CN1164670C - Syndiotactic polyphenylethylene/polyamide composite material - Google Patents
Syndiotactic polyphenylethylene/polyamide composite material Download PDFInfo
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Abstract
The present invention relates to a syndiotactic polystyrene/polyamide composite material which mainly solves the problems of high brittleness and low impact strength of a syndiotactic polystyrene material, and poor combination performance of a cross blend existing in the priot art. The present invention nicely solves the problems by adopting the technical scheme that sulfonated syndiotactic polystyrene is added into a syndiotactic polystyrene/polyamide material. The obtained composite material has the characteristics of high impact strength, high bending strength of the cross blend, and high tensile strength of the cross blend. The obtained composite material can be used in the industrial production of the syndiotactic polystyrene/ polyamide composite material.
Description
The present invention relates to syndiotactic polyphenylethylene/polyamide composite material.
Styrene polymer can be divided into random polystyrene, isotactic polyphenylacetylene, syndiotactic polystyrene.Random polystyrene is the general-purpose plastics that people know already, but its thermotolerance, chemical resistant properties are relatively poor, make it be difficult in the engineering plastics field and are applied.1985, Japanese bright dipping company at first used metallocene catalyst to make crystallinity syndiotactic polystyrene (EP210615).Henceforth, aspect the preparation of syndiotactic polystyrene particularly the Study of Catalyst aspect obtained very big progress (CN1210109A, CN1210108A, CN1210112A).Syndiotactic polystyrene is a kind of novel polyphenyl ethene, and it is different with general purpose polystyrene, has the following advantages: (1) fusing point height is 270 ℃.(2) degree of crystallinity height, Tc can be controlled at the scope of a broad, is fit to conventional plastics forming method.(3) heat-resisting, chemical resistance is good.
Syndiotactic polystyrene is a kind of novel engineering plastics, has fabulous development prospect, and potential market is boundless.The defective of syndiotactic polystyrene is that fragility is big, thereby has limited its range of application.Must carry out modification to it, with the application of commensurate structure material.The characteristic performance of the syndiotactic polystyrene after the improvement is that density is low, good toughness, good electrical property, can with other engineering plastics competition.The occasion that engineering plastics such as nearly all PET, PBT, PA, PPS are used can be used syndiotactic polystyrene.Aspect electrical equipment, electronics, can be used for high-frequency device, satellite antenna, phone, unicircuit, printed-wiring board (PWB), microwave stove etc.Aspect trolley part, can do safety lever, fuel tank, high temperature resistant motor part etc.Aspect wrapping material, can make heat-resisting, oil resistant, anti-vapor vessel, food packaging film etc.In addition, can also make high gloss insulating film, magnetic recording body, camera housing, fibre product and industrial membrane etc.
At present, the study on the modification of syndiotactic polystyrene mainly concentrates on and strengthens and blending and modifying two aspects.The former normally with glass fibre strengthen (EP508303, EP591823, US5200454, JP10017740).But because syndiotactic polystyrene is a kind of non-polar polymer, so the interface of polarity glass fibre and syndiotactic polystyrene bonding is poor, therefore, fiberglass surfacing need be used coupling agent treatment earlier.Also have report (EP591823) when syndiotactic polymerization of phenylethylene, to add a spot of alpha-methyl styrene and carry out copolymerization, and then with the copolymer grafted maleic anhydride, nationality bonds with the interface between reinforcing glass fiber and the syndiotactic polystyrene.However, adopting glass fibre filled method purely is not clearly to the raising of syndiotactic polystyrene impact property.And when syndiotactic polymerization of phenylethylene, add a spot of alpha-methyl styrene and carry out copolymerization, will make polymerization technique become complicated, also can the taxis and the performance of polymerisate be had a negative impact simultaneously.Industrial application is undesirable.
In order further to improve the impact property of syndiotactic polystyrene, document US 5391603, JP08319386, JP09052959, EP587098, EP546497, JP08157668 etc. have reported syndiotactic polystyrene and elastomerics (SEBS) and and PPO blending and modifying.Thermoplastic elastomer (SEBS) is hydrogenant styrene-butadiene-styrene block copolymer, and itself is diphasic system, and the consistency of it and syndiotactic polystyrene is relatively poor.When the two blend, be necessary to add expanding material.More typical expanding material has polyphenylene oxide (PPO) and SEBS graft copolymer and syndiotactic polystyrene and SEBS graft copolymer, and is wherein more excellent as the performance of the blend of expanding material with syndiotactic polystyrene and SEBS graft copolymer.In addition, also reported the blend of syndiotactic polystyrene and polyamide resin (PA).PA is a typical polar polymer and syndiotactic polystyrene is typical non-polar polymer, and consistency is relatively poor during the two blend, must add expanding material.More typical expanding material has polyphenylene oxide (PPO) grafted maleic anhydride multipolymer and syndiotactic polystyrene grafted maleic anhydride multipolymer.In the above-mentioned co-mixing system, have during except that syndiotactic polystyrene and polyphenylene oxide (PPO) blend preferably the consistency, other co-mixing system all needs to use expanding material.General expanding material all is the graft copolymer of syndiotactic polystyrene or polyphenylene oxide (PPO).Wherein, polyphenylene oxide is restricted its application owing to it yields poorly, price is high.The preparation of the graft copolymer of syndiotactic polystyrene normally earlier with its grafted maleic anhydride, obtains graft copolymer by other chemical reaction again.In order to make the syndiotactic polystyrene grafted maleic anhydride, must when syndiotactic polymerization of phenylethylene, add a spot of alpha-methyl styrene and carry out copolymerization.Its disadvantageous effect chatted in front and.In addition, as simple employing elastomerics (SEBS, SIS, SBS etc.) improve the shock strength of syndiotactic polystyrene, its unfavorable factor mainly shows: the one, adopt as above chat and graft copolymer as expanding material, the 2nd, though the shock strength of syndiotactic polystyrene is made moderate progress, the over-all properties of blend such as thermotolerance, tensile strength and modulus descend more.
The objective of the invention is to exist syndiotactic polystyrene material fragility big in the conventional art in order to overcome, shock strength is low, the shortcoming of the over-all properties difference of blend, and a kind of new syndiotactic polyphenylethylene/polyamide composite material is provided.This matrix material has the shock strength height, and the flexural strength of blend and the good characteristics of tensile strength.
The objective of the invention is to realize by following technical scheme: a kind of syndiotactic polyphenylethylene/polyamide composite material comprises following component in parts by weight:
A) syndiotactic polystyrene is 1～99 part;
B) sulfonated syndiotactic polyphenylethylene is 0.1～50 part, and molecular weight is 15～600,000, and a normality is greater than 98%;
C) polyamide resin is 0.9～98 part, and its sulfonation degree counts 1～20% with molar percentage;
D) mineral filler is or/and 1～50 part of auxiliary agent.
In the technique scheme, it is 50～95 parts in the preferable range of parts by weight syndiotactic polystyrene amount.Preferable range in the amount of parts by weight sulfonated syndiotactic polyphenylethylene is 1～20 part.Used polyamide resin is selected from polyamide 6, polyamide 66, polyamide 6 10, polyamide 1010, polymeric amide 4, polymeric amide 9, polymeric amide 46, polymeric amide 11, polymeric amide 12 or aromatic polyamides, and preferred version is a polyamide 6.In parts by weight, polyamide resin consumption preferable range is 5～60 parts.Mineral filler is bat wool or fleut, and wherein bat wool comprises glass fibre, carbon fiber, organic synthetic fibers, steel fiber or other natural fiber; Fleut comprises carbon black, kaolin, diatomite, carclazyte, polynite, titanium dioxide, silicon powder, lime carbonate, magnesiumcarbonate, barium carbonate, calcium sulfate, sal epsom, barium sulfate, aluminum oxide, glass powder or metal powder.Auxiliary agent comprises oxidation inhibitor, fire retardant, nucleator or impact modifying agent, and wherein oxidation inhibitor comprises antioxidant 1010, PEP36, Mark Ao-30 or BHT; Nucleator comprises Sodium Benzoate or p t butylbenzoic acid aluminium; Impact modifying agent comprises segmented copolymer, ABS or the urethane of segmented copolymer, vinylbenzene and different propylene of segmented copolymer, hydrogenated styrene and the divinyl of styrene-butadiene rubber(SBR), vinylbenzene and divinyl.
Sulfonated syndiotactic polyphenylethylene is meant the polymkeric substance that has polarity sulfonic acid group or sulfonate groups on the phenyl ring in the syndiotactic polystyrene molecule.Sulfonic acid group or sulfonate groups generally are distributed in the contraposition of phenyl ring, but position and adjacent reaction between being not precluded within.The sulfonation degree of sulfonated syndiotactic polyphenylethylene generally is controlled at 1～20 mole of %, because the introducing of sulfonic acid group makes sulfonated syndiotactic polyphenylethylene have certain wetting ability, needs drying treatment before therefore using.The sulfonated syndiotactic polyphenylethylene that the present invention uses can be neutralization or unneutralized, in and the contained metal ion of sulfonated syndiotactic polyphenylethylene can be potassium, sodium, lithium, barium, magnesium, manganese, zinc, copper, calcium, cobalt, iron, nickel plasma.The consumption of general sulfonated syndiotactic polyphenylethylene or sulfonated syndiotactic polyphenylethylene polymkeric substance is 0.1～50% of a syndiotactic polystyrene consumption, and optimum amount is 1～20% of a syndiotactic polystyrene consumption.
Used polymeric amide (C) can be suitability for industrialized production or the not kind of suitability for industrialized production among the present invention.Comprise polyamide 6 (nylon 6), polyamide 6 (nylon 66), polyamide 6 10 (NYLON610), polyamide 1010 0 (nylon 1010), polymeric amide 4 (nylon 4), polymeric amide 9 (nylon 9), polymeric amide 46 (nylon 46), polymeric amide 11 (Ni Long11), polymeric amide 12 (nylon 12) and aromatic polyamides etc.The polymeric amide consumption is 0.9～98% of a polymkeric substance total amount among the present invention, and optimum amount is 5～60%.If the consumption of polymeric amide surpasses 98%, then the water-intake rate of the water-intake rate of mixture and pure polymeric amide is approaching.
The syndiotactic polystyrene involved in the present invention and the mixture of polyamide resin can add filler and other auxiliary agents according to the needs of actual situation.Wherein filler can be fibrous or powdery, and bat wool comprises glass fibre, carbon fiber, organic synthetic fibers, steel fiber and other natural fiber etc.Fleut comprises carbon black, kaolin, diatomite, carclazyte, polynite, titanium dioxide, silicon powder, lime carbonate, magnesiumcarbonate, barium carbonate, calcium sulfate, sal epsom, barium sulfate, aluminum oxide and glass powder and metal powder etc.General Fibre diameter is at 5 to 20 microns, and length is at 0.05 to 50 millimeter.Powder diameter is between 200 order to 800 orders.Filler its surface before use needs to use coupling agent treatment, and treatment process gets final product according to a conventional method.Coupling agent commonly used has siloxanes coupling agent and titanate coupling agent etc.Preferable in the above-mentioned filler with glass fibre and glass powder effect.Wherein the add-on of filler is decided on practical situation, if amount of filler is excessive, then fillers dispersed difficulty, and blended complex forming process is difficulty also.
Other auxiliary agents comprise oxidation inhibitor, fire retardant, nucleator and impact modifying agent etc.Wherein oxidation inhibitor is important, and the adding of oxidation inhibitor mainly is in order to prevent polymkeric substance oxygenolysis when the high-temperature fusion blend.Oxidation inhibitor commonly used comprises antioxidant 1010 (four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin), PEP36 (2,6-di-t-butyl-4-aminomethyl phenyl tetramethylolmethane diphosphite fat), Mark AO-30 (1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane) and BHT (2, the 6-tertiary butyl-4-cresols) etc.The consumption of oxidation inhibitor is generally 0.1～1% (weight) of polymer loading.The adding of nucleator mainly is in order to improve the crystallinity of syndiotactic polystyrene, and nucleator commonly used has Sodium Benzoate and p-tert-butyl benzoic acid aluminium etc.The consumption of nucleator is generally 0.3～5% of polymer weight.The adding of impact modifying agent is in order further to improve the impact property of blended complex, impact modifying agent commonly used is rubber or elastomerics etc., segmented copolymer (the SB of styrene-butadiene rubber(SBR), vinylbenzene and divinyl for example, SBS), the segmented copolymer of segmented copolymer (SEBS), vinylbenzene and the different propylene of hydrogenated styrene and divinyl (SI, SIS) and ABS and Polyurethane etc.The consumption of impact modifying agent depends on the needs.Usually 5～20%.
The preparation method of sulfonated syndiotactic polyphenylethylene is as follows:
In 500 milliliters of round-bottomed flasks, put into 3.0 gram sPS (syndiotactic polystyrene) and 340 milliliters 1,2,4-trichlorobenzene (TCB), reflux (about 210 ℃) is all dissolved to sPS.Solution is chilled to 70～80 ℃ then, feeds nitrogen, and keep reaction soln at 70 ℃, slowly drip the sulfonated reagent of metering according to required sulfonation degree, stir fast simultaneously, 70 ℃ of reactions of constant temperature added 2 ml methanol termination reactions after 1 hour.After sulfonation reaction is finished,, should while hot sedimentation in reaction solution impouring 1200 ml methanol be gone out polymkeric substance immediately, after the filtration product be spent the night 70 ℃ of vacuum-dryings in order to prevent gel.
In order further to remove the sulfonated reagent of carrying secretly in the product, it is dissolved among the TCB methyl alcohol sedimentation, suction filtration earlier.To be deposited in then among the Waring Blender that fills methyl alcohol and grind to form thin slurry, polymkeric substance is put into the Soxhlet extractor behind the suction filtration again and used methyl alcohol extracting 14 hours, product is spent the night 70 ℃ of vacuum-dryings promptly gets purified SsPS (sulfonated syndiotactic polyphenylethylene) at last.
The measuring method of SsPS sulfonation degree is that SsPS sample 0.3～0.5 gram is dissolved in the trichloromethane methanol mixed solvent that volume ratio is 95:5, the SsPS sample that dissolving is good is indicator with phenolphthalein, with the methanol solution titration of NaOH to terminal, the amount according to the NaOH that is consumed calculates sulfonation degree.
The preparation method of syndiotactic polyphenylethylene/polyamide composite material of the present invention is as follows:
With each component by the prescription weighing good after, earlier dried mixed in blender, and then mediate in mixing roll or twin screw extruder, general condition is controlled at: temperature is 300 ℃, and rotating speed is 75 rev/mins, and mixing time depends on the circumstances, and is generally 5～15 minutes.The material that mixes is in forcing machine behind the extruding pelletization, through injector injection molding.Have good impact-resistance, water tolerance and mechanical property preferably by the blended complex that contains syndiotactic polystyrene of above-mentioned each component preparation.Be expected as electronic apparatus material, industrial structure material, automobile component, civil electric appliance parts and other machine part etc.
In syndiotactic polyphenylethylene/polyamide composite material, add sulfonated syndiotactic polyphenylethylene among the present invention, owing to have special interaction between the sulfonic acid group of sulfonated syndiotactic polyphenylethylene and the amide group of polymeric amide, as hydrogen bond action and coordination etc., promoted the compatibilization effect of whole matrix material greatly, improved the over-all properties of matrix material, the shock strength that makes syndiotactic polystyrene material is from 4.8 kilojoule/rice
2Bring up to 16.1 kilojoule/rice
2, having improved nearly 3 times, the flexural strength of matrix material has been brought up to 55.4MPa from 47.1MPa simultaneously, and tensile strength has been brought up to 50.3MPa from 30.1MPa simultaneously, has obtained effect preferably.
The present invention is further elaborated below by embodiment.
[embodiment 1]
The preparation of syndiotactic polystyrene and polyamide resin blends mixture
80 parts of (weight, as follows) (molecular weight is 350,000 to syndiotactic polystyrene, between normality greater than 97%, fusing point is 272 ℃) in, add 20 parts of polyamide 6s (PA6) (molecular weight is 18000) and 0.1 part of antioxidant 1010, in blender, do above-mentioned material mixed earlier, and then mixing kneading in twin screw extruder, mixing condition is: temperature is 290 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.
[embodiment 2]
The preparation of syndiotactic polystyrene, sulfonated syndiotactic polyphenylethylene and polycarbonate blending mixture
20 parts of (weight, as follows) in the syndiotactic polystyrene (molecular weight is 350,000, and a normality is greater than 97%, and fusing point is 272 ℃), add 20 parts of polycarbonate (molecular weight is 22000), 5 parts of sulfonated syndiotactic polyphenylethylenes (SsPS, sulfonation degree is 9.6 moles of %) and 0.1 part of antioxidant 1010 are done above-mentioned material mixed earlier in blender, and then mixing kneading in twin screw extruder, mixing condition is: temperature is 290 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.
[embodiment 3]
The preparation of syndiotactic polystyrene, sulfonated syndiotactic polyphenylethylene and polyamide resin blends mixture
20 parts of (weight, as follows) in the syndiotactic polystyrene (molecular weight is 350,000, and a normality is greater than 97%, and fusing point is 272 ℃), add 20 parts of PA6 (molecular weight is 18000), 5 parts of sulfonated syndiotactic polyphenylethylenes (SsPS, sulfonation degree is 9.6 moles of %) and 0.1 part of antioxidant 1010 are done above-mentioned material mixed earlier in blender, and then mixing kneading in twin screw extruder, mixing condition is: temperature is 290 ℃, and rotating speed is 75 rev/mins, and mixing time is 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.
[embodiment 4]
The preparation of syndiotactic polystyrene, sulfonated syndiotactic polyphenylethylene and polyamide resin blends mixture
80 parts of (weight, as follows) (molecular weight is 350,000 to syndiotactic polystyrene, between normality greater than 97%, fusing point is 272 ℃) in, add 20 parts of PA6 (molecular weight is 18000), 5 parts of sulfonated syndiotactic polyphenylethylene zinc salts (sulfonation degree is 9.6 moles of %) and 0.1 part of antioxidant 1010, above-mentioned material is dried mixed in blender earlier, and then mixing kneading in twin screw extruder, mixing condition is: temperature is 290 ℃, rotating speed is 75 rev/mins, and mixing time is 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.
[embodiment 5]
The preparation of syndiotactic polystyrene, sulfonated syndiotactic polyphenylethylene and polyamide resin blends mixture
80 parts of (weight, as follows) (molecular weight is 350,000 to syndiotactic polystyrene, between normality greater than 97%, fusing point is 272 ℃) in, add 20 parts of PA6 (molecular weight is 18000), 10 parts of sulfonated syndiotactic polyphenylethylene zinc salts (sulfonation degree is 9.6 moles of %) and 0.1 part of antioxidant 1010, above-mentioned material is dried mixed in blender earlier, and then mixing kneading in twin screw extruder, mixing condition is: temperature is 290 ℃, rotating speed is 75 rev/mins, and mixing time is 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.
[embodiment 6]
The preparation of syndiotactic polystyrene, sulfonated syndiotactic polyphenylethylene and polyamide resin blends mixture
80 parts of (weight, as follows) (molecular weight is 350,000 to syndiotactic polystyrene, between normality greater than 97%, fusing point is 272 ℃) in, add 20 parts of PA6 (molecular weight is 18000), 5 parts of sulfonated syndiotactic polyphenylethylene zinc salts (sulfonation degree is 4.7 moles of %) and 0.1 part of antioxidant 1010, above-mentioned material is dried mixed in blender earlier, and then mixing kneading in twin screw extruder, mixing condition is: temperature is 290 ℃, rotating speed is 75 rev/mins, and mixing time is 8 minutes.The material that mixes extruding pelletization in forcing machine.Pellet carries out performance test after molded or injection molding.
The performance of embodiment 1～6 mixture sees Table 1.
The performance table of table 1 syndiotactic polystyrene (sPS) and polyamide resin (PC) blended complex
*
| Embodiment | SPS/PA6/SsPS (weight) | Shock strength (kilojoule/rice 2) | Flexural strength (MPa) | Tensile strength (MPa) | Elongation at break (%) |
| 1 | 80/20/0 | 4.8 | 47.1 | 30.1 | 3.2 |
| 2 | 80/20/5 | 15.0 | 50.0 | 45.6 | 12.9 |
| 3 | 80/20/10 | 11.4 | 52.5 | 47.8 | 10.2 |
| 4 | 80/20/5 | 16.1 | 55.4 | 50.3 | 13.6 |
| 5 | 80/20/10 | 8.1 | 52.4 | 48.9 | 10.6 |
| 6 | 80/20/5 | 8.3 | 50.5 | 40.3 | 7.5 |
| sPS | 100/0/0 | 5.3 | 48.6 | 33.6 | 1.2 |
Annotate: in the above-mentioned data, shock strength and flexural strength adopt cantilever method to measure at normal temperatures.
Among the embodiment 2 and 3, adopt not in and sulfonated syndiotactic polyphenylethylene be expanding material, sulfonation degree is 9.6 moles of %.
Among the embodiment 4 and 5, the sulfonated syndiotactic polyphenylethylene zinc salt is an expanding material, and sulfonation degree is 9.6 moles of %.
Among the embodiment 6, adopt not in and sulfonated syndiotactic polyphenylethylene be expanding material, sulfonation degree is 4.7 moles of %.
Claims (8)
1, a kind of syndiotactic polyphenylethylene/polyamide composite material comprises following component in parts by weight:
A) syndiotactic polystyrene is 1～99 part, and molecular weight is 15～600,000, and a normality is greater than 98%;
B) sulfonated syndiotactic polyphenylethylene is 0.1～50 part, and its sulfonation degree counts 1～20% with molar percentage;
C) polyamide resin is 0.9～98 part;
D) mineral filler is or/and 1～50 part of auxiliary agent.
According to the described syndiotactic polyphenylethylene/polyamide composite material of claim 1, it is characterized in that 2, the syndiotactic polystyrene amount is 50～95 parts in parts by weight.
According to the described syndiotactic polyphenylethylene/polyamide composite material of claim 1, it is characterized in that 3, the sulfonated syndiotactic polyphenylethylene amount is 1～20 part in parts by weight.
4,, it is characterized in that polyamide resin is selected from polyamide 6, polyamide 66, polyamide 6 10, polyamide 1010, polymeric amide 4, polymeric amide 9, polymeric amide 46, polymeric amide 11, polymeric amide 12 or aromatic polyamides according to the described syndiotactic polyphenylethylene/polyamide composite material of claim 1.
5,, it is characterized in that polyamide resin is a polyamide 6 according to the described syndiotactic polyphenylethylene/polyamide composite material of claim 4.
6,, it is characterized in that in parts by weight polyamide resin amount be 5～60 parts according to the described syndiotactic polyphenylethylene/polyamide composite material of claim 1.
7, according to the described syndiotactic polyphenylethylene/polyamide composite material of claim 1, it is characterized in that mineral filler is bat wool or fleut, wherein bat wool comprises glass fibre, carbon fiber, organic synthetic fibers, steel fiber or other natural fiber; Fleut comprises carbon black, kaolin, diatomite, carclazyte, polynite, titanium dioxide, silicon powder, lime carbonate, magnesiumcarbonate, barium carbonate, calcium sulfate, sal epsom, barium sulfate, aluminum oxide, glass powder or metal powder.
8, according to the described syndiotactic polyphenylethylene/polyamide composite material of claim 1, it is characterized in that auxiliary agent comprises oxidation inhibitor, fire retardant, nucleator or impact modifying agent, wherein oxidation inhibitor comprises antioxidant 1010, PEP36, Mark Ao-30 or BHT; Nucleator comprises Sodium Benzoate or p t butylbenzoic acid aluminium; Impact modifying agent comprises segmented copolymer, ABS or the urethane of segmented copolymer, vinylbenzene and different propylene of segmented copolymer, hydrogenated styrene and the divinyl of styrene-butadiene rubber(SBR), vinylbenzene and divinyl.
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| CN102070852B (en) * | 2010-12-30 | 2012-08-15 | 宁波今山电子材料有限公司 | Modified polystyrene plastic |
| CN102775691B (en) * | 2012-08-10 | 2014-04-30 | 常熟市慧丰塑料制品有限公司 | Composite wire and cable sheath material |
| CN103642209A (en) * | 2013-11-18 | 2014-03-19 | 安徽宜万丰电器有限公司 | Waterproof temperature-resistant modified nylon material for automobile plastic members |
| CN103694695B (en) * | 2013-12-19 | 2016-10-05 | 上海日之升新技术发展有限公司 | A kind of fiber glass reinforced halogen-free flame retardant PA6/PS alloy material and preparation method thereof |
| CN105524461B (en) * | 2016-01-05 | 2018-02-02 | 广州市聚赛龙工程塑料股份有限公司 | A kind of fiber glass reinforced halogen-free flame retardant of resistance to gasoline sPS composites and preparation method thereof |
| CN113444326A (en) * | 2021-07-22 | 2021-09-28 | 广东粤化新材料技术开发有限公司 | High-toughness polystyrene resin and preparation method thereof |
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