CN101050257A - Method for preparing EPDM g-SAN toughening agent containing high quantity EPDM - Google Patents
Method for preparing EPDM g-SAN toughening agent containing high quantity EPDM Download PDFInfo
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Abstract
This invention discloses a method for preparing EPDM-g-SAN toughening agent with a high EPDM content. The method comprises: dissolving EPDM in an inert good solvent, adding mixed monomers of styrene and acrylonitrile, initiator and co-dispersant, stirring at a low speed to uniform mixing, dropping dispersant aqueous solution under high speed stirring, dropping deionized water, heating under nitrogen protection, filtering out the product, washing with water, and drying to obtain EPDM-g-SAN toughening agent with 50-75% of EPDM. When the EPDM-g-SAN toughening agent is melt-blended with SAN resin, an engineering plastic AES is obtained, which has high weathering, aging, yellowing and impact resistance. The method has such advantages as low solvent consumption, high monomer conversion rate, high grafting rate and simple product post-treatment. The EPDM-g-SAN toughening agent has high toughening efficiency.
Description
Technical field
The present invention relates to the preparation of toughner, be specifically related to a kind of synthetic method of graft copolymer EPDM-g-SAN toughner.
Background technology
Ethylene-propylene-diene monomer (EPDM) is to contain the carbon-to-carbon double bond that is easy to oxidation in a large number at synthetic cis-1,4-polybutadiene rubber and the used high-cis cis-1,4-polybutadiene rubber of St-An graft copolymer (ABS) with vinylbenzene (St) and vinyl cyanide (An) mix monomer (St-An) graft copolymer (AES), a kind of polystyrene toughened resin that causes the Weather-resistant xanthochromia poor performance of ABS and develop, at first gone into operation in 1970 by Copolymer-Rubber company, after this Japanese bright dipping oil company, JSR company and German Bayer company go into operation in succession.The preparation method of AES has two kinds of direct synthesis technique and blending methods.Direct synthesis technique is by predefined EPDM/St-An ratio of components, and low AES is used as engineering plastics with the directly synthetic EPDM content of solution polymerization process.Blending method is earlier synthetic EPDM content up to 50～70% graft copolymer EPDM-g-SAN, carry out melt blending with EPDM-g-SAN and St-An graft copolymer (SAN resin) by the ratio of components of setting by the user in molding process then and prepare the AES engineering plastics, wherein g represents grafting.
The AES of direct synthesis technique preparation, its EPDM content is fixed by ratio of components, so the shock strength of goods is single.Can process the different goods of shock strength easily for satisfying the user, the industrial direct synthesis technique that do not adopt is produced AES, but earlier synthetic EPDM content makes AES with SAN resin melt blending again up to 50～70% EPDM-g-SAN.At present, the EPDM-g-SAN of high EPDM content synthetic and prepare AES in states such as U.S., moral, day suitability for industrialized production on a large scale with the SAN resin alloy.The AES engineering plastics are widely used in makes automobile and motorcycle accessories, fishing gear, fishery and agricultural Turnover Box, suitcase, container is because its excellent weather resisteant, also be widely used in outdoor goods such as making house loam cake, door and window, billboard, swimming pool ornament layer, technical economic benefit is remarkable.China's there be limited evidence currently of is carried out the study on the synthesis as the EPDM-g-SAN of toughner, and its suitability for industrialized production more is unrealized.Minority producer prepares the used EPDM-g-SAN of AES and still relies on import.
The EPDM molecular chain mainly is made of ethylene unit, propylene units and a small amount of non-conjugated dienes such as ethylidene norbornene (ENB).ENB structural unit side group carbon-carbon double key.EPDM-g-SAN adopt main chain saturated, have only EPDM and the St-An of a small amount of side group carbon-carbon double key to prepare, so the AES that makes with the SAN resin alloy has the Weather-resistant xanthochromia performance of excellence by graft copolymerization.Has good consistency owing to the component of the contained grafted chain of EPDM-g-SAN is identical with the SAN resin, so prepared AES has good toughness.In addition, the water-intake rate of AES resin also is better than ABS resin.
In theory, EPDM-g-SAN can prepare by technology such as solution polymerization, suspension polymerization and letex polymerizations, but realizes the industrialized solution polymerization process that has only.World industry developed country all adopts blending method to produce AES at present, the industrial solution graft copolymerization legal (hereinafter referred solution method) that then adopts is produced EPDM-g-SAN toughner, its building-up process is at first with normal hexane and chlorobenzene mixed solvent dissolving EPDM, add St-An and initiator dicumyl peroxide again, 120 ℃ of reactions 22 hours, with a large amount of methyl alcohol product EPDM-g-SAN precipitation is reclaimed then.The remarkable shortcoming of solution method is that monomer conversion is low, generally can only reach about 75% (wt), solvent load is big, (EPDM+St+An)/and the ratio of solvent (wt/wt) is lower than 1/4, and promptly solvent accounts for more than 80% of whole polymerization system quality, and product need be used a large amount of methanol extractions, the waste liquid that is reclaimed is solvent, residual monomer and methanol mixture, with the process complexity that each component is separated the purification recycle, facility investment is big, causes the high enterprise of production cost.Japanese Patent JP48017895 discloses the directly method of synthetic AES of a kind of aqueous suspension polymerization that adopts solubilizing agent, but this method is 10 times of the EPDM quality as the normal hexane consumption of solvent, monomer conversion only is 70.8%, solvent aftertreatment difficulty, and the EPDM content of the AES that makes is only for about 26wt%, product belongs to the AES engineering plastics, can not be used as toughner.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists with the synthetic EPDM-g-SAN of solution method at present, provide a kind of EPDM content height, monomer conversion and percentage of grafting height, solvent load few, product and solvent aftertreatment are easy, the preparation method of the EPDM-g-SAN toughner of product form homogeneous.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of EPDM-g-SAN toughner of high EPDM content comprises the steps and processing condition:
(1) in reactor, add EPDM and inertia good solvent, EPDM is fully dissolved after, add the mix monomer of initiator and St, An again, mix; The mass ratio of described St and An is 70: 30～50: 50; The mass ratio of described EPDM and mix monomer St-An is 5: 5～7: 3; Described initiator is selected from dibenzoyl peroxide (BPO), 1,1-bis(t-butylperoxy)-3,3, one or more in 5-trimethyl-cyclohexane, the peroxidation 2 ethyl hexanoic acid tert-butyl ester; Initiator amount is 1～2.5% of a mix monomer quality;
(2) add dispersion aids, under stirring at low speed, dripping concentration is the aqueous solution of 1～4wt% main dispersant, improves stirring velocity gradually to stirring at a high speed; Add deionized water, constitute EPDM/St-An suspension graft copolymerization system; Described main dispersant is one or more in polyvinyl alcohol, cellulose ethers and the polyacrylic acid sodium salt; The main dispersant consumption be inertia good solvent, EPDM, St and An quality and 0.3～1%; Described dispersion aids is aniorfic surfactant or nonionic surface active agent, and dispersion aids and main dispersant mass ratio are 1: 3～1: 15; The consumption of described deionized water is: by weight, the ratio of the moisture content weight sum of deionized water and aqueous dispersant and inertia good solvent, EPDM, St and An weight sum is 3: 1～3: 2;
(3) adjust stirring velocity to middling speed,, reaction system is warming up to 75～90 ℃, under nitrogen protection isothermal reaction 16-24 hour with water-bath or oil bath heating;
(4) with the reaction system cooling, discharging also leaches product, makes EPDM-g-SAN toughner after the washing oven dry.
Described inertia good solvent is selected from one or more the mixture in benzene, toluene, normal heptane, hexanaphthene, dimethylbenzene, the pimelinketone, preferred toluene, and its consumption is 1.5～2.5 times of EPDM quality.
The adding mode of described initiator and St, An mix monomer is that initiator is dissolved in mix monomer in advance and adds EPDM solution in the lump, and perhaps initiator is dissolved in solvent in advance, splashes into EPDM/St-An solution then.
The mass ratio of described EPDM and St-An is preferably 55: 45～and 65: 35.
Aniorfic surfactant is a kind of of sodium lauryl sulphate and Sodium dodecylbenzene sulfonate or two kinds.Described nonionic surface active agent is a kind of of water miscible polyoxyethylenesorbitan sorbitan monooleate (Tween60) and polyoxyethylene sorbitan monostearate (Tween80) or two kinds.
Dispersion aids and main dispersant mass ratio be preferably 1: 5～and 1: 10.
Inventive principle: in the EPDM/St-An system, along with the raising of EPDM consumption, the corresponding minimizing of St-An consumption.The small amounts of monomer amount is difficult to dissolve a large amount of EPDM, thereby can't make dispersible EPDM/St-An solution.Employing adds a small amount of solvent in EPDM/St-An method can make dispersible solution, thereby suspension polymerization can be carried out smoothly.
The advantage and the beneficial effect that have with respect to prior art the present invention are:
(1) the EPDM content of the EPDM-g-SAN toughner of the present invention's preparation is up to 50～70%; The monomer conversion of graft copolymerization system is more than 90%, to reach as high as 98%.The percentage of grafting of EPDM-g-SAN is 40～65%.Prepared toughner is the Powdered of diameter 0.1～2.0mm or pearl particle.
(2) to prepare the legal solvent load of the used suspension graft copolymerization of EPDM-g-SAN few in the present invention, only is EPDM and St-An quality sum 1～2 times, and product and solvent reclaim easily, and last handling process is simple.
(3) the EPDM-g-SAN toughner and the SAN resin of application the present invention preparation make AES with two roller warm-up mills or twin screw extruder melt blending, and the EPDM/AES mass percent is 15～35% o'clock, the corresponding 32.6～60.8KJ/m that reaches of the notched Izod impact strength of AES
2
Description of drawings
Fig. 1 is the attenuated total reflectance attenuated total refraction infrared light figure spectrogram of EPDM-g-SAN after EPDM, SAN and the extracting.
Embodiment
The invention will be further described below in conjunction with embodiment.The contriver has many successful examples to the present invention after research and testing, enumerates part embodiment below, but the scope of protection of present invention is not limited to the scope of embodiment statement.
In three mouthfuls of round-bottomed flasks of 1000ml that condensing reflux pipe, agitator, oil bath heating temperature controller be housed, add EPDM48g, toluene 90g, 60 ℃ of following stirring at low speed dissolvings 12 hours, add and dissolved the 20.8g vinylbenzene of 0.48g BPO and the mix monomer of 11.2g vinyl cyanide.The control stirring velocity is 150 rev/mins, stirs to add sodium lauryl sulphate powder 0.12g after 10 minutes, continues to stir 5 minutes.With 45g concentration is that 2% polyvinyl alcohol-224 (PVA-224) aqueous solution is added drop-wise in the reaction system, dropwises in 15 minutes.Simultaneously stirring velocity is brought up to 1200 rev/mins gradually.The 250g deionized water is slowly added in the flask, and logical nitrogen 15 minutes improves 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 3 times, place vacuum drying oven,, make diameter and be the EPDM-g-SAN toughner about 0.5mm by following Infrared spectroscopy 80 ℃ of oven dry 8 hours with tap water.The monomer conversion of reaction system is 98%, and the EPDM content of EPDM-g-SAN is 60.5%.
The measuring method of monomer conversion and percentage of grafting is as follows: EPDM-g-SAN wraps up with filter paper with the synthetic suspension method, and putting into apparatus,Soxhlet's is solvent extraction 48h with acetone, isolates free SAN, purified product in 80 ℃ of vacuum-dryings to constant weight.Monomer conversion (CR), percentage of grafting (GR) and grafting efficiency (GE) calculating formula are as follows:
In the formula, W is pure EPDM-g-SAN quality; A is an EPDM quality among the EPDM-g-SAN.
The method of calculation of EPDM/AES
Infrared spectroscopy:
It is in blocks to remain grafts, EPDM and the hot pressing of SAN resin in this example 1 after the prepared EPDM-g-SAN extracting, goes up test at infrared spectrophotometer SP2000 (Britain Pye Unicam Ltd.).
The attenuated total reflectance attenuated total refraction infrared spectrogram of EPDM-g-SAN as shown in Figure 1 after EPDM, SAN and the extracting.From figure as can be seen, purification graft copolymer infrared spectra is the feature stretching vibration absorption peak that C ≡ N group has appearred in the 2238cm-1 place in wave number, the charateristic avsorption band of single-substituted ring occurred at 760cm-1 and 701cm-1, and these absorption peaks do not occur in the infrared spectrogram of EPDM.Can prove EPDM molecular chain SAN side chain in the grafting really thus, promptly graft copolymerization has taken place in EPDM and St and An.
EPDM-g-SAN toughner and SAN resin roller temperature with 165 ℃ on warm-up mill of present embodiment preparation is mixing, promptly make the AES engineering plastics of excellent combination property.After testing, the relation of its socle girder notched Izod impact strength and EPDM/AES ratio is as shown in table 1.By table 1 as seen, when the EPDM/AES quality ratio is lower than 12.5%, the socle girder notched Izod impact strength of AES increases slowly, the EPDM/AES quality ratio is between 12.5～15%, the socle girder notched Izod impact strength of AES sharply increases, after the EPDM/AES quality ratio was higher than 15%, the increase of socle girder notched Izod impact strength was just slow.This shows that suspension method EPDM-g-SAN just can effectively improve the toughness of AES at low consumption, the EPDM/AES quality ratio be 15% o'clock promptly up to 36.9KJ/m
2, it is to the toughening efficiency height of SAN resin.
The relation of table 1 notched Izod impact strength and EPDM/AES ratio
| The content (%) of EPDM in AES | 5 | 10 | 12.5 | 15 | 20 | 25 | 35 |
| Notched Izod impact strength (KJm -2) | 1.9 | 4.4 | 7.0 | 36.9 | 46.5 | 58.9 | 60.5 |
Embodiment 2
In three mouthfuls of round-bottomed flasks of 1000ml that condensing reflux pipe, agitator, oil bath heating temperature controller be housed, add EPDM36g, pimelinketone 30g, normal heptane 24g, 60 ℃ of following stirring at low speed dissolvings 12 hours, add and dissolved the 27g vinylbenzene of the 0.16g peroxidation 2 ethyl hexanoic acid tert-butyl ester and 0.2g dibenzoyl peroxide and the mix monomer of 9g vinyl cyanide.The control stirring velocity is 120 rev/mins, stirs to add Sodium dodecylbenzene sulfonate powder 0.08g after 10 minutes, continues to stir 5 minutes.With 30g concentration is that 4% methylated cellulose aqueous solution is added drop-wise in the reaction system, dropwises in 15 minutes, adjusts stirring velocity simultaneously and brings up to 1200 rev/mins gradually.The 350g deionized water is slowly added in the flask, and logical nitrogen 15 minutes improved temperature of reaction to 75 ℃ in 5 minutes under nitrogen protection.React and system is cooled to room temperature, discharging after 16 hours.With 200 order filter clothes product is leached, with product washing three times, place vacuum drying oven, promptly make diameter and be the EPDM-g-SAN toughner about 0.4mm 80 ℃ of oven dry 8 hours down with tap water.The monomer conversion 91% of reaction system, the EPDM content of EPDM-g-SAN is 52.4%.
With mixing on the EPDM-g-SAN toughner of preparation and the SAN resin warm-up mill, promptly make the AES of excellent combination property with 165 ℃ roller temperature.Be respectively 15%, 20% and at 25% o'clock at the EPDM/AES quality ratio, the socle girder notched Izod impact strength is respectively 24.2KJ/m
2, 35.3KJ/m
2And 39.8KJ/m
2
Embodiment 3
In three mouthfuls of round-bottomed flasks of 1000ml that condensing reflux pipe, agitator, oil bath heating temperature controller be housed, add EPDM56g, dimethylbenzene 140g, 60 ℃ of following stirring at low speed dissolvings 11 hours, add and dissolved 0.6gl, 1-bis(t-butylperoxy)-3,3, the 13.2g vinylbenzene of 5-trimethylammonium cyclohexane and the mix monomer of 10.8g vinyl cyanide.The control stirring velocity is 160 rev/mins, stirs to add 0.12g Sodium dodecylbenzene sulfonate powder, 0.1gT polyoxyethylenesorbitan sorbitan monooleate (Tween80) after 10 minutes, continues to stir 5 minutes.With 66g concentration is that 1% methylated cellulose aqueous solution is added drop-wise in the reaction system, dropwises in 15 minutes, adjusts stirring velocity simultaneously and brings up to 1000 rev/mins gradually.The 264g deionized water is slowly added in the flask, and logical nitrogen 15 minutes improved temperature of reaction to 90 ℃ in 5 minutes under nitrogen protection.React and system is cooled to room temperature, discharging after 24 hours.With 200 order filter clothes product is leached, with product washing three times, place vacuum drying oven, promptly make diameter and be the EPDM-g-SAN toughner about 0.4mm 80 ℃ of oven dry 8 hours down with tap water.The monomer conversion 96% of reaction system, the EPDM content of EPDM-g-SAN is 70.9%.With mixing on toughner and the SAN resin warm-up mill, promptly make the AES of excellent combination property with 165 ℃ roller temperature.Be respectively 15%, 20% and at 25% o'clock at the EPDM/AES quality ratio, the socle girder notched Izod impact strength is respectively 37.9KJ/m
2, 49.6KJ/m
2And 59.8KJ/m
2
Embodiment 4
At heating oil cauldron, hot oil pump, a stainless steel condensation reflux device that has been equipped with automatic temperature control instrument, add EPDM 1008g, toluene 1890g in the stainless steel cauldron of the 20L chuck heating of material automatic temperature control instrument in the 1.1KW agitator of band variable-frequence governor and the still, 60 ℃ of following stirring at low speed dissolvings 12 hours, add and dissolved the 399g vinylbenzene of 10gBPO and the mix monomer of 231g vinyl cyanide, the control stirring velocity is 100 rev/mins, add 2.52g polyoxyethylene sorbitan monostearate (Tween60) after 15 minutes, continue to stir 5 minutes.With 945g concentration is that 2% the PVA-224 aqueous solution is added drop-wise in the reactor, when dripping stirring velocity is brought up to 400 rev/mins gradually, dropwises in 30 minutes.The 5250g deionized water is slowly added in the reactor, add in 10 minutes.Logical nitrogen 15 minutes improves temperature of reaction to 80 ℃ in 10 minutes under nitrogen protection.After the isothermal reaction 20 hours, system is cooled to room temperature, discharging.With 200 order filter clothes product is leached, with product washing three times, place vacuum drying oven with tap water, promptly make the 1576g diameter and be the toughner EPDM-g-SAN about 0.9mm 80 ℃ of oven dry 8 hours down, the monomer whose transformation efficiency is 90.2%, and EPDM content is 62.4%.With toughner and SAN resin with different proportionings warm-up mill on the mixing AES resin that promptly makes excellent combination property of 165 ℃ roller temperature, be respectively 15%, 20% and at 25% o'clock at the EPDM/AES quality ratio, the socle girder notched Izod impact strength of AES is respectively 32.6KJ/m
2, 44.2KJ/m
2, 56.6KJ/m
2
Embodiment 5～7
The experimental formula of embodiment 5～7, reaction times, temperature of reaction are as shown in table 2.In three mouthfuls of round-bottomed flasks of 1000ml that condensing reflux pipe, agitator, oil bath heating temperature controller be housed, add EPDM and solvent,, add and dissolved the vinylbenzene of initiator and the mix monomer of vinyl cyanide 60 ℃ of following stirring at low speed dissolvings 15 hours.The control stirring velocity is 180 rev/mins, stirs to add sodium lauryl sulphate powder 0.12g after 10 minutes, continues to stir 5 minutes.With concentration is that 2% polyvinyl alcohol-224 (PVA-224) aqueous solution is added drop-wise in the reaction system, dropwises in 15 minutes.Simultaneously stirring velocity is brought up to 1200 rev/mins gradually.Deionized water is slowly added in the flask, and logical nitrogen 15 minutes improves the temperature of reaction temperature of reaction in 5 minutes under nitrogen protection.Reaction is cooled to room temperature with system, discharging after finishing.With 200 order filter clothes product is leached, with product washing 3 times, place vacuum drying oven, promptly make EPDM-g-SAN toughner 80 ℃ of oven dry 8 hours with tap water.
EPDM-g-SAN toughner and SAN resin roller temperature with 165 ℃ on warm-up mill of preparation is mixing, promptly make the AES engineering plastics of excellent combination property.
| Title | Consumption and experimental result | ||
| Example 5 | Example 6 | Example 7 | |
| EPDM styrene/g acrylonitrile/g benzene/g normal heptane/g dimethylbenzene/g BPO/g reaction temperature/℃ reaction time/h conversion ratio/% gum content/% impact strength (EPDM/AES, 15wt%)/KJm-2Shock strength (EPDM/AES, 25wt%)/KJm -2Shock strength (EPDM/AES, 35wt%)/KJm -2 | 52 19.6 8.4 0 0 90 0.48 80 22 92.8 66.7 19.8 27.9 34.1 | 44 21.6 14.4 40 60 0 0.4 85 16 90.6 57.4 39.4 50.1 69.7 | 48 17.6 14.4 80 0 0 0.52 80 20 93.4 61.6 38.7 48.5 62.0 |
Claims (8)
1, a kind of preparation method of EPDM-g-SAN toughner of high EPDM content is characterized in that comprising the steps and processing condition:
(1) in reactor, add EPDM and inertia good solvent, EPDM is fully dissolved after, add the mix monomer of initiator and St, An again, mix; The mass ratio of described St and An is 70: 30～50: 50; The mass ratio of described EPDM and mix monomer St-An is 5: 5～7: 3; Described initiator is selected from dibenzoyl peroxide, 1,1-bis(t-butylperoxy)-3,3, one or more in 5-trimethyl-cyclohexane, the peroxidation 2 ethyl hexanoic acid tert-butyl ester; Initiator amount is 1～2.5% of a mix monomer quality;
(2) add dispersion aids, under stirring at low speed, dripping concentration is the aqueous solution of 1～4wt% main dispersant, improves stirring velocity gradually to stirring at a high speed; Add deionized water, constitute EPDM/St-An suspension graft copolymerization system; Described main dispersant is one or more in polyvinyl alcohol, cellulose ethers and the polyacrylic acid sodium salt; The main dispersant consumption be inertia good solvent, EPDM, St and An quality and 0.3～1%; Described dispersion aids is aniorfic surfactant or nonionic surface active agent, and dispersion aids and main dispersant mass ratio are 1: 3～1: 15; The consumption of described deionized water is: by weight, the ratio of the moisture content weight sum of deionized water and aqueous dispersant and inertia good solvent, EPDM, St and An weight sum is 3: 1～3: 2;
(3) adjust stirring velocity to middling speed,, reaction system is warming up to 75～90 ℃, under nitrogen protection isothermal reaction 16-24 hour with water-bath or oil bath heating;
(4) with the reaction system cooling, discharging also leaches product, makes EPDM-g-SAN toughner after the washing oven dry.
2, the preparation method of the EPDM-g-SAN toughner of a kind of high EPDM content according to claim 1, it is characterized in that described inertia good solvent is selected from one or more the mixture in benzene, toluene, normal heptane, hexanaphthene, dimethylbenzene, the pimelinketone, its consumption is 1.5～2.5 times of EPDM quality.
3, the preparation method of the EPDM-g-SAN toughner of a kind of high EPDM content according to claim 2 is characterized in that described inertia good solvent is a toluene.
4, the preparation method of the EPDM-g-SAN toughner of a kind of high EPDM content according to claim 1, the adding mode that it is characterized in that described initiator and St, An mix monomer is that initiator is dissolved in mix monomer in advance and adds EPDM solution in the lump, perhaps initiator is dissolved in solvent in advance, splashes into EPDM/St-An solution then.
5, the preparation method of the EPDM-g-SAN toughner of a kind of high EPDM content according to claim 1, the mass ratio that it is characterized in that described EPDM and St-An is 55: 45～65: 35.
6, the preparation method of the EPDM-g-SAN toughner of a kind of high EPDM content according to claim 1 is characterized in that aniorfic surfactant is a kind of of sodium lauryl sulphate and Sodium dodecylbenzene sulfonate or two kinds.
7, the preparation method of the EPDM-g-SAN toughner of a kind of high EPDM content according to claim 1 is characterized in that described nonionic surface active agent is a kind of of water miscible polyoxyethylenesorbitan sorbitan monooleate and polyoxyethylene sorbitan monostearate or two kinds.
8, the preparation method of the EPDM-g-SAN toughner of a kind of high EPDM content according to claim 1 is characterized in that described dispersion aids and main dispersant mass ratio are 1: 5～1: 10.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560282B (en) * | 2009-05-26 | 2011-02-02 | 金发科技股份有限公司 | PEB-g-SAN toughener and preparation method thereof as well as engineering plastics AEBS |
| CN102127192A (en) * | 2010-12-06 | 2011-07-20 | 宁波镇洋化工发展有限公司 | Continuous bulk preparation method of acrylonitrile-ethylene propylene diene monomer (EPDM)-styrene (AES) resin |
| CN102898759A (en) * | 2012-09-27 | 2013-01-30 | 上海锦湖日丽塑料有限公司 | Acrylonitrile-ethylene-styrene (AES) resin composition and preparation method thereof |
-
2007
- 2007-04-28 CN CNB2007100277442A patent/CN100567351C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560282B (en) * | 2009-05-26 | 2011-02-02 | 金发科技股份有限公司 | PEB-g-SAN toughener and preparation method thereof as well as engineering plastics AEBS |
| CN102127192A (en) * | 2010-12-06 | 2011-07-20 | 宁波镇洋化工发展有限公司 | Continuous bulk preparation method of acrylonitrile-ethylene propylene diene monomer (EPDM)-styrene (AES) resin |
| CN102127192B (en) * | 2010-12-06 | 2012-10-17 | 宁波镇洋化工发展有限公司 | Continuous bulk preparation method of acrylonitrile-ethylene propylene diene monomer (EPDM)-styrene (AES) resin |
| CN102898759A (en) * | 2012-09-27 | 2013-01-30 | 上海锦湖日丽塑料有限公司 | Acrylonitrile-ethylene-styrene (AES) resin composition and preparation method thereof |
| CN102898759B (en) * | 2012-09-27 | 2015-05-13 | 上海锦湖日丽塑料有限公司 | Acrylonitrile-ethylene-styrene (AES) resin composition and preparation method thereof |
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| CN100567351C (en) | 2009-12-09 |
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