CN101348545A - Method for preparing EPT rubber graft by emulsion method - Google Patents
Method for preparing EPT rubber graft by emulsion method Download PDFInfo
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- CN101348545A CN101348545A CNA2007101191896A CN200710119189A CN101348545A CN 101348545 A CN101348545 A CN 101348545A CN A2007101191896 A CNA2007101191896 A CN A2007101191896A CN 200710119189 A CN200710119189 A CN 200710119189A CN 101348545 A CN101348545 A CN 101348545A
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Abstract
The invention relates to a method for synthesizing a styrene-ethylene propylene terpolymer-acrylonitrile graft through an emulsion polymerization method. The obtained styrene- ethylene propylene terpolymer-acrylonitrile graft can be used for preparing a styrene- ethylene propylene terpolymer-acrylonitrile graft resin through mixing with SAN. Because of the simple emulsification process and the high grafting efficiency, the method can save production cost and is characterized by continuous production.
Description
Technical field
The invention belongs to chemical field, particularly emulsion polymerization prepares the method for macromolecular compound.
Background technology
Vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin is a kind of engineering plastics new variety of developing at ABS weathering resistance difference.(be called for short: EPDM) the molecular chain double bond content is few, so the weathering resistance of vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin than the high 4-8 of ABS doubly for terpolymer EP rubber in vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin.Thermostability, water-intake rate and the shock strength of vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin all are better than ABS resin, and other performances are then similar to ABS.Vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin is not only the splendid resin of a kind of weathering resistance, and because EPDM rubber phase second-order transition temperature is low, make vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin have the excellent more low-temperature impact resistance of forming than acrylate, vinylbenzene and acrylonitrile of graft copolymer, thereby be used in automobile component more and more and other needs long, safe and reliable plastics of life-span.Do not need the advantage of application to make vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin more competitive on price.In the E-consumer field,, the weathering resistance of vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin also can keep the original fresh beautiful color of goods better by life-time service even also meaning.
The preparation method of vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing has two kinds of direct synthesis technique and blending methods.Direct synthesis technique is by predefined vinyl cyanide, EPDM, vinylbenzene ratio of components, directly synthetic with solution polymerization, letex polymerization or suspension polymerization, the product that obtains be a kind of be main chain with EPDM, be the novel vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing of side chain with the styrene-acrylonitrile copolymer.The blend rule is to utilize capacity increasing technique that EPDM and styrene-acrylonitrile copolymer are mixed with under molten state.
US3642950, the suspension polymerization type reaction that US3876727 describes is: EPDM suspends in water with the granulation dispersive, adds vinylbenzene and vinyl cyanide in two steps, causes radical polymerization.Fs adds a spot of vinylbenzene and vinyl cyanide, and both also generate styrene-acrylonitrile copolymer simultaneously, but its molecular weight are less except that to the EPDM grafting, and system does not have being separated of real meaning, and graftomer is transparent, says in essence to be polymerization in homogeneous phase; Simultaneously because EPDM concentration height helps the raising of percentage of grafting.Subordinate phase adds a large amount of vinylbenzene and vinyl cyanide and reacts, the molecular weight that generate styrene-acrylonitrile copolymer this moment increases gradually, be grafted to the effect that styrene-acrylonitrile copolymer side chain on the EPDM plays compatilizer between EPDM and the styrene-acrylonitrile copolymer, form good surface reaction, and realize micron-scale phase separation gradually.To contain different dienes (as ethylidene norbornene; Dicyclopentadiene; 1,4 one hexadiene etc.) therefore EPDM repeated experiments, the shock strength of the polymkeric substance that obtains infer that they have similar percentage of grafting near (socle girder impacts about 411J/m); But if select not double bond containing ethylene-propylene rubber(EPR) for use, the product impact property can obviously reduce (32J/m).
Research about vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin solution polymerization is more, and single still, two still and the operation of three stills are arranged, can intermittence or continuous production.US416608, US3876727, US4314041 describes its model experiment: 40g EPDM (mooney viscosity 66, ethylene/propene (mass ratio)=50/50, ethylidene norbornene: 8.7C=C/1000C) be dissolved in the benzene of 1400g 50/50 (mass ratio) and the mixing solutions of normal hexane.Then, to wherein adding 450g vinylbenzene, 150g vinyl cyanide and 6.0g benzoyl peroxide (once or at twice adding), 70 ℃ of following graft reactions 20 hours, the product impact property can reach 328J/m.
The solution polymerization of vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin has just realized continuous production processes as far back as 1975.The available solvent of solution polymerization is more, and the single solvent or the mixed solvent of toluene, benzene, normal hexane, chloroform etc. arranged.It is reported, make the mechanical property of the synthetic AES of solvent, be better than the mixed solvent of benzene, toluene and they and other solvent with the mixing solutions of toluene, benzene, methylene dichloride.
Letex polymerization is compared with other polymerization processs has some outstanding advantages: because polymerization system is in the state of good fluidity all the time in polymerization process, therefore, the reaction heat that radical polymerization is emitted is easy to pass by water (1); (2) rate of polymerization is more much higher than common body equilibrium polymerization; (3) product of the molecular weight ratio body of polymerisate or solution polymerization is much higher; (4) polymerisate generates with the latex form, thereby processing ease; (5) be easy to control molecular weight of product by adding chain-transfer agent, thus the character of control final product; (6) polymerization process and product latex all are medium with water, so safety and environmental problem are less.
US4788250, US3435096 has described typical letex polymerization: the crosslinked EPDM latex that emulsification is good is heated to 70 ℃ in water-bath, remove solvent, then to wherein adding vinylbenzene, vinyl cyanide, Vinylstyrene, cumene hydroperoxide (antioxidant that is used for oxidation system), lauryl mercaptan (as chain-transfer agent) etc.Its total reaction time is shorter, about 3 hours.There is 25% styrene-acrylonitrile copolymer resin to be grafted on the EPDM, it is suitable grafting to take place and the molecular weight of grafted styrene-acrylonitrile copolymer resin does not take place, but emulsifying process is comparatively complicated, and adding linking agent Vinylstyrene makes grafting efficiency lower in polymerization system, is unfavorable for saving production cost.
Summary of the invention
The purpose of this invention is to provide the method that a kind of emulsion polymerization prepares vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing, to solve the problem that mass polymerization does not readily conduct heat and the solution polymerization solvent amount of expending is big.
The method of a kind of emulsion polymerization prepared vinylbenzene-terpolymer EP rubber provided by the invention-acrylonitrile grafting thing is characterized in that, in turn includes the following steps:
(1) in terpolymer EP rubber/normal hexane rubber cement, adds emulsifying agent and carry out emulsification, obtain ethylene-propylene rubber(EPR) latex;
Described terpolymer EP rubber is the 3rd monomer with ethylidene norbornene; The quality solid content of described terpolymer EP rubber/normal hexane rubber cement is 9-16%; Said emulsifying agent is a saponified emulsification system in nilox resin and the potassium hydroxide emulsion process;
(2) with the ethylene-propylene rubber(EPR) latex of different emulsifying process gained temperature at 60-70 ℃, under the initiator effect, carry out 9-16 hour polyreaction with monomer, promptly get vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing;
Said different emulsifying process specifically is divided into following several: under the protection of inert gas situation, and terpolymer EP rubber/normal hexane rubber cement and monomer emulsification together, the disposable adding of initiator; Or terpolymer EP rubber/independent emulsification of normal hexane rubber cement, monomer dropping or disposable adding; Or desolventizing after terpolymer EP rubber/independent emulsification of normal hexane rubber cement, the disposable adding of monomer; Said monomer is vinylbenzene and vinyl cyanide, and the mass ratio of vinylbenzene and vinyl cyanide is (2.5-3.5): 1; Said initiator is a Potassium Persulphate, one of or isopropyl benzene hydroperoxide/ferrous sulfate/glucose/trisodium phosphate redox system, redox system isopropyl benzene hydroperoxide/ferrous sulfate/glucose/trisodium phosphate mass ratio is followed successively by: (96-99): 1: (56-59): (46-49).
The preferred 6000-16000r/min of the stirring velocity of emulsion process of the present invention.
Emulsifying agent in the inventive method is a saponified emulsification system in nilox resin and the potassium hydroxide emulsion process, and the emulsifying agent consumption is the 3.5-8.5% of the oil phase total mass of vinylbenzene, terpolymer EP rubber, normal hexane and vinyl cyanide composition.
Emulsion process adds deionized water, and its quality is the 100-200% of the oil phase total mass of vinylbenzene, terpolymer EP rubber, normal hexane and vinyl cyanide composition.
The quality of the Potassium Persulphate in the inventive method is the 0.6-1.5% of monomer total mass.
Initiator also can be isopropyl benzene hydroperoxide/ferrous sulfate/glucose/trisodium phosphate redox system, and the isopropyl benzene hydroperoxide consumption is the 0.40-0.50% of terpolymer EP rubber, vinylbenzene and vinyl cyanide quality summation.
Vinylbenzene-terpolymer EP rubber that the present invention makes-acrylonitrile grafting thing can (be called for short: SAN) resin be that the ratio of 10-15% is carried out blending according to the rubber quality mark, obtains vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin with styrene-acrylonitrile copolymer.
The present invention has synthesized vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing with method of emulsion polymerization, and polymerization process is stable, and the products obtained therefrom grafting efficiency can reach 33-71%, and shock strength reaches 150-152J/m.Compared with prior art, the present invention utilizes the terpolymer EP rubber rubber cement of manufacturer to carry out emulsification, then under initiator causes, carry out the emulsion graft copolymerization of vinylbenzene, vinyl cyanide, the vinylbenzene-terpolymer EP rubber that makes-acrylonitrile grafting thing can prepare vinylbenzene-terpolymer EP rubber-acrylonitrile grafting resin by the blending with SAN; The inventive method emulsifying process is simple, and therefore the grafting efficiency height can save production cost, and possesses the quantity-produced of realization feature.
Embodiment
Below be specific embodiments of the invention, but the present invention is not limited only to these embodiment.
Embodiment 1
At first, in there-necked flask, add terpolymer EP rubber/normal hexane rubber cement 92g (solid content 9.873% (massfraction)), vinylbenzene 30g, vinyl cyanide 10g, nilox resin 5.28g; Take by weighing 2.64g potassium hydroxide, add in the constant pressure funnel with 50g deionized water dilution back, with constant pressure funnel, there-necked flask, protection of inert gas pipe and high-speed stirring instrument assemble, and inert gas tube is led to below the oil phase liquid level.Open the protection of inert gas pipe; fully air in the displacement there-necked flask is opened and is stirred, and shearing rate is 6000r/min; earlier oil phase is mixed; open constant pressure funnel again, with 1-8 drip/speed of s drips potassium hydroxide aqueous solution, on one side saponification emulsification on one side; add deionized water 150g altogether; can see significantly that in emulsion process system external phase becomes water by oil phase, obtain white emulsion, stop to stir, closing protection of inert gas.
Rubber/monomer emulsion that emulsification is good joins in the reactor that has backflow, heating, stirring, protection of inert gas; open air in the abundant metathesis reactor of protection of inert gas; to guarantee not having air in the reactor; open stirring, reflux condensation mode; after being heated to 65 ℃; add initiator potassium persulfate 0.32g (Potassium Persulphate being dissolved the disposable adding in back) with the 10g deionized water; behind the question response 10h; stopped reaction; recording monomer conversion is 75.85%; the latex particle particle diameter is 144.3nm, and the latex particle size is constant substantially in following examples.Emulsion in the reactor is poured in the beaker cools off.
The configuration pH value is 3 glacial acetic acid aqueous solution, add the Glacial acetic acid breakdown of emulsion while the emulsion that stirs in the beaker, washing, drying obtains product 44.70g, adopt the Soxhlet method for extracting to survey percentage of grafting, the percentage of grafting that obtains vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing is 196.8%, and grafting efficiency is 54.75%.
Embodiment 2
At first, in there-necked flask, add terpolymer EP rubber/normal hexane rubber cement 62g (solid content 14.65% (massfraction)),, join in the there-necked flask after the dissolving with 30g normal hexane dissolving nilox resin 5.28g; Take by weighing 2.64g potassium hydroxide, add in the constant pressure funnel with 50g deionized water dilution back, with constant pressure funnel, there-necked flask, protection of inert gas pipe and high-speed stirring instrument assemble, and inert gas tube is led to below the oil phase liquid level.Open the protection of inert gas pipe; fully replace air in the there-necked flask; open and stir, earlier oil phase is mixed, open constant pressure funnel again; with 1-8 drip/speed of s drips potassium hydroxide aqueous solution; the emulsification on one side of saponification on one side adds deionized water 150g altogether, can see significantly that in emulsion process system external phase becomes water by oil phase; obtain white emulsion, stop to stir, closing protection of inert gas.
The rubber latex that emulsification is good joins and has backflow; heating; stir; in the reactor of protection of inert gas; open air in the abundant metathesis reactor of protection of inert gas; to guarantee not having air in the reactor; open and stir; reflux condensation mode; after being heated to 65 ℃; add 0.16g Potassium Persulphate (it being dissolved) with the 5g deionized water; begin to drip 30g vinylbenzene and 10g vinyl cyanide mix monomer; when adding a half, monomer adds remaining initiator 0.16g (it being dissolved) with the 5g deionized water; dripping monomer speed is 4～6/s; behind the question response 10h, stopped reaction, recording monomer conversion is 47.4%.Emulsion in the reactor is poured in the beaker cools off.
Configuration PH is 3 glacial acetic acid aqueous solution, add the Glacial acetic acid breakdown of emulsion while the emulsion that stirs in the beaker, washing, drying obtains product 33.32g, with acetone is extraction agent, use the Soxhlet method for extracting to measure, the percentage of grafting that obtains vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing is 151.8%, and grafting efficiency is 55.84%.
Embodiment 3
The material add-on is with embodiment 2, shearing rate is 10000r/min during emulsification, 30g vinylbenzene and 10g vinyl cyanide mix monomer are after the emulsion system temperature is raised to 65 ℃, disposable adding, initiator potassium persulfate 0.32g (it being dissolved) with the 10g deionized water after system temperature is raised to 65 ℃, disposable adding.Behind the question response 10h, stopped reaction, recording monomer conversion is 61.16%.Emulsion in the reactor is poured in the beaker cools off.
Configuration PH is 3 glacial acetic acid aqueous solution, add the Glacial acetic acid breakdown of emulsion while the emulsion that stirs in the beaker, washing, drying obtains product 38.83g, with acetone is extraction agent, use the Soxhlet method for extracting to measure, the percentage of grafting that obtains vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing is 192.6%, and grafting efficiency is 50.1%.
Embodiment 4
Emulsifying process and material add-on are with embodiment 2, with the heating of the rubber latex magnetic agitation after emulsification air distillation, slough normal hexane solvent 120ml, adding monomer and initiator carry out polyreaction in sloughing the rubber latex of solvent, and its technology and material add-on are with embodiment 2.Finally recording monomer conversion is 41.84%.Emulsion in the reactor is poured in the beaker cools off.
Configuration PH is 3 glacial acetic acid aqueous solution, add the Glacial acetic acid breakdown of emulsion while the emulsion that stirs in the beaker, washing, drying obtains product 31.10g, with acetone is extraction agent, use the Soxhlet method for extracting to measure, the percentage of grafting that obtains vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing is 93.71%, and grafting efficiency is 33.14%.
Embodiment 5
Emulsifying process and material add-on are with embodiment 2, with the heating of the rubber latex magnetic agitation after emulsification air distillation, slough normal hexane solvent 118ml, in sloughing the rubber latex of solvent, add monomer and initiator and carry out its technology of polyreaction and material add-on with embodiment 3.Finally recording monomer conversion is 74.97%.Emulsion in the reactor is poured in the beaker cools off.
Configuration PH is 3 glacial acetic acid aqueous solution, add the Glacial acetic acid breakdown of emulsion while the emulsion that stirs in the beaker, washing, drying obtains product 44.35g, with acetone is extraction agent, use the Soxhlet method for extracting to measure, the percentage of grafting that obtains vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing is 181.7%, and grafting efficiency is 53.2%.
Embodiment 6
At first, in there-necked flask, add terpolymer EP rubber/normal hexane rubber cement 63.43g (solid content 14.32% (massfraction)), vinylbenzene 39.87g, vinyl cyanide 13.21g, nilox resin 4.69g; Take by weighing 2.35g potassium hydroxide, add in the constant pressure funnel with 50g deionized water dilution back, with constant pressure funnel, there-necked flask, protection of inert gas pipe and high-speed stirring instrument assemble, and inert gas tube is led to below the oil phase liquid level.Open the protection of inert gas pipe; fully replace air in the there-necked flask; open and stir, earlier oil phase is mixed, open constant pressure funnel again; with 1-8 drip/speed of s drips potassium hydroxide aqueous solution; the emulsification on one side of saponification on one side adds deionized water 150g altogether, can see significantly that in emulsion process system external phase becomes water by oil phase; obtain white emulsion, stop to stir, closing protection of inert gas.
Then that emulsification is good rubber/monomer emulsion joins and has backflow; heating; stir; in the reactor of protection of inert gas; open air in the abundant metathesis reactor of protection of inert gas; to guarantee not having air in the reactor; open and stir; reflux condensation mode; after being heated to 65 ℃; with 10g deionized water dissolving ferrous sulfate; glucose and trisodium phosphate; join reduction system in the reactor earlier then; make it in reactor, add oxygenant behind the homodisperse more in two batches; add 1/3 of oxygenant total mass earlier; reaction is carried out adding remaining oxygenant again after half an hour; it adds quality and is respectively: isopropyl benzene hydroperoxide 0.2797g; ferrous sulfate 0.00286g, glucose 0.1678g, trisodium phosphate 0.1368g.Stop heating behind the reaction 16h, recording monomer conversion is 63.47%, emulsion in the reactor is poured in the beaker cools off.
Configuration PH is 3 glacial acetic acid aqueous solution, add the Glacial acetic acid breakdown of emulsion while the emulsion that stirs in the beaker, washing, drying obtains product 38.83g, with acetone is extraction agent, use the Soxhlet method for extracting to measure, the percentage of grafting that obtains vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing is 231.12%, grafting efficiency 70.87%.
Embodiment 7
All technological processs all change terpolymer EP rubber/normal hexane rubber cement 46g (solid content 9.873% (massfraction)), vinylbenzene 15.2120g, vinyl cyanide 5.0707g, nilox resin 2.320g to some extent with embodiment 1 the same just adding amount of medicines; 1.160g potassium hydroxide dilutes with the 50g deionized water, add deionized water 90g after the emulsification altogether, add initiator potassium persulfate 0.1623g (Potassium Persulphate being dissolved the disposable adding in back) with the 10g deionized water, behind the question response 10h, stopped reaction, recording monomer conversion is 52.69%, and the scattering of light result is 163.1nm, emulsion in the reactor is poured in the beaker cools off.
The configuration pH value is 3 glacial acetic acid aqueous solution, add the Glacial acetic acid breakdown of emulsion while the emulsion that stirs in the beaker, washing, drying obtains product 13.01g, adopt the Soxhlet method for extracting to survey percentage of grafting, the percentage of grafting that obtains vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing is 135.32%, and grafting efficiency is 48.56%.
Embodiment 8
All technological processs all change terpolymer EP rubber/normal hexane rubber cement 46g (solid content 9.873% (massfraction)), vinylbenzene 20.9899g, vinyl cyanide 6.9966g, nilox resin 3.3293g to some extent with embodiment 1 the same just adding amount of medicines; 1.6647g potassium hydroxide dilutes with the 50g deionized water, add deionized water 90g after the emulsification altogether, add initiator potassium persulfate 0.2239g (Potassium Persulphate being dissolved the disposable adding in back) with the 10g deionized water, behind the question response 10h, stopped reaction, recording monomer conversion is 51.76%, and the scattering of light particle diameter is 132.5nm, emulsion in the reactor is poured in the beaker cools off.
The configuration pH value is 3 glacial acetic acid aqueous solution, add the Glacial acetic acid breakdown of emulsion while the emulsion that stirs in the beaker, washing, drying obtains product 17.8151g, adopt the Soxhlet method for extracting to survey percentage of grafting, the percentage of grafting that obtains vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing is 148.27%, and grafting efficiency is 46.53%.
Claims (6)
1. the method for emulsion polymerization prepared vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing is characterized in that, in turn includes the following steps:
(1) in terpolymer EP rubber/normal hexane rubber cement, adds emulsifying agent and carry out emulsification, obtain ethylene-propylene rubber(EPR) latex;
Described terpolymer EP rubber is the 3rd monomer with ethylidene norbornene; The quality solid content of described terpolymer EP rubber/normal hexane rubber cement is 9-16%; Said emulsifying agent is a saponified emulsification system in nilox resin and the potassium hydroxide emulsion process;
(2) with the ethylene-propylene rubber(EPR) latex of different emulsifying process gained temperature at 60-70 ℃, under the initiator effect, carry out 9-16 hour polyreaction with monomer, promptly get vinylbenzene-terpolymer EP rubber-acrylonitrile grafting thing;
Said different emulsifying process specifically is divided into following several: under the protection of inert gas situation, and terpolymer EP rubber/normal hexane rubber cement and monomer emulsification together, the disposable adding of initiator; Or terpolymer EP rubber/independent emulsification of normal hexane rubber cement, monomer dropping or disposable adding; Or desolventizing after terpolymer EP rubber/independent emulsification of normal hexane rubber cement, the disposable adding of monomer; Said monomer is vinylbenzene and vinyl cyanide, and the mass ratio of vinylbenzene and vinyl cyanide is (2.5-3.5): 1; Said initiator is a Potassium Persulphate, one of or isopropyl benzene hydroperoxide/ferrous sulfate/glucose/trisodium phosphate redox system, redox system isopropyl benzene hydroperoxide/ferrous sulfate/glucose/trisodium phosphate mass ratio is followed successively by: (96-99): 1: (56-59): (46-49).
2. according to the method for claim 1, the stirring velocity that it is characterized in that emulsion process wherein is 6000-16000r/min.
3. according to the method for claim 1, it is characterized in that emulsifying agent consumption wherein is the 3.5-8.5% of the oil phase total mass of vinylbenzene, terpolymer EP rubber, normal hexane and vinyl cyanide composition.
4. according to the method for claim 1, it is characterized in that emulsion process wherein adds deionized water, its quality is the 100-200% of the oil phase total mass of vinylbenzene, terpolymer EP rubber, normal hexane and vinyl cyanide composition.
5. according to the method for claim 1, the quality that it is characterized in that Potassium Persulphate wherein is the 0.6-1.5% of monomer total mass.
6. according to the method for claim 1, it is characterized in that isopropyl benzene hydroperoxide consumption wherein is the 0.40-0.50% of terpolymer EP rubber, vinylbenzene and vinyl cyanide quality summation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102074589B (en) * | 2009-11-20 | 2013-01-09 | 比亚迪股份有限公司 | Solar cell backboard and preparing process thereof |
| CN109517373A (en) * | 2018-11-20 | 2019-03-26 | 安徽江淮汽车集团股份有限公司 | A kind of PA6/AES composite material and preparation method |
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| NL165762C (en) * | 1969-12-10 | 1981-05-15 | Montedison Spa | PROCESS FOR PREPARING ENTPOLYMERS. |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102074589B (en) * | 2009-11-20 | 2013-01-09 | 比亚迪股份有限公司 | Solar cell backboard and preparing process thereof |
| CN109517373A (en) * | 2018-11-20 | 2019-03-26 | 安徽江淮汽车集团股份有限公司 | A kind of PA6/AES composite material and preparation method |
| CN109517373B (en) * | 2018-11-20 | 2020-11-03 | 安徽江淮汽车集团股份有限公司 | PA6/AES composite material and preparation method thereof |
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