CN101560281A - EPM-g-MAN toughener and preparation method thereof as well as engineering plastics AEMS - Google Patents
EPM-g-MAN toughener and preparation method thereof as well as engineering plastics AEMS Download PDFInfo
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- CN101560281A CN101560281A CNA2009100397636A CN200910039763A CN101560281A CN 101560281 A CN101560281 A CN 101560281A CN A2009100397636 A CNA2009100397636 A CN A2009100397636A CN 200910039763 A CN200910039763 A CN 200910039763A CN 101560281 A CN101560281 A CN 101560281A
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Abstract
The invention discloses an EPM-g-MAN toughener and a preparation method thereof as well as engineering plastics AEMS. In the preparation method, ethylene propylene rubber and methyl methacrylate as well as acrylonitrile serve as raw material to synthesize graft copolymer EPM-g-MAN by a suspension graft copolymerization method. In the method, EPM is dissolved in organic solvent, and the mixed solution is added with MMA-AN mixed monomer, evocating agent and assistant dispersant to be stirred at low temperature to be evenly mixed; then, the mixture is dripped with dispersant water solution under the high speed agitation and the needed de-ionized water for reaction when the mixed solution is heated up under the nitrogen protection. The product is filtered, washed and dried after the reaction, so that granular toughener EPM-g-MAN with the EPM content of 47.5-68.7% can be obtained. The monomer conversion rate of an EPM/ MMA-AN suspension graft copolymerization system is 85-94.82%, and the grafting percent reaches as high as 40%. The synthesized EPM-g-MAN can be mixed with SAN resin to prepare the high-impact engineering plastics AEMS with excellent weather aging yellowing resistant property, and the notch impact strength of the AEMS is 17-59.3kJ/m<2>.
Description
Technical field
The present invention relates to a kind of technology of preparing of graft copolymer EPM-g-MAN toughner and the engineering plastics AEMS for preparing with the SAN resin alloy thereof.
Background technology
Terpolymer EP rubber (EPDM) has good toughening effect with the graft copolymer EPDM-g-SAN of vinylbenzene and acrylonitrile (St-AN) to the SAN resin, and the goods of its blend AES are the good high-impact plastics of a class weather-resistant performance.But because EPDM-g-SAN and SAN resin all contain a large amount of vinyl cyanide (AN) unit, under the high temperature action of melt blending, the AN unit can form the poly-imine structure of conjugation of high Chromaticity, causes the AES yellowing brown.
EPDM-g-SAN generally adopts solution graft copolymerization legal synthetic, but monomer conversion, percentage of grafting and the grafting efficiency of EPDM/St-AN solution graft copolymerization system are lower, and residual monomer reclaims difficulty, and product is lower to the toughening efficiency of SAN.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of EPM-g-MAN toughner that can not cause the blend serious discoloration in the course of processing is provided, and this EPM-g-MAN toughner and SAN resin alloy can be prepared the high-impact engineering plastics AEMS of Weather-resistant xanthochromia excellent performance.
EPM-g-MAN toughner of the present invention, make by following component and weight percentage:
Ethylene propylene rubber 45～65%, monomer 35～55%, described monomer are the mixture of methyl methacrylate (MMA) and vinyl cyanide (AN).
Above-mentioned preferred weight percentage ratio is: ethylene propylene rubber 45～60%, monomer 40～55%.
In the above-mentioned monomer, the weight percent of methyl methacrylate and vinyl cyanide is respectively 95～75%, and 5～25%.The present invention is complementary the polarity and the SAN resin of the grafted chain of formation by regulating the monomer blends ratio of MMA and AN, can improve the consistency of EPM-g-MAN and SAN resin effectively.
Another object of the present invention provides the suspension polymerization preparation method of above-mentioned EPM-g-MAN toughner.Specifically comprise the steps:
(1) EPM is dissolved in the organic solvent, makes the EPM glue;
(2) under stirring at low speed, add methyl methacrylate and vinyl cyanide mix monomer, treat that it mixes the back and adds initiator and dispersion aids;
(3) drip aqueous dispersant, slowly improve stirring velocity to 800～1200rpm simultaneously, drip distilled water or deionized water then, make system become suspension polymerization system, water accounts for 55～65% of whole suspension polymerization system total mass in the suspension polymerization system; Water is distilled water or deionized water, and oil phase is EPM, mix monomer, solvent toluene and initiator B PO is miscible forms;
(4) logical nitrogen carries out suspension polymerization under 70～90 ℃, reacts and reduces to room temperature after 15～25 hours, discharging, filtration, recovery product, washing, dewaters, is dried to constant weight, promptly obtains granular toughner EPM-g-MAN.
In above-mentioned preparation method, described step (1) is that solid EPM is added fully dissolving in the organic solvent, and the consumption of organic solvent is to occupy 56.5～63% of machine solvent, EPM and monomer total mass, and restir is made the EPM glue.
In above-mentioned preparation method, described organic solvent is preferably one or more the mixed solvent in benzene,toluene,xylene, normal heptane, Skellysolve A, normal hexane and the hexanaphthene.
In above-mentioned preparation method, described initiator is preferably a kind of of dibenzoyl peroxide (BPO), dilauroyl peroxide, peroxide tert pivalate ester, peroxy dicarbonate ethylhexyl and the peroxidation 2 ethyl hexanoic acid tert-butyl ester; The consumption of initiator is to account for 0.3～0.9% of EPM and monomer total mass.
In above-mentioned preparation method, described dispersion aids is preferably sodium lauryl sulphate (SDS), Sodium dodecylbenzene sulfonate, sodium oleate, sodium stearate, naphthene sulfonic acid hydrogen sodium, water-soluble phenylethene-maleic anhydride (SMA) multipolymer, carboxymethyl cellulose; Its consumption is to account for 0.06～0.2% of EPM and monomer total mass.
In above-mentioned preparation method, described dispersion agent is preferably polyvinyl alcohol (PVA), alkyl polyoxyethylene ether, polyacrylamide, Vltra tears (HPMC); Its consumption is 0.5～0.8% of EPM, monomer and an organic solvent total mass.
Further purpose of the present invention provides the high-impact engineering plastics AEMS that above-mentioned EPM-g-MAN toughner and SAN resin alloy prepare.
EPM-g-MAN and SAN resin alloy can be made engineering plastics AEMS, and the quality of EPM is 10～30% of AEMS in AEMS.
Because the rubber phase of AEMS is saturated rubber EPM, its macromole is the carbon-carbon double key not, so AEMS has excellent heat oxygen aging resistance, Weather-resistant and ageing-resistant xanthochromia performance.With the plastic fittings of AEMS preparation, especially outdoor accessory, its anti-Weather xanthochromia performance be engineering plastics such as ABS and HIPS can not compare.In world industrially developed country, AES has been used to prepare automobile and motorcycle accessories, house loam cake and exterior wall, outdoor electrical instrumentation shell etc., and purposes more and more widely.
Compared with prior art, the present invention has following beneficial effect:
In order to prepare the toughner that in the course of processing, can not cause the blend serious discoloration, the present invention adopt the more weak MMA of polarity with a small amount of AN as comonomer to reduce the consumption of AN, thereby reduce the AN unit content of grafted chain, and adopt the ethylene propylene rubber (EPM) that does not contain the carbon-to-carbon double bond that is easy to oxidation as the grafting matrix, its thermostability and Weather-resistant xanthochromia performance are better than terpolymer EP rubber.
The present invention adopts continuously stirring suspension grafting copolymerization process, makes the oil phase of polymerization system remain dispersion state, thereby can form the grafted chain that is evenly distributed on the EPM molecular chain.Suspension polymerization is easy to conduct heat, and no local superheating phenomenon takes place, and polymerization process is stable, thereby is easy to control.By adjusting the batching mass ratio of EPM and the monomeric batching mass ratio of copolymerization, comonomer, make monomer conversion up to more than the 85wt%, monomer conversion, percentage of grafting and the grafting efficiency of graft copolymerization system have been improved, thereby the consistency that has improved EPM-g-MAN and SAN resin significantly reaches the toughening efficiency to the SAN resin, the notched Izod impact strength of the AEMS that makes is increased substantially, can prepare the high high-impact engineering plastics AEMS of Weather-resistant xanthochromia excellent performance and glossiness.
Suspension grafting copolymerization process of the present invention is compared with solution method, and the remarkable advantage of suspension method is that solvent load is few, (EPM+MMA-AN)/mass ratio of solvent is about 1: 1.5 only, solution polymerization then needs about 1: 4.Because the monomer concentration height of suspension system organic phase so monomer conversion, percentage of grafting and grafting efficiency significantly improve, reaches about 90%.Product need not reclaim with methyl alcohol or ethanol sedimentation, has saved a large amount of methyl alcohol or ethanol.Waste liquid only is made up of moisture content, solvent and small amounts of monomer, and solvent is easy to reclaim and separates and the purification recycle, thereby significantly reduces product postprocessing facility investment and production cost.This new technology of suspension graft copolymerization can be avoided the existing critical defect of solution method effectively.
Embodiment
The invention will be further described below in conjunction with embodiment, and the contriver has many successful examples to the present invention after research and testing, enumerates the part specific embodiment below, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
The basic recipe of embodiment 1 and enforcement prescription are as shown in table 1.The AN/MMA mass ratio that feeds intake is that the synthetic operation process of 15/85 o'clock EPM-g-MAN is as follows:
In three mouthfuls of round-bottomed flasks of 1000ml that condensing reflux pipe, agitator, oil bath heating temperature controller be housed, add EPM 60g, toluene 150g,, add the mix monomer of 34g methyl methacrylate and 6g vinyl cyanide 60 ℃ of fully dissolvings 16 hours down.The control stirring velocity is 200 rev/mins, stirs to add 0.6gBPO and 0.132gSDS after 30 minutes, stirs to make it to mix in 15 minutes.With 72g concentration is that 2% polyvinyl alcohol-224 (PVA-224) aqueous solution is added drop-wise in the reaction system, dropwises in 30 minutes, adjusts stirring velocity simultaneously and brings up to 1000 rev/mins gradually.The 385g deionized water is slowly added in the flask, and logical nitrogen 15 minutes improved temperature of reaction to 80 ℃ in 5 minutes under nitrogen protection.React and system is cooled to room temperature, discharging after 20 hours.With 200 order filter clothes product is leached, with product washing three times, place vacuum drying oven, promptly make diameter and be the EPM-g-MAN toughner about 0.5mm 80 ℃ of oven dry 8 hours down with tap water.The monomer conversion of reaction system is 89.1%, and the EPM content of EPM-g-MAN is 62.7%.
With the preparation EPM-g-MAN toughner and SAN resin warm-up mill on mixing with 165 ℃ roller temperature, the EPM content of blend AEMS: the EPM/AEMS quality percentage is 25wt%.Is 170～175 ℃ mold pressings at vulcanizing press with the upper and lower mould temperature with laminating, makes the thick material sheet of 4.3～4.7mm.Be processed into the test with notched test piece batten of standard by standard GB 1843-96.The socle girder notched Izod impact strength of measuring sample is 55kJ/m
2
With the operating process of the synthetic EPM-g-MAN of other different AN/MMA proportionings among the embodiment 1 and the preparation method of AEMS, and the preparation method of the operating process of embodiment 2, embodiment 3, embodiment 4, embodiment 5 and embodiment 6 synthetic EPM-g-SAN and AEMS is identical with the aforesaid operations process.The relation of the notched Izod impact strength of the monomer conversion (CR) of the consumption of the batching mass ratio of two kinds of comonomers, EPM/MMA-AN mass ratio, initiator, solvent load and PVA consumption and graft copolymerization system, percentage of grafting (GR), grafting efficiency (GE) and AEMS is shown in table 1, table 2, table 3, table 4 and table 5, and the relation of the notched Izod impact strength of EPM/AEMS mass ratio and AEMS, tensile strength and flexural strength is as shown in table 6.
In the table of table 1 (a) and back, the transformation rate (CR) of the basic proportioning of BPO, toluene, PVA and SDS, oil phase/(water+oil phase) mass ratio: O/ (W+O)/wt%, reaction system, the percentage of grafting (GR) of product and grafting efficiency (GE) calculate with following formula respectively
BPO consumption/wt%=BPO/ (EPM+MMA-AN)
Toluene consumption/wt%=toluene/(toluene+EPM+MMA-AN)
PVA consumption/wt%=PVA/ (EPM+MMA-AN+ toluene)
SDS consumption/wt%=SDS/ (EPM+MMA-AN)
O/ (W+O)/wt%=(EPM+MMA-AN+ toluene)/(EPM+MMA-AN+ toluene+distilled water)
Table 1 (a) embodiment 1 prescription and reaction conditions
The relation of CR, GR, GE and the AEMS notched Izod impact strength of table 1 (b) embodiment 1 monomeric charge quality and grafting system
*The EPM content of AEMS: the EPM/AEMS percentage is 25wt%.
Table 2 (a) embodiment 2 prescription and reaction conditionss
The relation of CR, GR, GE and the AEMS notched Izod impact strength of table 2 (b) embodiment 2EPM/MMA-AN mass ratio and grafting system
*The EPM content of AEMS: the EPM/AEMS percentage is 25wt%.
Table 3 (a) embodiment 3 prescription and reaction conditionss
The relation of CR, GR, GE and the AEMS notched Izod impact strength of table 3 (b) embodiment 3BPO consumption and grafting system
*The EPM content of AEMS: the EPM/AEMS percentage is 25wt%.
Table 4 (a) embodiment 4 prescription and reaction conditionss
The CR of table 4 (b) embodiment 4 solvent loads and grafting system and the relation of AEMS notched Izod impact strength
*The EPM content of AEMS: the EPM/AEMS percentage is 25wt%.
Table 5 (a) embodiment 5 prescription and reaction conditionss
The CR of table 5 (b) embodiment 5PVA consumption and grafting system and the relation of AEMS notched Izod impact strength
*The EPM content of AEMS: the EPM/AEMS percentage is 25wt%.
Table 6 (a) embodiment 6 prescription and reaction conditionss
Table 6 (b) embodiment 6EPM-g-MAN is to the toughening effect of SAN resin
Claims (10)
1, a kind of EPM-g-MAN toughner is characterized in that being made by following component and weight percentage:
Ethylene propylene rubber 45～65%
Monomer 35～55%
Described monomer is the mixture of methyl methacrylate and vinyl cyanide.
2, toughner as claimed in claim 1 is characterized in that following component and weight percentage make:
Ethylene propylene rubber 45～60%
Monomer 40～55%
Described monomer is the mixture of methyl methacrylate and vinyl cyanide.
3, toughner as claimed in claim 1 or 2 is characterized in that the weight percent of described methyl methacrylate and vinyl cyanide is respectively 95～75%, 5～25%.
4, the preparation method of the described toughner of claim 1 is characterized in that adopting the suspension polymerization preparation, comprises the steps:
(1) EPM is dissolved in the organic solvent, makes the EPM glue;
(2) under stirring at low speed, add methyl methacrylate and vinyl cyanide mix monomer, treat that it mixes the back and adds initiator and dispersion aids;
(3) drip aqueous dispersant, slowly improve stirring velocity to 800～1200rpm simultaneously, drip distilled water or deionized water then, make system become suspension polymerization system, water accounts for 55～65% of whole suspension polymerization system total mass in the suspension polymerization system;
(4) logical nitrogen carries out suspension polymerization under 70～90 ℃, reacts and reduces to room temperature after 15～25 hours, discharging, filtration, recovery product, washing, dewaters, is dried to constant weight, promptly obtains granular toughner EPM-g-MAN.
5, preparation method as claimed in claim 4, it is characterized in that described step (1) is for adding solid EPM fully dissolving in the organic solvent, the consumption of organic solvent is to occupy 56.5～63% of machine solvent, EPM and monomer total mass, and restir is made the EPM glue.
6,, it is characterized in that described organic solvent is one or more the mixed solvent in benzene,toluene,xylene, normal heptane, Skellysolve A, normal hexane and the hexanaphthene as claim 4 or 5 described preparation methods.
7, preparation method as claimed in claim 4 is characterized in that described initiator is a kind of of dibenzoyl peroxide, dilauroyl peroxide, peroxide tert pivalate ester, peroxy dicarbonate ethylhexyl and the peroxidation 2 ethyl hexanoic acid tert-butyl ester; The consumption of initiator is to account for 0.3～0.9% of EPM and monomer total mass.
8, preparation method as claimed in claim 4 is characterized in that described dispersion aids is sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium oleate, sodium stearate, naphthene sulfonic acid hydrogen sodium, water-soluble phenylethene-copolymer-maleic anhydride, carboxymethyl cellulose; Its consumption is to account for 0.06～0.2% of EPM and monomer total mass.
9, preparation method as claimed in claim 4 is characterized in that described dispersion agent is polyvinyl alcohol, alkyl polyoxyethylene ether, polyacrylamide, Vltra tears; Its consumption is 0.5～0.8% of EPM, monomer and an organic solvent total mass.
10, a kind of engineering plastics AEMS is characterized in that being made by EPM-g-MAN toughner and SAN resin alloy, and the quality of EPM is 10～30% of AEMS in AEMS.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832601A (en) * | 2016-12-27 | 2017-06-13 | 天津金发新材料有限公司 | A kind of resistance to ultralow temperature, polypropene composition of scratch-resistant and preparation method thereof |
| CN106832575A (en) * | 2016-12-27 | 2017-06-13 | 天津金发新材料有限公司 | A kind of Antibacterial polypropylene composition of resistance to ultralow temperature and preparation method thereof |
| CN106832600A (en) * | 2016-12-27 | 2017-06-13 | 天津金发新材料有限公司 | A kind of polypropene composition of resistance to ultralow temperature and preparation method thereof |
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2009
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832601A (en) * | 2016-12-27 | 2017-06-13 | 天津金发新材料有限公司 | A kind of resistance to ultralow temperature, polypropene composition of scratch-resistant and preparation method thereof |
| CN106832575A (en) * | 2016-12-27 | 2017-06-13 | 天津金发新材料有限公司 | A kind of Antibacterial polypropylene composition of resistance to ultralow temperature and preparation method thereof |
| CN106832600A (en) * | 2016-12-27 | 2017-06-13 | 天津金发新材料有限公司 | A kind of polypropene composition of resistance to ultralow temperature and preparation method thereof |
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