CN1528798A - Maleic anhydride graft styrene-butadiene-styrene solvent heat-synthesizing method - Google Patents
Maleic anhydride graft styrene-butadiene-styrene solvent heat-synthesizing method Download PDFInfo
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- CN1528798A CN1528798A CNA2003101079417A CN200310107941A CN1528798A CN 1528798 A CN1528798 A CN 1528798A CN A2003101079417 A CNA2003101079417 A CN A2003101079417A CN 200310107941 A CN200310107941 A CN 200310107941A CN 1528798 A CN1528798 A CN 1528798A
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Abstract
The invention provides a solvent synthesis method of maleic anhydride graft styrene-butadiene -styrene, placing styrene-butadiene-styrene resin (SBS), maleic anhydride, initiator and comonomer in high pressure kettle to dissolve in solvent, reacting at a certain temperature and in a certain time, and then washing and drying to obtain SBS-maleic anhydride graft copolymer. It is simple, has high grafting rate and convenient for large-scale production. The prepared SBS-g-MAH is used in the compatilizer of the mixture of SBS with polycarbonate, polyester, nylon, polyurethane, polyvinyl chloride and so on.
Description
Technical field:
The present invention relates to a kind of maleic anhydride graft styrene-butadiene-styrene solvent process for thermosynthesizing, relate in particular to a kind of solvent thermal synthesis method that in autoclave, adopts and prepare the method for styrene-butadiene-styrene block copolymer (the SBS)-maleic anhydride graft copolymer (SBS-g-MAH) of functionalization.The invention belongs to the polymer science field.
Background technology:
The SBS resin is to be basic synthetic ternary block polymer by divinyl (B) and two kinds of monomers of vinylbenzene (S).The SBS resin is a kind of rubber elastomer, and except that as the rubber applications, it is by widely as the plasticized modifier of plastics.But because it is nonpolar material, poor with polarity plastics such as consistencies such as nylon, polyester, as directly unsatisfactory as the plasticized modifier effect of polarity plastics.In order to improve the consistency of it and other plastics, often must add compatilizer to reduce particle diameter, reduce interfacial tension, make alternate can mixing, with better its performance of improving.The compatilizer of SBS co-mixing system commonly used has: the multipolymer of maleic anhydride graft SBS, vinylbenzene and maleic anhydride, vinylbenzene and Sipacril 2739OF, vinylbenzene and methylmethacrylate copolymer, vinylbenzene and glycidyl methacrylate copolymer, methyl methacrylate and glycidyl methacrylate copolymer etc.Wherein maleic anhydride graft SBS has been because performance has kept the performance of SBS substantially, is compatilizer preferably, does compatilizer and is of practical significance very much so prepare the SBS of functionalization.(DavidD.Jiang, Charles A.Wilkie, Journal of Polymer Science such as Jiang, Part A:PolymerChemistry, 35,1997,965-972) and (M.Fischer, G.P.Hellmann, Polymer such as Fischer, 37,1996,4547-4554) with grafting solution method maleic anhydride (MAH), Lee and Chen (Wen-Fu Lee, Ying-Jou Chen, J.Appl.Polym.Sci., 82,2001,2641-2650) use the grafting solution method N-isopropylacrylamide.Grafting solution method rate higher (3-8%wt), but reaction conditions and device more complicated, solvent load is big, is difficult to reclaim, and is not easy to scale operation.Wilhelm and Felisberti (Helena Maria Wilhelm, Maria Isabel Felisberti, J.Appl.Polym.Sci., 83,2002,2953-2960) with the reaction of HAAKE Banbury mixer research SBS fusion-grafting maleic anhydride (MAH), melting graft reaction is simple, and is fully mixed but reactant is difficult to, react also inhomogeneous, percentage of grafting is also lower, is lower than 3.5%wt, and is easy to crosslinked.
Summary of the invention:
The objective of the invention is to above-mentioned defective at prior art, a kind of maleic anhydride graft styrene-butadiene-styrene solvent process for thermosynthesizing is provided, and the percentage of grafting that the function SBS multipolymer of preparation is obtained is higher, and solvent load is few, equipment is simple, is convenient to scale operation.
For realizing such purpose, in technical scheme of the present invention, the preparation method's reaction mechanism that adopts is different from the past solution method or scorification prepares graft copolymer, SBS resin and reactant are dissolved in a small amount of solvent, more than the boiling point of solvent, react, system is in (is similar under the postcritical state) under the solvent ebullient state and react, make SBS fully to contact like this with reactant, react completely, thereby the percentage of grafting of the function SBS multipolymer of preparation is higher.
The present invention adopts autoclave, in autoclave, put into and be equivalent to SBS resin 1-20 SBS good solvent doubly, add 40.00-99.99%SBS resin, the maleic anhydride of 0.10-75.00%, the initiator of 0.01-20.00% and the common monomer of 0.00-60%, each composition weight percent sum is 100%.Put into 45-270 ℃ baking oven after the autoclave lid tightened, placed 0.5-50 hour, use water cooling then, open autoclave, solution is poured in the flocculation agent that is equivalent to its volume 1-10 times, on magnetic stirring apparatus, stirred (rotating speed 5-1000 rev/min) 0.1-10 hour, to remove unreacted matters, suction filtration then, the powder that suction filtration is obtained in 40-200 ℃ of vacuum drying oven dry 5-30 hour promptly obtain the SBS-maleic anhydride graft copolymer.
SBS good solvent of the present invention is 1,2-ethylene dichloride, 1,2-methylene dichloride, normal hexane, chloroform, benzene, tetrahydrofuran (THF), tetracol phenixin, toluene, dimethylbenzene.
Flocculation agent of the present invention is ethanol, acetone, methyl alcohol, ethylene glycol, deionized water, ether, glycerine, is the poor solvent of SBS.
Monomer altogether of the present invention is vinylformic acid, α-Jia Jibingxisuan, Methyl Methacrylate, acrylamide, vinylbenzene, hexanolactam, vinyl pyrrolidone, but is the response type monomer of a class electron donor.
Initiator of the present invention is azo-bis-isobutyl cyanide (AIBN), dicumyl peroxide (DCP), benzamide (BPO), t-butyl peroxide (TBP).
The present invention's method for preparing the SBS-maleic anhydride graft copolymer different from the past, conversion unit is simple, because reaction is to be under the similar postcritical state, so graft copolymer percentage of grafting height (being not less than 5.0%wt) that obtains, and than solution method, solvent load is few, is convenient to scale operation.The SBS-g-MAH of the present invention preparation is used for the compatilizer of blends such as SBS and non-polar polymer such as polycarbonate, polyester, nylon, urethane, polyvinyl chloride, can obtains the good comprehensive properties matrix material, wide application prospect is arranged.
Embodiment:
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1:
In autoclave, put into the benzene of 50ml, add 8gSBS resin, 1g maleic anhydride, 100mgBPO, the autoclave lid tightened put into 130 ℃ baking oven, placed 8 hours, use water cooling then, open autoclave, solution is poured in the ethylene glycol of 250ml, on magnetic stirring apparatus, stirred (150 rev/mins of rotating speeds) 1 hour, to remove unreacted matters, suction filtration then, the powder that suction filtration is obtained in 70 ℃ of vacuum drying ovens dry 12 hours, promptly obtaining percentage of grafting is the SBS-maleic anhydride graft copolymer of 5.5%wt.
Embodiment 2:
In autoclave, put into the acetone of 50ml, add 10gSBS resin, 2g maleic anhydride, 135mgBPO and acrylamide 0.8g, the autoclave lid tightened put into 110 ℃ baking oven, placed 6 hours, use water cooling then, open autoclave, solution is poured in the ethylene glycol of 300ml, on magnetic stirring apparatus, stirred (200 rev/mins of rotating speeds) 1 hour, to remove unreacted matters, suction filtration then, the powder that suction filtration is obtained in 80 ℃ of vacuum drying ovens dry 12 hours, promptly obtaining percentage of grafting is the SBS-maleic anhydride graft copolymer of 7.0%wt.
Embodiment 3:
In autoclave, put into the dimethylbenzene of 50ml, add the 10gSBS resin, 1.5g maleic anhydride, 1.5 milliliters of 150mgBPO and Methyl Methacrylates, the autoclave lid tightened put into 160 ℃ baking oven, placed 7 hours, use water cooling then, open autoclave, solution is poured in the acetone of 300ml, on magnetic stirring apparatus, stirred (200 rev/mins of rotating speeds) 1 hour, to remove unreacted matters, suction filtration then, the powder that suction filtration is obtained in 80 ℃ of vacuum drying ovens dry 12 hours, promptly obtaining percentage of grafting is the SBS-maleic anhydride graft copolymer of 10.0%wt.
With the SBS-g-MAH of the inventive method preparation compatilizer, make the snappiness performance of blend improve greatly as SBS and nylon (PA) blend; The SBS-g-MAH of preparation makes the snappiness of matrix material obviously improve as the expanding material of SBS and polyester blend.
Claims (4)
1, a kind of maleic anhydride graft styrene-butadiene-styrene solvent process for thermosynthesizing, it is characterized in that: in autoclave, put into and be equivalent to styrene-butadiene-styrene resin 1-20 styrene-butadiene-styrene good solvent doubly, add 40.00-99.99% styrene-butadiene-styrene resin, the maleic anhydride of 0.10-75.00%, the common monomer of the initiator of 0.01-20.00% and 0.00-60%, each composition weight percent sum is 100%, put into 45-270 ℃ baking oven after the autoclave lid tightened, placed 0.5-50 hour, use water cooling then, open autoclave, solution is poured in the flocculation agent that is equivalent to its volume 1-10 times, be to stir suction filtration after 0.1-10 hour on 5-1000 rev/min the magnetic stirring apparatus at rotating speed, the powder that suction filtration is obtained in 40-200 ℃ of vacuum drying oven dry 5-30 hour, promptly obtain styrene-butadiene-styrene-maleic anhydride graft copolymer, wherein, described monomer altogether is a vinylformic acid, α-Jia Jibingxisuan, Methyl Methacrylate, acrylamide, vinylbenzene, hexanolactam, vinyl pyrrolidone.
2, maleic anhydride graft styrene-butadiene-styrene solvent process for thermosynthesizing as claimed in claim 1, it is characterized in that described styrene-butadiene-styrene good solvent is 1,2-ethylene dichloride, 1,2-methylene dichloride, normal hexane, chloroform, benzene, tetrahydrofuran (THF), tetracol phenixin, toluene, dimethylbenzene.
3, maleic anhydride graft styrene-butadiene-styrene solvent process for thermosynthesizing as claimed in claim 1 is characterized in that described flocculation agent is ethanol, acetone, methyl alcohol, ethylene glycol, deionized water, ether, glycerine.
4, maleic anhydride graft styrene-butadiene-styrene solvent process for thermosynthesizing as claimed in claim 1 is characterized in that described initiator is azo-bis-isobutyl cyanide, dicumyl peroxide, benzoyl peroxide amine, t-butyl peroxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310107941 CN1218977C (en) | 2003-10-16 | 2003-10-16 | Maleic anhydride graft styrene-butadiene-styrene solvent heat-synthesizing method |
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| CN 200310107941 CN1218977C (en) | 2003-10-16 | 2003-10-16 | Maleic anhydride graft styrene-butadiene-styrene solvent heat-synthesizing method |
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| CN1218977C CN1218977C (en) | 2005-09-14 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284897B (en) * | 2008-06-05 | 2010-06-02 | 上海交通大学 | Dissolvant hot preparation process for inarching polyisobutene co-polymer with maleic anhydride |
| CN102627829A (en) * | 2012-03-23 | 2012-08-08 | 董久红 | Composite fiberboard prepared with waste acrylonitrile-butadiene-styrene (ABS) plastics and preparation method thereof |
| WO2012159867A1 (en) | 2011-05-23 | 2012-11-29 | Bostik S.A. | Wax-containing hot melt adhesives and disposable absorbent articles |
| CN107090061A (en) * | 2017-05-10 | 2017-08-25 | 无锡金运工程塑料有限公司 | A kind of polarity TPE modified plastics synthesis techniques |
| CN111019535A (en) * | 2019-10-28 | 2020-04-17 | 茂泰(福建)鞋材有限公司 | Environment-friendly combined sole and manufacturing method thereof |
| CN111976252A (en) * | 2020-08-28 | 2020-11-24 | 河南银金达新材料股份有限公司 | Flexible thermal shrinkage composite film formed by tape casting and preparation method thereof |
-
2003
- 2003-10-16 CN CN 200310107941 patent/CN1218977C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284897B (en) * | 2008-06-05 | 2010-06-02 | 上海交通大学 | Dissolvant hot preparation process for inarching polyisobutene co-polymer with maleic anhydride |
| WO2012159867A1 (en) | 2011-05-23 | 2012-11-29 | Bostik S.A. | Wax-containing hot melt adhesives and disposable absorbent articles |
| CN102627829A (en) * | 2012-03-23 | 2012-08-08 | 董久红 | Composite fiberboard prepared with waste acrylonitrile-butadiene-styrene (ABS) plastics and preparation method thereof |
| CN102627829B (en) * | 2012-03-23 | 2013-09-11 | 董久红 | Composite fiberboard prepared with waste acrylonitrile-butadiene-styrene (ABS) plastics and preparation method thereof |
| CN107090061A (en) * | 2017-05-10 | 2017-08-25 | 无锡金运工程塑料有限公司 | A kind of polarity TPE modified plastics synthesis techniques |
| CN111019535A (en) * | 2019-10-28 | 2020-04-17 | 茂泰(福建)鞋材有限公司 | Environment-friendly combined sole and manufacturing method thereof |
| CN111019535B (en) * | 2019-10-28 | 2021-07-09 | 茂泰(福建)鞋材有限公司 | Environment-friendly combined sole and manufacturing method thereof |
| CN111976252A (en) * | 2020-08-28 | 2020-11-24 | 河南银金达新材料股份有限公司 | Flexible thermal shrinkage composite film formed by tape casting and preparation method thereof |
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| CN1218977C (en) | 2005-09-14 |
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