CN102516464A - Epoxypropyl methacrylate grafting acrylonitrile butadiene styrene (ABS) copolymer and preparation method thereof - Google Patents
Epoxypropyl methacrylate grafting acrylonitrile butadiene styrene (ABS) copolymer and preparation method thereof Download PDFInfo
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- CN102516464A CN102516464A CN2011103897763A CN201110389776A CN102516464A CN 102516464 A CN102516464 A CN 102516464A CN 2011103897763 A CN2011103897763 A CN 2011103897763A CN 201110389776 A CN201110389776 A CN 201110389776A CN 102516464 A CN102516464 A CN 102516464A
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Abstract
The invention discloses an epoxypropyl methacrylate grafting acrylonitrile butadiene styrene (ABS) copolymer and a preparation method thereof. The epoxypropyl methacrylate grafting ABS copolymer is prepared by fusing the ABS, epoxypropyl methacrylate, ABS high rubber powder, peroxide initiator and grafted copolymer. The epoxypropyl methacrylate is adopted to graft and modify the ABS to prepare the ABS copolymer, the epoxypropyl methacrylate grafting ABS copolymer can serve as a compatilizer when the ABS is mixed with the polycarbonate, polyester, nylon, polyurethane, polyvinyl chloride and the like, and prepared composite materials has good comprehensive performance and application prospect. In formula of the copolymer, the ABS high rubber powder is added to solve the problem that ABS granules are easily tumefied when encounter liquid. In addition, fusion and grafting are performed on a double-screw extrusion machine, grafting rate of prepared ABS copolymer is high, a reaction device is simple, and mass production is facilitated.
Description
Technical field
The present invention relates to the Acrylonitrile Butadiene technical field, particularly relate to a kind of GMA grafted ABS multipolymer and preparation method thereof.
Background technology
ABS resin is with propylene fine (A), divinyl (B) and the general name that three kinds of monomers of vinylbenzene (S) are a series of polymkeric substance of basic synthetic, is most widely used engineering plastics.For broadened application scope and the raw-material performance of raising, be the important channel of exploitation new capability ABS resin with the ABS blending and modifying, thereby enjoy attention and concern always with other polymer blending.Through blend, can improve shock strength, thermotolerance, the chemical resistance of ABS, give flame retardant resistance and static resistance, or reduce cost, have industrial significance.
But owing to the consistency of ABS and a lot of polymkeric substance is not very desirable, the compatilizer of palpus interpolation often reduces IT to reduce particle diameter, makes alternate can mixing, with better its performance of improving.ABS system compatilizer commonly used has the multipolymer of multipolymer, TEB 3K and SY-Monomer G of multipolymer, vinylbenzene and SY-Monomer G of multipolymer, vinylbenzene and methylacrylic acid of multipolymer, vinylbenzene and the TEB 3K of ABS grafted maleic anhydride, vinylbenzene and maleic anhydride, does compatilizer and is of practical significance very much so prepare functionalization ABS.S. BALAKRISHNAN etc. studies the reaction of ABS fusion-grafting maleic anhydride; Graft product has good toughening effect to polycarbonate (PC); But maleic anhydride at high temperature is prone to distillation, and is big to the pungency of human body, and equipment is corrosive.
Summary of the invention
Technical problem to be solved by this invention is the defective that overcomes existing capability ABS; A kind of GMA grafted ABS multipolymer and preparation method thereof is provided; Compatilizer when this multipolymer can be used as blend such as ABS and polycarbonate, polyester, nylon, urethane, SE obtains the good comprehensive properties matrix material.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
According to listed as parts by weight, GMA grafted ABS multipolymer of the present invention is to be prepared from 100 parts of ABS, 1～10 part of GMA, 5～20 parts of ABS high glue powders, 0.1～1 part of peroxide initiator, the fusion of 0.5～10 part of graft copolymerization body.
Further, above-mentioned GMA grafted ABS multipolymer is to be prepared from 100 parts of ABS, 1～5 part of GMA, 10～15 parts of ABS high glue powders, 0.1～0.5 part of peroxide initiator, the fusion of 0.5～5 part of graft copolymerization body.
Best, aforementioned multipolymer is to be prepared from 100 parts of ABS, 4 parts of GMAs, 15 parts of ABS high glue powders, 0.3 part of peroxide initiator, the fusion of 3 parts of graft copolymerization bodies.
In the aforementioned multipolymer, the butadiene content of said ABS high glue powder is 70% (weight).Peroxide initiator was preferably Di Cumyl Peroxide 99 DCP, BM BPO, azo-bis-isobutyl cyanide AIBN or t-butyl hydroperoxide TBHP.Said graft copolymerization body is vinylformic acid, α-Jia Jibingxisuan, vinylbenzene, TEB 3K, EMA, acrylic amide, hexanolactam or vinyl pyrrolidone.
The present invention also provides the preferred preparation method of aforementioned GMA grafted ABS multipolymer: get GMA, graft copolymerization body and peroxide initiator and mix, add the ABS high glue powder then and mix, add ABS at last and mix; Add extruding pelletization in the twin screw extruder; The gained pellet is dry, get pellet solution with dissolution with solvents, pellet solution is poured in the precipitation agent; Filter; Washing precipitation, drying had both got GMA grafted ABS multipolymer.
Further, above-mentioned pellet and sedimentary drying are in 40～200 ℃ vacuum drying oven dry 5～24 hours; Said solvent is an acetone, 1,2-ethylene dichloride, 1,2-methylene dichloride, normal hexane, chloroform or tetracol phenixin; Said precipitation agent is zero(ppm) water, methyl alcohol or ethanol.
Compared with prior art; The present invention adopts GMA that ABS is carried out graft modification to prepare Acrylonitrile Butadiene; Compatilizer when can be used for blend such as ABS and polycarbonate, polyester, nylon, urethane, SE; The composite material combination property that obtains is better, and good application prospects is arranged.In the prescription of multipolymer, add the ABS high glue powder and avoided the ABS pellet to meet liquid swollen problem, while fusion-grafting on twin screw extruder, the percentage of grafting of gained Acrylonitrile Butadiene is high, and conversion unit is simple, is convenient to scale operation.
Embodiment
Embodiment 1: at first, 1 part of GMA is mixed (obtaining mixture A) mutually with 0.3 part initiator; Secondly, mixture A mixes (obtaining mixture B) with 15 parts ABS high glue powder mutually, mixes fully, evenly.At last; 100 parts of ABS pellets are mixed with mixture B; Mix fully, evenly the back adds extruding pelletization in the twin screw extruder, and each section temperature of feed opening to head is respectively: 140 ℃, 150 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 200 ℃.Pellet is placed after 24 hours in 80 ℃ vacuum drying oven; With solvent pellet is dissolved to remove unreacted small-molecule substance fully; Then solution is poured in a large amount of precipitation agents; And with the throw out repetitive scrubbing, drying is 24 hours in 80 ℃ vacuum drying oven, promptly gets ABS-GMA graft copolymer.
Embodiment 2: at first, 3 parts of GMAs are mixed (obtaining mixture A) mutually with 0.3 part initiator; Secondly, mixture A mixes (obtaining mixture B) with 15 parts ABS high glue powder mutually, mixes fully, evenly.At last; 100 parts of ABS pellets are mixed with mixture B; Mix fully, evenly the back adds extruding pelletization in the twin screw extruder, and each section temperature of feed opening to head is respectively: 140 ℃, 150 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 200 ℃.Pellet is placed after 24 hours in 80 ℃ vacuum drying oven; With solvent pellet is dissolved to remove unreacted small-molecule substance fully; Then solution is poured in a large amount of precipitation agents; And with the throw out repetitive scrubbing, drying is 24 hours in 80 ℃ vacuum drying oven, promptly gets ABS-GMA graft copolymer.
Embodiment 3: at first, 5 parts of GMAs are mixed (obtaining mixture A) mutually with 0.3 part initiator; Secondly, mixture A mixes (obtaining mixture B) with 15 parts ABS high glue powder mutually, mixes fully, evenly.At last; 100 parts of ABS pellets are mixed with mixture B; Mix fully, evenly the back adds extruding pelletization in the twin screw extruder, and each section temperature of feed opening to head is respectively: 140 ℃, 150 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 200 ℃.Pellet is placed after 24 hours in 80 ℃ vacuum drying oven; With solvent pellet is dissolved to remove unreacted small-molecule substance fully; Then solution is poured in a large amount of precipitation agents; And with the throw out repetitive scrubbing, drying is 24 hours in 80 ℃ vacuum drying oven, promptly gets ABS-GMA graft copolymer.
Embodiment 4: at first, 1 part of GMA and a certain amount of graft copolymerization body (mol ratio is 1:1) are mixed (obtaining mixture A) mutually with 0.3 part initiator; Secondly, mixture A mixes (obtaining mixture B) with 15 parts ABS high glue powder mutually, mixes fully, evenly.At last, 100 parts of ABS pellets are mixed with mixture B, mix fully; Evenly the back adds extruding pelletization in the twin screw extruder, and pellet was placed in 80 ℃ vacuum drying oven after 24 hours, with solvent pellet was dissolved to remove unreacted small-molecule substance fully; Then solution is poured in a large amount of precipitation agents; And with the throw out repetitive scrubbing, drying is 24 hours in 80 ℃ vacuum drying oven, promptly gets ABS-GMA graft copolymer.
Embodiment 5: at first, 3 parts of GMAs and a certain amount of graft copolymerization body (mol ratio is 1:1) are mixed (obtaining mixture A) mutually with 0.3 part initiator; Secondly, mixture A mixes (obtaining mixture B) with 15 parts ABS high glue powder mutually, mixes fully, evenly.At last, 100 parts of ABS pellets are mixed with mixture B, mix fully; Evenly the back adds extruding pelletization in the twin screw extruder, and pellet was placed in 80 ℃ vacuum drying oven after 24 hours, with solvent pellet was dissolved to remove unreacted small-molecule substance fully; Then solution is poured in a large amount of precipitation agents; And with the throw out repetitive scrubbing, drying is 24 hours in 80 ℃ vacuum drying oven, promptly gets ABS-GMA graft copolymer.
Embodiment 6: at first, 4 parts of GMAs and a certain amount of graft copolymerization body (mol ratio is 1:1) are mixed (obtaining mixture A) mutually with 0.3 part initiator; Secondly, mixture A mixes (obtaining mixture B) with 15 parts ABS high glue powder mutually, mixes fully, evenly.At last, 100 parts of ABS pellets are mixed with mixture B, mix fully; Evenly the back adds extruding pelletization in the twin screw extruder, and pellet was placed in 80 ℃ vacuum drying oven after 24 hours, with solvent pellet was dissolved to remove unreacted small-molecule substance fully; Then solution is poured in a large amount of precipitation agents; And with the throw out repetitive scrubbing, drying is 24 hours in 80 ℃ vacuum drying oven, promptly gets ABS-GMA graft copolymer.
Performance evaluation:
The sample percentage of grafting adopts analyses, and the result is as shown in table 1, and percentage of grafting is higher.
The preparation of matrix material: the multipolymer of embodiment 5 preparation is used for the blending and modifying of PC and ABS, and as shown in table 2 by following standard testing performance, performance of composites is better behind the interpolation Acrylonitrile Butadiene.
The tensile property test is undertaken by GB/T1040-1992, and specimen size is 150*10*4mm, and rate of extension is 50mm/min.
The bending property test is undertaken by GB-T 3356-1999, and specimen size is 80*10*4mm, and crooked speed is 2mm/min.
The socle girder notched Izod impact strength is undertaken by GB/T1843-1996, and specimen size is 80*10*4mm, and notch depth is 2mm.Concrete performance is shown as follows:
The percentage of grafting of table 1 GMA grafted ABS multipolymer
Each item performance (weight part) of table 2 matrix material
Claims (10)
1. GMA grafted ABS multipolymer; It is characterized in that: according to listed as parts by weight, it is to be prepared from 100 parts of ABS, 1～10 part of GMA, 5～20 parts of ABS high glue powders, 0.1～1 part of peroxide initiator, the fusion of 0.5～10 part of graft copolymerization body.
2. according to the said GMA grafted ABS of claim 1 multipolymer, it is characterized in that: it is to be prepared from 100 parts of ABS, 1～5 part of GMA, 10～15 parts of ABS high glue powders, 0.1～0.5 part of peroxide initiator, the fusion of 0.5～5 part of graft copolymerization body.
3. according to the said GMA grafted ABS of claim 2 multipolymer, it is characterized in that: it is to be prepared from 100 parts of ABS, 4 parts of GMAs, 15 parts of ABS high glue powders, 0.3 part of peroxide initiator, the fusion of 3 parts of graft copolymerization bodies.
4. according to the arbitrary said GMA grafted ABS multipolymer of claim 1 to 3, it is characterized in that: the butadiene content of said ABS high glue powder is 70% (weight).
5. according to the arbitrary said GMA grafted ABS multipolymer of claim 1 to 3, it is characterized in that: said peroxide initiator is Di Cumyl Peroxide 99 DCP, BM BPO, azo-bis-isobutyl cyanide AIBN or t-butyl hydroperoxide TBHP.
6. according to the arbitrary said GMA grafted ABS multipolymer of claim 1 to 3, it is characterized in that: said graft copolymerization body is vinylformic acid, α-Jia Jibingxisuan, vinylbenzene, TEB 3K, EMA, acrylic amide, hexanolactam or vinyl pyrrolidone.
7. the preparation method of the arbitrary said GMA grafted ABS multipolymer of claim 1 to 6 is characterized in that: get GMA, graft copolymerization body and peroxide initiator and mix, add the ABS high glue powder then and mix; Add ABS at last and mix, add extruding pelletization in the twin screw extruder, the gained pellet is dry; Get pellet solution with dissolution with solvents; Pellet solution is poured in the precipitation agent, filtered washing precipitation; Drying had both got GMA grafted ABS multipolymer.
8. according to the preparation method of the said GMA grafted ABS of claim 7 multipolymer, it is characterized in that: said pellet and sedimentary drying are in 40～200 ℃ vacuum drying oven dry 5～24 hours.
9. according to the preparation method of the said GMA grafted ABS of claim 7 multipolymer, it is characterized in that: said solvent is an acetone, 1,2-ethylene dichloride, 1,2-methylene dichloride, normal hexane, chloroform or tetracol phenixin.
10. according to the preparation method of the said GMA grafted ABS of claim 7 multipolymer, it is characterized in that: said precipitation agent is zero(ppm) water, methyl alcohol or ethanol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110389776 CN102516464B (en) | 2011-11-30 | 2011-11-30 | Epoxypropyl methacrylate grafting acrylonitrile butadiene styrene (ABS) copolymer and preparation method thereof |
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| CN 201110389776 CN102516464B (en) | 2011-11-30 | 2011-11-30 | Epoxypropyl methacrylate grafting acrylonitrile butadiene styrene (ABS) copolymer and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044907A (en) * | 2013-01-11 | 2013-04-17 | 长春工业大学 | Modified polyamide and preparation method thereof |
| CN103756299A (en) * | 2013-12-13 | 2014-04-30 | 上海金发科技发展有限公司 | High-performance glass fiber reinforced PA/ABS alloy material, and preparation method thereof |
| CN104088032A (en) * | 2014-06-30 | 2014-10-08 | 太仓天龙化纤有限公司 | Healthcare stretch yarn |
| CN104356322A (en) * | 2014-11-26 | 2015-02-18 | 重庆可益荧新材料有限公司 | Chemically modified waste PC/ABS alloy material and preparation method thereof |
| CN104877297A (en) * | 2015-05-26 | 2015-09-02 | 江苏浩宇电子科技有限公司 | Preparation method for easy-to-color 3D printing supplies |
| CN109370145A (en) * | 2018-10-31 | 2019-02-22 | 江苏亿超工程塑料有限公司 | A kind of preparation method of waste and old ABS/PBT composite material |
| CN111393587A (en) * | 2019-12-20 | 2020-07-10 | 赣州能之光新材料有限公司 | Multi-monomer grafted ABS high-rubber-powder copolymer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186081A (en) * | 1996-12-26 | 1998-07-01 | 中国科学院长春应用化学研究所 | Graft copolymerization of acrylonitrile-butadiene-styrene |
| CN1978574A (en) * | 2005-12-06 | 2007-06-13 | 皮立生 | Fireproof environmental-protectiongel forming agent |
-
2011
- 2011-11-30 CN CN 201110389776 patent/CN102516464B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186081A (en) * | 1996-12-26 | 1998-07-01 | 中国科学院长春应用化学研究所 | Graft copolymerization of acrylonitrile-butadiene-styrene |
| CN1978574A (en) * | 2005-12-06 | 2007-06-13 | 皮立生 | Fireproof environmental-protectiongel forming agent |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044907A (en) * | 2013-01-11 | 2013-04-17 | 长春工业大学 | Modified polyamide and preparation method thereof |
| CN103756299A (en) * | 2013-12-13 | 2014-04-30 | 上海金发科技发展有限公司 | High-performance glass fiber reinforced PA/ABS alloy material, and preparation method thereof |
| CN104088032A (en) * | 2014-06-30 | 2014-10-08 | 太仓天龙化纤有限公司 | Healthcare stretch yarn |
| CN104356322A (en) * | 2014-11-26 | 2015-02-18 | 重庆可益荧新材料有限公司 | Chemically modified waste PC/ABS alloy material and preparation method thereof |
| CN104877297A (en) * | 2015-05-26 | 2015-09-02 | 江苏浩宇电子科技有限公司 | Preparation method for easy-to-color 3D printing supplies |
| CN109370145A (en) * | 2018-10-31 | 2019-02-22 | 江苏亿超工程塑料有限公司 | A kind of preparation method of waste and old ABS/PBT composite material |
| CN111393587A (en) * | 2019-12-20 | 2020-07-10 | 赣州能之光新材料有限公司 | Multi-monomer grafted ABS high-rubber-powder copolymer and preparation method thereof |
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| CN102516464B (en) | 2013-08-07 |
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