CN101560281B - 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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- CN101560281B CN101560281B CN2009100397636A CN200910039763A CN101560281B CN 101560281 B CN101560281 B CN 101560281B CN 2009100397636 A CN2009100397636 A CN 2009100397636A CN 200910039763 A CN200910039763 A CN 200910039763A CN 101560281 B CN101560281 B CN 101560281B
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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 one type of high-impact plastics that the weather-resistant performance is good.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 conjugation of high Chromaticity and gather imine structure, 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 in the course of processing, can not cause the blend serious discoloration 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, process by following component and weight percentage:
Ethylene propylene rubber 45~65%, monomer 35~55%, said monomer are the mixture of TEB 3K (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 TEB 3K 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 through 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 TEB 3K 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 zero(ppm) water or vaal 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 zero(ppm) water or vaal 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, said 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 processed the EPM glue.
In above-mentioned preparation method, said 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, said initiator is preferably a kind of of BPO (BPO), dilauroyl peroxide, peroxide tert pivalate ester, peroxy dicarbonate ethylhexyl and the peroxo-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, said dispersion aids is preferably sodium lauryl sulphate (SDS), X 2073, sodium oleate, StNa, naphthene sulfonic acid hydrogen sodium, water-soluble phenylethene-maleic anhydride (SMA) multipolymer, CMC 99.5; Its consumption is to account for 0.06~0.2% of EPM and monomer total mass.
In above-mentioned preparation method, said dispersion agent is preferably Z 150PH (PVA), alkyl polyoxyethylene ether, SEPIGEL 305, 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.The industrially developed country in the world, AES have 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 be prepared in the toughner that can not cause the blend serious discoloration in the course of processing; 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 on the EPM molecular chain, form the grafted chain that is evenly distributed.Suspension polymerization is easy to conduct heat, and no local superheating phenomenon takes place, and polymerization process is stable, thereby is easy to control.Through 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, and the notched Izod impact strength of the AEMS that makes is increased substantially, and 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 merely about 1: 1.5, and solution polymerization then needs about 1: 4.Because the monomer concentration of suspension system organic phase is high, 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
Below in conjunction with embodiment the present invention is described further, the contriver through research and test, has many successful examples to the present invention, enumerates the part specific embodiment below, but the scope that the present invention requires to protect is not limited to the scope that embodiment explains.
Embodiment 1
The basic recipe of embodiment 1 is as shown in table 1 with the enforcement prescription.The AN/MMA mass ratio that feeds intake is that the synthetic operation process of 15/85 o'clock EPM-g-MAN is following:
In three mouthfuls of round-bottomed flasks of 1000ml that condensing reflux pipe, whisking appliance, oil bath heating temperature controller be housed, add EPM 60g, toluene 150g,, add the mix monomer of 34g TEB 3K 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% Z 150PH-224 (PVA-224) aqueous solution is added drop-wise in the reaction system, in 30 minutes, dropwises, and 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 to dry 8 hours down at 80 ℃ with tap water, promptly making diameter is the EPM-g-MAN toughner about 0.5mm.The monomer conversion of reaction system is 89.1%, and the EPM content of EPM-g-MAN is 62.7%.
With mixing with 165 ℃ roller temperature on EPM-g-MAN toughner for preparing and the SAN resin warm-up mill, the EPM content of blend AEMS: the EPM/AEMS quality percentage is 25wt%.Using laminating is 170~175 ℃ of mold pressings at vulcanizing press with the upper and lower mould temperature, processes 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+zero(ppm) 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 prescriptions and reaction conditions
The relation of CR, GR, GE and the AEMS notched Izod impact strength of table 2 (b) embodiment 2 EPM/MMA-AN mass ratioes and grafting system
* the EPM content of AEMS: the EPM/AEMS percentage is 25wt%.
Table 3 (a) embodiment 3 prescriptions and reaction conditions
The relation of CR, GR, GE and the AEMS notched Izod impact strength of table 3 (b) embodiment 3 BPO consumptions and grafting system
* the EPM content of AEMS: the EPM/AEMS percentage is 25wt%.
Table 4 (a) embodiment 4 prescriptions and reaction conditions
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 prescriptions and reaction conditions
The CR of table 5 (b) embodiment 5 PVA consumptions 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 prescriptions and reaction conditions
Table 6 (b) embodiment 6 EPM-g-MAN are to the toughening effect of SAN resin
Claims (9)
1. EPM-g-MAN toughner is characterized in that being processed by following component and weight percentage:
Ethylene propylene rubber 45~65%
Monomer 35~55%
Said monomer is the mixture of TEB 3K and vinyl cyanide;
The preparation method of said toughner is to adopt 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 TEB 3K 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 zero(ppm) water or vaal 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.
2. toughner as claimed in claim 1 is characterized in that following component and weight percentage process:
Ethylene propylene rubber 45~60%
Monomer 40~55%
Said monomer is the mixture of TEB 3K and vinyl cyanide.
3. according to claim 1 or claim 2 toughner is characterized in that the weight percent of said TEB 3K and vinyl cyanide is respectively 95~75%, 5~25%.
4. toughner as claimed in claim 1 is characterized in that said step (1) for solid EPM being 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 processed the EPM glue.
5. like claim 1 or 4 described toughner, it is characterized in that said organic solvent is one or more the mixed solvent in benzene,toluene,xylene, normal heptane, Skellysolve A, normal hexane and the hexanaphthene.
6. toughner as claimed in claim 1 is characterized in that said initiator is a kind of of BPO, dilauroyl peroxide, peroxide tert pivalate ester, peroxy dicarbonate ethylhexyl and the peroxo-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.
7. toughner as claimed in claim 1 is characterized in that said dispersion aids is sodium lauryl sulphate, X 2073, sodium oleate, StNa, naphthene sulfonic acid hydrogen sodium, water-soluble phenylethene-copolymer-maleic anhydride, CMC 99.5; Its consumption is to account for 0.06~0.2% of EPM and monomer total mass.
8. toughner as claimed in claim 1 is characterized in that said dispersion agent is Z 150PH, alkyl polyoxyethylene ether, SEPIGEL 305, Vltra tears; Its consumption is 0.5~0.8% of EPM, monomer and an organic solvent total mass.
9. engineering plastics is characterized in that being made by EPM-g-MAN toughner and SAN resin alloy according to claim 1, and the quality of EPM is 10~30% of engineering plastics in said engineering plastics.
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