, and obtains terpolymer resin.
Described total monomer weight is the weight sum of aromatic vinyl monomer, acrylic monomer and SY-Monomer G (GMA).
Described molecular weight regulator is a lauryl mercaptan; Described oil-soluble initiator is Diisopropyl azodicarboxylate (AINBN) or Di Cumyl Peroxide 99 (DCP); Described dispersion agent comprises organic dispersing agent and inorganic dispersant, and the consumption of organic dispersing agent is the 0.1wt%～0.5wt% of monomer total amount, and the consumption of inorganic dispersant is the 0.8wt%～1.5wt% of monomer total amount; Described dispersion aids is X 2073 (DP) or sodium lauryl sulphate (DBS).
Described dispersion agent is active calcium phosphate (TPC), Natvosol (CMC) or Z 150PH (PVA).
Described dispersion agent is active calcium phosphate (TPC).
Compared with prior art, terpolymer resin of the present invention adopts the suspension method preparation, and suspension polymerization is to be prepared one of important method of superpolymer by vinyl monomer; Because water is a dispersion medium; Heat of polymerization can be got rid of rapidly, thereby temperature of reaction controls easily, and production technique is simple; The finished product of processing is the homogeneous granules shape, but product is without processing of granulation straight forming and application.
Suspension polymerization process of the present invention at first is dissolved in the monomer phase with initiator, regulator, and monomer then is scattered in the dispersion medium water under strong the shearing mutually, and monomer droplet constitutes disperse phase, and water constitutes external phase.The monomer (drop) that is in disperse phase is with final very low usually by the solvability of its polymkeric substance that forms and dispersion medium (external phase).The volume(tric)fraction of monomer phase (or disperse phase) is usually at 0.1-0.5.
Polyreaction can be carried out under low volume parts, but too low volume parts can cause productive rate too low.Under the high volume parts, external phase is not enough to fill the space between the dispersive drop very little.Because monomer droplet is not separated fully, add polymer particle like this because before the polymerization single polymerization monomer unreacted finishes, the very soft not sclerosis of particle, being easy to be sticked together causes the implode reaction to take place.Under the standard state, because the existence of disperse phase is fully and each other isolated, polymerization is just independently carried out radical polymerization in drop inside at each to drop to each other.
The suspension polymerization process generally is that monomer is dispersed into drop under shearing action; Stable suspersion adopts oil-soluble initiator in aqueous dispersant, in drop, carry out polymerization; Each monomer droplet is similar to the mass polymerization system; Its polymeric chemical is identical with mass polymerization, and aspect the requiring of reactor drum, suspension polymerization general requirement reactor drum has functions such as the dispersion of shearing, circulation mixing, heat transfer and suspension.Terpolymer polymerization mixing speed specific to this research is not high more good more, and the effect that is stirred in the suspension polymerization has two aspects, is on the one hand to shear to disperse, and then owing to stir the turbulent flow that produces, can cause the coalescence of drop on the other hand.At the suspension polymerization initial stage, there is a disperse phase stable region, that is to say that in a suitable mixing speed scope, dispersant liquid drop is in a kind of steady state, and is too high or too low, dispersed phase drop is all unstable.If at the beginning, disperse phase is just unstable, proceeds to system viscosity in polymerization and increases, and when coalescence is preponderated, certainly will lump, and causes the system unstability and implode, and this situation especially mostly occurs under the suspension agent activity is not very high situation.
The oar type of polymeric kettle with oblique oar and turbine oar for well, 3L polymeric kettle mixing speed with 400～600rpm for well.The amplification of suspension polymerization is a criterion with specific volume power Pv and cycle index Nc generally.On the basis of 3L polymeric kettle test-results, be amplified criterion with Pv, in conjunction with the lot of test experience, the mixing speed of confirming the 30L polymeric kettle is 180～220rpm.
Suspension polymerization also need add the few stable agent usually, adheres to each other to stop the small droplets that constantly increases in the polymerization process medium viscosity, and polymkeric substance is disperseed with round granular, keeps polymerization system stable.Initial emulsive drop and both distribution of sizes of polymer beads that form thus just depend on the balance between this two states of fusion of division and drop of drop.And this balance is controlled by the type of stirring rake conversely, velocity of shear, and the kind of used stablizer and concentration.
Generally speaking; Suspension polymerization comes down to by means of the stronger stirring and the effect of suspension agent, with monomer be dispersed in the immiscible medium of monomer in, monomer carries out mass polymerization with the form of small droplets; In each small droplets, monomeric polymerization process is similar with mass polymerization.Because monomer stirs under the dual function with suspension agent in brute force in system and is dispersed into tiny drop, so suspension polymerization has its unique distinction again, and promptly area of dissipation is big, so solved difficult problem of dispelling the heat in mass polymerization.Shortcoming is that the reply final product separates, cleans, and just can obtain the higher granulated polymer of purity owing to adopt dispersion agent.
Suspension polymerization is when transformation efficiency 20% left and right sides, and monomer-polymkeric substance drop surfaces of tacky bonds easily, therefore also needs the dispersion agent of capacity, the protection of water medium.
Dispersion agent has play a part so just, and the dispersion process diagram of dispersion agent is as shown in Figure 1.
The mechanism of action of suspension dispersive agent is following:
1, adsorbs or is distributed in the surface of monomer droplet or polymer beads; The polymer beads that makes monomer droplet or polymerization formation is before unhardened; Effectively isolate through dispersant layer; Avoid monomer droplet or polymer particle to be bonded together, cause that system viscosity sharply rises, cause temperature of reaction implode out of control.
2, the dispersion agent of polymer forms adsorption layer on the surface of polymer beads, and the polymer beads surface electric charge is increased, and improves the intergranular reactive force that forms editsteric hindrance.
The suspension polymerization that the monomer oil phase carries out in water; Typical stablizer has following several kinds: Z 150PH-vinyl acetate (hydrolysate of Z 150PH acetic ester 80-90%); Vinylpyrrolidone polymer; Polyacrylate, ether of cellulose and natural gum and inorganics such as calcium phosphate, lime carbonate, nanometer breeze etc.The used suspension agent of suspension polymerization is divided into inorganic and organic two kinds, according to practical experience, and the suspension polymerization of styrenic monomers, optimal suspension agent is the combination of calcium phosphate and X 2073.
The present invention has used the dispersion agent that accounts for monomer total amount 0.1～3%, recommends to use the consumption that accounts for monomer total amount 0.1～0.5% when adopting organic dispersing agent, and when using inorganic dispersant with between 0.8～1.5% for well.
The present invention preferably accounts for the active calcium phosphate of monomer total amount 0.8～1.5% and makes the polymeric dispersion agent.
Dispersion aids of the present invention is one of X 2073 (DP) or sodium lauryl sulphate (DBS) etc.; Consumption is recommended to account for monomer total amount 0.001～0.1% and is got final product; Do not have the effect of dispersion aids very little; Many then to monomer emulsification transition, the polymer particle of formation is too little, causes product yield to reduce.
The consumption of initiator all has considerable influence to polymerization rate and product property, and the oil-soluble initiator that invention is used can be one of Diisopropyl azodicarboxylate (AIBN) or Di Cumyl Peroxide 99 (DCP) etc., and its consumption preferably accounts for monomer total amount 0.1～1%.
Molecular weight regulator, promptly chain-transfer agent is through chain transfer reaction high molecular molecular chain length to be shortened, thereby plays the effect of regulating molecular weight, its consumption preferably accounts for monomer total amount 0.1～1%.
The copolyreaction temperature directly influences the performance of polymerization rate and product.The copolyreaction temperature is relevant with selected initiator, and the lowest decomposition temperature of initiator is exactly the minimum of temperature of reaction.The copolyreaction temperature can not be too high, and Tai Gaoyi causes implode.The copolyreaction temperature is not only relevant with speed of response, and influential to gathering rate unexpectedly, that is to say; It not only influences the molecular weight of product; Also influence the molecular structure of product, thereby in the research of processing condition, the copolyreaction temperature is a very important parameter.
The present invention is the polyreaction under the normal pressure situation, selects for use AIBN (Diisopropyl azodicarboxylate) to make initiator, and its transformation period, corresponding time-temperature concerned as follows:
AIBN decomposition temperature: ℃ 82 70 64 60 50
In addition, the boiling point of vinyl cyanide is 78 ℃.
So the optimal reaction temperature that this research is selected is 65～75 ℃, be 5～10 hours corresponding reaction time.
The present invention selects for use the another consideration of suspension method operational path synthesis of ternary multipolymer to be: although continuous bulk can obtain more purified product, and the energy-saving production technology environmental protection, its facility investment is higher; And the emulsion method Production Flow Chart is long, and discharge of wastewater is many, not environmental protection; Suspension method can obtain than the purified product of emulsion method, and the relative emulsion method of waste water that produces wants much less, and technology controlling and process is simple, conducts heat easily, and equipment is ready-made.
At last, terpolymer use cost of the present invention is lower by 1/3rd to 1/2nd than purposes analogous products on the market, has fabulous cost performance, because its molecular weight has also reached the polymkeric substance rank, so the thermal stability problems that do not exist easy to use.
Description of drawings
Fig. 1 is the dispersion process figure of dispersion agent;
Fig. 2 is the molecular weight and the MWD of multipolymer in the embodiment of the invention 1;
Fig. 3 is the infrared spectrum of multipolymer in the embodiment of the invention 1.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed explanation, wherein prepare percentage ratio in the example for being benchmark, i.e. the monomer total amount with vinylbenzene+vinyl cyanide+GMA=100 weight part.
Also have, the molecular weight of terpolymer uses GPC (GPC) analysis and characterization, and structure elucidation uses infrared spectroscopy (IR method).
With the vinylbenzene that accounts for monomer total amount 50.0%, account for monomer total amount 36.0% vinyl cyanide, account for monomer total amount 0.3% whole molecular weight regulator lauryl mercaptans, account for monomer total amount 0.2% whole oil-soluble initiator Diisopropyl azodicarboxylates, account for monomer total amount 1.5% whole dispersion agent active calcium phosphates, account for monomer total amount 0.01% whole dispersion aids X 2073es and with the total monomer weight ratio be that 1.5: 1 deionized water is mixed in the reaction kettle; With stir under be warming up to 65～80 ℃; Reacted 0.5 hour; After will accounting for the vinylbenzene of monomer total amount 8.0%, the SY-Monomer G (GMA) that accounts for the vinyl cyanide of monomer total amount 4% and account for monomer total amount 2% again and mixing; In 2 hours; Drip continuously in reaction kettle, continue reaction 1 hour, be warming up to 95 ℃ of slakings 1 hour again.Discharging is filtered in stock chest and with washed with de-ionized water 3 times, then products therefrom is dried to constant weight under 90 ℃ then, sieve at last the finished product terpolymer resin.
Product yield 94.6%, number-average molecular weight are 7.09*10
4
Fig. 2 is the molecular weight and the MWD of the terpolymer resin that makes through aforesaid method, and Fig. 3 is the ir spectra of terpolymer resin, can know that by spectrogram the epoxy characteristic group in the polymkeric substance exists.
Among Fig. 3 at 1620～1680cm
-1The zone does not have characteristic peak to occur, and the two keys of no C=C in the polymerisate are described, this proves that on the one hand cinnamic polyreaction is completely, has proved that on the other hand GMA also participates in reaction with two keys.At 1253cm
-1(the symmetric vibration absorption peak of epoxide group), 915cm
-1And 861cm
-1The absorption peak that (two absorption peaks of the asymmetric vibration of epoxide group) are located has shown the existence of epoxide group; 3200～3600cm
-1The zone does not have tangible hydroxyl absorption peak, shows that the epoxide group among the GMA seldom or does not basically have open loop.
In addition, infrared spectrum shows, therefore the not monomeric existence of GMA in the sample can assert tentatively that the GMA monomer when participating in polyreaction, is to carry out polyaddition reaction with the form of opening two keys, forms the multipolymer of vinylbenzene, vinyl cyanide and GMA.
Result from polymericular weight can extrapolate the epoxide group of a SAN molecular chain existence more than 1 simultaneously; And this just this polymkeric substance can make polymer terminal group and its generation ring-opening reactions such as PA, PC, PBT, PET, the basic reason of molecular chain generation branching chain extension.
Embodiment 2
With the vinylbenzene that accounts for monomer total amount 62.2%, account for monomer total amount 20.8% vinyl cyanide, account for monomer total amount 0.3% whole molecular weight regulator lauryl mercaptans, account for monomer total amount 0.2% whole oil-soluble initiator Diisopropyl azodicarboxylates, account for monomer total amount 1.5% whole dispersion agent active calcium phosphates, account for monomer total amount 0.01% whole dispersion aids X 2073es and with the total monomer weight ratio be that 1.5: 1 deionized water is mixed in the reaction kettle; With stir under be warming up to 65～80 ℃; Reacted 0.5 hour; After will accounting for the vinylbenzene of monomer total amount 8.0%, the SY-Monomer G (GMA) that accounts for the vinyl cyanide of monomer total amount 4.0% and account for monomer total amount 5% again and mixing; In 2 hours; Drip in reaction kettle continuously, and then continue reaction 1 hour, be warming up to 95 ℃ of slakings 1 hour again.Discharging is filtered in stock chest and with washed with de-ionized water 3 times, then products therefrom is dried to constant weight under 90 ℃ then, sieve at last the finished product.
Product yield 94.1%, number-average molecular weight are 6.89*10
4
Embodiment 3
With the vinylbenzene that accounts for monomer total amount 60.0%, account for monomer total amount 18.0% vinyl cyanide, account for monomer total amount 0.3% whole molecular weight regulator lauryl mercaptans, account for monomer total amount 0.2% whole oil-soluble initiator Diisopropyl azodicarboxylates, account for monomer total amount 1.5% whole dispersion agent active calcium phosphates, account for monomer total amount 0.01% whole dispersion aids X 2073es and with the total monomer weight ratio be that 1.5: 1 deionized water is mixed in the reaction kettle; With stir under be warming up to 70 ℃; Reacted 0.5 hour; To account for the vinylbenzene of monomer total amount 8.0% again, the SY-Monomer G (GMA) that accounts for the vinyl cyanide of monomer total amount 4.0% and account for monomer total amount 10% was blended in 2 hours; Drip continuously in reaction kettle; And then continue reaction 1 hour, be warming up to 95 ℃ of slakings 1 hour again.Discharging is filtered in stock chest and with washed with de-ionized water 3 times, then products therefrom is dried to constant weight under 90 ℃ then, sieve at last the finished product.
Product yield 93.1%, number-average molecular weight are 5.65*10
4
Embodiment 4
With the vinylbenzene that accounts for monomer total amount 77.0%, account for monomer total amount 6.0% vinyl cyanide, account for monomer total amount 0.3% whole molecular weight regulator lauryl mercaptans, account for monomer total amount 0.2% whole oil-soluble initiator Diisopropyl azodicarboxylates, account for monomer total amount 1.5% whole dispersion agent active calcium phosphates, account for monomer total amount 0.01% whole dispersion aids X 2073es and with the total monomer weight ratio be that 1.5: 1 deionized water is mixed in the reaction kettle; With stir under be warming up to 70 ℃; Reacted 0.5 hour; To account for the vinylbenzene of monomer total amount 8.0% again, the SY-Monomer G (GMA) that accounts for the vinyl cyanide of monomer total amount 4.0% and account for monomer total amount 5.0% was blended in 2 hours; Drip continuously in reaction kettle; And then continue reaction 1 hour, be warming up to 95 ℃ of slakings 1 hour again.Discharging is filtered in stock chest and with washed with de-ionized water 3 times, then products therefrom is dried to constant weight under 90 ℃ then, sieve at last the finished product.
Product yield 94.1%, number-average molecular weight are 5.34*10
4
Embodiment 5
With the vinylbenzene that accounts for monomer total amount 44.5%, account for monomer total amount 13.5% vinyl cyanide, account for monomer total amount 0.3% whole molecular weight regulator lauryl mercaptans, account for monomer total amount 0.2% whole oil-soluble initiator Diisopropyl azodicarboxylates, account for monomer total amount 1.5% whole dispersion agent active calcium phosphates, account for monomer total amount 0.01% whole dispersion aids X 2073es and with the total monomer weight ratio be that 1.5: 1 deionized water is mixed in the reaction kettle; With stir under be warming up to 70 ℃; Reacted 0.5 hour; To account for the vinylbenzene of monomer total amount 8.0% again, the SY-Monomer G (GMA) that accounts for the vinyl cyanide of monomer total amount 4.0% and account for monomer total amount 30% was blended in 2 hours; Drip continuously in reaction kettle; And then continue reaction 1 hour, be warming up to 95 ℃ of slakings 1 hour again.Discharging is filtered in stock chest and with washed with de-ionized water 3 times, then products therefrom is dried to constant weight under 90 ℃ then, sieve at last the finished product.
Product yield 93.7%, number-average molecular weight are 5.08*10
4
Embodiment 6
With the vinylbenzene that accounts for monomer total amount 65.5%, account for monomer total amount 22.0% vinyl cyanide, account for monomer total amount 0.3% whole molecular weight regulator lauryl mercaptans, account for monomer total amount 0.2% whole oil-soluble initiator Diisopropyl azodicarboxylates, account for monomer total amount 1.5% whole dispersion agent active calcium phosphates, account for monomer total amount 0.01% whole dispersion aids X 2073es and with the total monomer weight ratio be that 1.5: 1 deionized water is mixed in the reaction kettle; With stir under be warming up to 70 ℃; Reacted 0.5 hour; To account for the vinylbenzene of monomer total amount 8.0% again, the SY-Monomer G (GMA) that accounts for the vinyl cyanide of monomer total amount 4.0% and account for monomer total amount 0.5% was blended in 2 hours; Drip continuously in reaction kettle; And then continue reaction 1 hour, be warming up to 95 ℃ of slakings 1 hour again.Discharging is filtered in stock chest and with washed with de-ionized water 3 times, then products therefrom is dried to constant weight under 90 ℃ then, sieve at last the finished product.
Product yield 95.7%, number-average molecular weight are 8.24*10
4
Embodiment 7
With the α-Jia Jibenyixidanti that accounts for monomer total amount 25.0%, account for monomer total amount 8.0% vinyl cyanide, account for monomer total amount 0.1% whole molecular weight regulator lauryl mercaptans, account for monomer total amount 0.1% whole oil-soluble initiator Diisopropyl azodicarboxylates (AINBN), account for monomer total amount 0.1% whole dispersion agent Natvosols (CMC), account for monomer total amount 0.1% whole dispersion aids X 2073es (DP) and with the total monomer weight ratio be that 1: 1 deionized water is mixed in the reaction kettle; With stir under be warming up to 65 ℃; Reacted 2 hours; To account for the α-Jia Jibenyixidanti of monomer total amount 25.0% again, the SY-Monomer G (GMA) that accounts for the vinyl cyanide of monomer total amount 4.0% and account for monomer total amount 6.0% was blended in 2 hours; Drip continuously in reaction kettle; And then continue reaction 3 hours, be warming up to 95 ℃ of slakings 0.5 hour again.Discharging is filtered in stock chest and with washed with de-ionized water 1 time then; Then products therefrom is dried to constant weight under 90 ℃; Sieve at last the finished product terpolymer resin, the number-average molecular weight of this terpolymer resin is that the melt index of 50000,235 ℃/2.16kg is 5g/10min.
Embodiment 8
With the α that accounts for monomer total amount 50.0%-chloro-styrene monomer, account for monomer total amount 10% the Alpha-Methyl acrylonitrile monemer, account for monomer total amount 1% whole molecular weight regulator lauryl mercaptans, account for monomer total amount 1% whole oil-soluble initiator Di Cumyl Peroxide 99s (DCP), account for monomer total amount 0.5% whole polyethylene of dispersing agent alcohol (PVA), account for monomer total amount 0.001% whole dispersion aids sodium lauryl sulphate (DBS) and with the total monomer weight ratio be that 2.5: 1 deionized water is mixed in the reaction kettle; With stir under be warming up to 80 ℃; Reacted 0.5 hour; To account for the α-chloro-styrene monomer of monomer total amount 10.0% again, the SY-Monomer G (GMA) that accounts for the Alpha-Methyl acrylonitrile monemer of monomer total amount 5.0% and account for monomer total amount 3.0% was blended in 0.5 hour; Drip continuously in reaction kettle; And then continue reaction 0.5 hour, be warming up to 95 ℃ of slakings 2 hours again.Discharging is filtered in stock chest and with washed with de-ionized water 5 times then; Then products therefrom is dried to constant weight under 90 ℃; Sieve at last the finished product terpolymer resin, the number-average molecular weight of this terpolymer resin is that the melt index of 90000,235 ℃/2.16kg is 15g/10min.
Above-mentioned dispersion agent comprises organic dispersing agent and inorganic dispersant, and the consumption of organic dispersing agent is the 0.1wt%～0.5wt% of monomer total amount, and the consumption of inorganic dispersant is the 0.8wt%～1.5wt% of monomer total amount.
Account within the gross weight 0.5～30% according to mentioned above principle GMA consumption, all belong to category of the present invention, and the GMA content 0.5～5% o'clock compatilizer that is used as two kinds of polymkeric substance preferably, and its consumption is better with 0.5～5%; GMA content 5～30% is o'clock preferably as chainextender, and its chain extension effect is being 0.1～0.5% o'clock most pronounced effects with the conversion of epoxy group; The GMA content 1～10% o'clock matting agent as polymkeric substance or its alloy preferably, preferable amount 2～5%, more preferably 3～6% consumption.
Above-mentioned preparation example is only explained ter-polymers of the present invention and preparation technology thereof, but they can not limit protection scope of the present invention.To its any modification and variation of doing, all is according to spirit of the present invention and thought within the scope of patent claim requirement protection of the present invention.
Claims (3)
1. the preparation method of a terpolymer resin, this terpolymer resin comprises following component and content:
Aromatic vinyl monomer 50wt%～85wt%;
Acrylic monomer 10wt%～40wt%;
SY-Monomer G (GMA) 0.5wt%～30wt%
It is characterized in that this method adopts suspension polymerization process, may further comprise the steps:
(1) be 100% to do benchmark with total monomer weight; With the part of the part of aromatic vinyl monomer 50wt%～85wt%, acrylic monomer 10wt%～40wt%, molecular weight regulator 0.1wt%～1wt%, oil-soluble initiator 0.1wt%～1wt%, dispersion agent 0.1wt%～3wt%, dispersion aids 0.001wt%～0.1wt%, with the total monomer weight ratio be that 1～2.5: 1 deionized water is mixed in the reaction kettle; Under stirring, be warming up to 65～80 ℃, reacted 0.5～2 hour;
(2) remaining aromatic vinyl monomer, acrylic monomer and the SY-Monomer G (GMA) that accounts for monomer total amount 0.5wt%～30wt% are mixed, and in 0.5～2 hour, drip in aforesaid reaction vessel;
(3) continue reaction 0.5～3 hour again, be warming up to 95 ℃ of slakings 0.5～2 hour;
(4) discharging is in stock chest, filters and with washed with de-ionized water 1～5 time, the gained filter cake is dried to constant weight under 90 ℃, sieves, and obtains terpolymer resin;
Described molecular weight regulator is a lauryl mercaptan; Described oil-soluble initiator is Diisopropyl azodicarboxylate (AINBN) or Di Cumyl Peroxide 99 (DCP); Described dispersion agent comprises organic dispersing agent and inorganic dispersant, and the consumption of organic dispersing agent is the 0.1wt%～0.5wt% of monomer total amount, and the consumption of inorganic dispersant is the 0.8wt%～1.5wt% of monomer total amount; Described dispersion aids is X 2073 (DP) or sodium lauryl sulphate (DBS); Described dispersion agent is active calcium phosphate (TPC), Natvosol (CMC) or Z 150PH (PVA).
2. the preparation method of terpolymer resin according to claim 1 is characterized in that, described total monomer weight is the weight sum of aromatic vinyl monomer, acrylic monomer and SY-Monomer G (GMA).
3. the preparation method of terpolymer resin according to claim 1 is characterized in that, described dispersion agent is active calcium phosphate (TPC).
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| CN102443253B (en) * | 2011-09-20 | 2013-06-05 | 贵州省复合改性聚合物材料工程技术研究中心 | Method for one-step preparation of super-tough polybutylene terephthalate |
| CN102492076A (en) * | 2011-12-06 | 2012-06-13 | 深圳市科聚新材料有限公司 | Compatilizer, preparation method thereof and engineering plastics using compatiblizer |
| CN102604352B (en) * | 2012-01-18 | 2016-05-18 | 上海锦湖日丽塑料有限公司 | Containing regeneration PC and regenerative PET halogen-free fire-proof resin composition and preparation method |
| CN105254789B (en) * | 2015-10-20 | 2019-02-05 | 佳易容相容剂江苏有限公司 | A kind of copolymerzation with cross-linking resin and preparation method thereof |
| KR101940038B1 (en) * | 2015-11-30 | 2019-01-18 | 주식회사 엘지화학 | Transparent thermoplastic resin and method for preparing the resin |
| CN105566839B (en) * | 2016-02-01 | 2018-04-17 | 佳易容相容剂江苏有限公司 | A kind of high-performance anti-aging ABS/GF composite materials and preparation method thereof |
| CN105924557A (en) * | 2016-05-16 | 2016-09-07 | 佳易容相容剂江苏有限公司 | Long-chain branch copolymer resin and preparation method thereof |
| CN108314761A (en) * | 2018-02-12 | 2018-07-24 | 金发科技股份有限公司 | A kind of graft copolymer and its preparation method and application containing reactive group |
| CN109293825A (en) * | 2018-08-30 | 2019-02-01 | 铨盛聚碳科技股份有限公司 | A kind of compatilizer and preparation method thereof with high-content epoxy group |
| CN111303438B (en) * | 2020-04-07 | 2022-03-01 | 嘉兴华雯化工股份有限公司 | Delustering agent for ABS (acrylonitrile butadiene styrene), PC (polycarbonate)/ABS (acrylonitrile butadiene styrene) alloy and preparation method thereof |
| CN111607183B (en) * | 2020-06-08 | 2022-05-13 | 张家港威迪森化学有限公司 | Styrene-acrylic copolymer resin and preparation method and application thereof |
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