CN101817959B - Flame-retardant styrene resin composition for large-scale thin wall parts and preparation method thereof - Google Patents
Flame-retardant styrene resin composition for large-scale thin wall parts and preparation method thereof Download PDFInfo
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- CN101817959B CN101817959B CN200910247757A CN200910247757A CN101817959B CN 101817959 B CN101817959 B CN 101817959B CN 200910247757 A CN200910247757 A CN 200910247757A CN 200910247757 A CN200910247757 A CN 200910247757A CN 101817959 B CN101817959 B CN 101817959B
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Abstract
The invention relates to a flame-retardant styrene resin composition for large-scale thin wall parts and a preparation method thereof. The composition comprises the following components in part by weight: 60 to 82 parts of rubber-modified styrene resin, 1 to 5 parts of impact modifier, 1 to 5 parts of phosphorus compound, 8 to 17 parts of flame retardant and 3 to 7 parts of flame retardant synergist. The preparation method comprises the steps of: respectively putting the components in a high speed mixer for premixing; adding the obtained premix into a double-screw extruder; and conveying, melting, cutting, extruding, cooling and granulating to obtain the product. The invention has the advantages that: by adding aromatic phosphate with low molecular weight into the flame-retardant styrene resin composition, the fluidness of the composition is improved, the toughness and heat stability of the composition are not reduced and reach UL94 1.6mmV0, the generation of weld lines in the molding process of the large-scale thin wall parts is effectively inhibited, the molding period is shortened, the surface gloss of the products is improved, and the weld line problem in the molding process of the large-scale thin wall parts is effectively solved.
Description
Technical field
The present invention relates to a kind of resin combination and preparation method thereof, especially relate to a kind of flame-retardant styrene resin composition and preparation method who is used for large-scale thin wall parts.
Background technology
Owing to have good rigidity, processibility and surface luster; Phenylethylene resin series is widely used at multiple industrial circle; Like household electrical appliances, office equipment and stamping machine duplicating machine panel etc., usually these occasions have proposed higher requirement to the flame retardant resistance of material, need reach the UL94V0 level usually.
Phenylethylene resin series such as HIPS and ABS oxygen index have only 18.0, belong to inflammable material, need to add halogen compounds, P contained compound and inorganic combustion inhibitor usually and give the phenylethylene resin series flame retardant properties; Wherein halogen flame particularly bromide fire retardant be widely used in the flame-retardant styrene resin; Mainly comprise tetrabromo-bisphenol, TDE, 2,4; 6-tribromo triple phenoxyl-1; 3,5-triazine, ethylidene-(two tetrabromo phthalimide), brominated epoxy oligomer, tetrabromophthalate-(2-ethylhexyl) ester, wherein TDE becomes the maximum fire retardant of usage quantity among the HIPS with its higher flame retarding efficiency and lower cost.
In recent years, household electrical appliances and office equipment demand constantly increase, and the user has higher requirement to outward appearance simultaneously, and in order to control cost, the manufacturer more and more tends to use the lower HIPS of price to replace ABS.Compare with ABS, rubber size is bigger usually among the HIPS, and its molding shows lower toughness and relatively poor surface luster.In addition, fill mould moulding and large-sized thin wall parts for many cast gates and can form more significantly weld bond usually, influence product appearance and physical strength.
In order to improve the weld bond of molding, need take all factors into consideration from die design, processing conditions and material character.Reducing cast gate quantity perhaps moves on to weld bond to material appearance and the less position of influence; Can improve product appearance; But can not fundamentally prevent the generation of weld bond and be applicable to all products, and die design brings higher cost usually; As for processing factors; Also be proved to be influential like melt temperature, injection pressure, die temperature etc. to weld bond intensity; But; The importance of a certain particular process factor has dependency to material, and the melt temperature that for example improves the weld bond place can improve weld bond intensity, but because fire retardant degraded and small molecules are separated out negative impacts such as the gas trace that causes, filamentary silver also can not be ignored; Improving the valid approach of weld bond is to improve material flowability; For example to add molecular weight be 1000～5000 particular polyesters to publication number for the CN1160408C patent has been described in ABS; When improving weld bond outward appearance and surface luster, do not reduce modulus in flexure, but toughness of material and Vicat softening point descend significantly along with the increase of amount of polyester; For filled polymer; The type of packing material and character are very big to weld line strength and products appearance influence; For example the CN14896148A patent has been described the wollastonite replacement talcum enhancing PC/ABS compsn of specific length-to-diameter ratio; Weld bond intensity is had clear improvement, but this invention belongs to the packing material category, is not suitable for the present invention; In addition, japanese patent application publication No. JP-153443/97 uses the grafting rubbers styrene polymer with specified range storage modulus, utilizes the higher elastic resilience of rubber particles that weld bond is controlled in the acceptable scope.
In sum; Through improving material flowability is to improve the simple and effective approach of weld bond; But as select high matrix resin or two problems of raising lubricant addition existence of flowing for use: (1) material flowability improves limited, can not avoid the generation of weld bond fully; (2) improve processing aid content and often cause material thermostability and modulus to descend, cause negative impact.Find through long-term experiment; In the flame-retardant styrene resin; Add a small amount of low-molecular-weight aromatic phosphate acid ester and not only can greatly improve material flowability, the more important thing is and to play good plastification to matrix resin among the ABS and fire retardant, increase the fusion faculty that the material injection moulding adds man-hour; Thereby effectively prevent the generation of weld bond, be specially adapted to the large-scale thin wall parts that outward appearance is had relatively high expectations.
In addition, in resin combination, add aforesaid SULPHOSUCCINIC ACID ESTER and also have following advantage: (1) synergistic is fire-retardant, can reduce bromide fire retardant content, improves material thermostability and toughness; (2) heat-resisting very little to material with the toughness influence.In halogen-free flame retardant PC/ABS, repeatedly prove; The adding of aromatic phosphate acid ester is very big to the heat-resisting influence of material; It is plasticising type fire retardant that result of the present invention can be interpreted as aromatic phosphate acid ester; When improving material flowability fire retardant played and helped the dispersive effect, offset the negative impact that the adding of aromatic phosphate acid ester brings.
Summary of the invention
The object of the invention is exactly for the defective that overcomes above-mentioned prior art existence a kind of generation, assurance products appearance and the physical strength of weld bond, lower-cost flame-retardant styrene resin composition that is used for large-scale thin wall parts and preparation method thereof of preventing to be provided.
The object of the invention can be realized through following technical scheme:
A kind of flame-retardant styrene resin composition that is used for large-scale thin wall parts is characterized in that, said composition comprises following component and weight part content:
The styron 60～82 of modified rubber;
Impact modifying agent 1～5;
P contained compound 1～5;
Fire retardant 8～17;
Fire retarding synergist 3～7.
The styron of described modified rubber is that rubber is dispersed in the styron with particulate forms; Through transmission electron microscope observing is sea-island structure; Be selected from high-impact polystyrene, styrene butadiene-acrylonitrile copolymer or cinnamic acrylic ester-acrylonitrile copolymer; Preferred high-impact polystyrene, the styron melt flow rate(MFR) of this modified rubber is 4～15g/10min, preferred 8～12g/10min.
Described impact modifying agent is selected from one or more in styrene-butadiene block copolymer, vinylbenzene-ethylene propylene rubber segmented copolymer or the styrene butadiene graft copolymer, and the content of rubber is 50～80wt% in this impact modifying agent.
Described P contained compound is selected from the aromatic phosphate acid ester that following formula is represented:
Wherein, R
1, R
2, R
4, R
5Be selected from aromatic base or the substituted aromatic group of alkyl of C6～C20 respectively, R
3Be selected from a kind of in Resorcinol, bisphenol-A, the quinhydrones, polymkeric substance n is 0～6.
Described aromatic phosphate acid ester is selected from one or more in triphenylphosphate, dihydroxyphenyl propane-diphenyl phosphate or the Resorcinol-diphenyl phosphate, preferred dihydroxyphenyl propane-diphenyl phosphate.
Described fire retardant is selected from tetrabromo-bisphenol; TDE, 2,4,6-tribromo triple phenoxyl-1; 3, one or more in 5-triazine, ethylidene-(two tetrabromo phthalimide), brominated epoxy oligomer or tetrabromophthalate-(2-ethylhexyl) ester.
Described fire retarding synergist is for containing sb oxide, and this contains sb oxide and is selected from Antimony Trioxide: 99.5Min, stibnate or the colloidal antimony pentoxide one or more, and preferable particle size is not less than 2000 purpose Antimony Trioxide: 99.5Mins.
Described flame-retardant styrene resin composition also comprises other auxiliary agent, is selected from lubricant, oxidation inhibitor, thermo-stabilizer, anti-dripping agent, photostabilizer, the pigment one or more.
A kind of preparation method who is used for the flame-retardant styrene resin composition of large-scale thin wall parts is characterized in that, this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
The styron 60～82 of modified rubber,
Impact modifying agent 1～5,
P contained compound 1～5,
Fire retardant 8～17,
Fire retarding synergist 3～7;
(2) said components is placed high-speed mixer premix 20min, temperature is controlled at 40～60 ℃, obtains pre-composition;
(3) pre-composition that obtains is joined in the twin screw extruder that has accurate temperature regulating device and gas barrier; The control extrusion temperature is 180～240 ℃, and screw speed is 200～400rpm, and screw slenderness ratio is not less than 30; Extrude cooling granulation through conveying, fusion, shearing, obtain product.
Compared with prior art, the present invention improves material flowability through in flame-retardant styrene resin composition, adding low-molecular-weight aromatic phosphate acid ester, and does not reduce toughness and thermostability; Can reach UL941.6mmV0; Under the prerequisite that does not reduce toughness and thermostability, make material obtain super-high fluidity, in the large-scale thin wall parts moulding process, suppressed the generation of weld bond effectively; Shortened shaping cycle; Improve the surface luster of goods, under the prerequisite that does not increase cost, just can solve the weld bond problem in the large-scale thin wall parts moulding process simply and effectively, had significant marketable value and economic worth.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Embodiment 1-3
A kind of preparation method who is used for the flame-retardant styrene resin composition of large-scale thin wall parts, this method may further comprise the steps:
(1) according to following component and preparation raw material: high-impact polystyrene: HIPS-1:MI=6.2g/10min, HIPS-2:MI=12.8g/10min; Styrene-butadiene block copolymer: SBS: rubber content 65%; Dihydroxyphenyl propane-diphenyl phosphate: the PX-200 that BDP:Daihachi Co.Ltd provides, phosphorus content are 8.6%; Fire retardant: DBDPE: TDE, the F-8010 that Dead Sea bromine provides; BEO: brominated epoxy oligomer, open to beautify and learn the F-2016K that provides; Antimony Trioxide: 99.5Min: Sb
2O
3: the prosperous antimony industry of Hunan China, purity＞99.8%, particle diameter are 4000 orders.Other components: oxidation inhibitor 168, antioxidant 1010, vapour crust elite; Lubricant: N, N-ethylidene-bis-stearamides EBS:HONEYWELL.Each component concentration is as shown in table 1.
(2) said components is placed high-speed mixer premix 20min, temperature is controlled at 50 ℃, obtains pre-composition;
(3) pre-composition that obtains is joined in the twin screw extruder that has accurate temperature regulating device and gas barrier; The temperature in each section of control twin screw extruder district is 180 ℃, 200 ℃, 210 ℃, 230 ℃, 240 ℃; Screw speed is 300rpm, and screw slenderness ratio is 40, extrudes cooling granulation through conveying, fusion, shearing; The particle that obtains in 80 ℃ of dry 2h, obtains product in hot-air oven.
Comparative Examples 1-3
(1) according to following component and preparation raw material: high-impact polystyrene: HIPS-1:MI=6.2g/10min, HIPS-2:MI=12.8g/10min; Styrene-butadiene block copolymer: SBS: rubber content 65%; Fire retardant: DBDPE: TDE, the F-8010 that Dead Sea bromine provides; BEO: brominated epoxy oligomer, open to beautify and learn the F-2016K that provides; Antimony Trioxide: 99.5Min: Sb
2O
3: the prosperous antimony industry of Hunan China, purity＞99.8%, particle diameter are 4000 orders.Other components: oxidation inhibitor 168, antioxidant 1010, vapour crust elite; Lubricant: N, N-ethylidene-bis-stearamides EBS:HONEYWELL.Each component concentration is as shown in table 1.
(2) said components is placed high-speed mixer premix 20min, temperature is controlled at 50 ℃, obtains pre-composition;
(3) pre-composition that obtains is joined in the twin screw extruder that has accurate temperature regulating device and gas barrier; The temperature in each section of control twin screw extruder district is 180 ℃, 200 ℃, 210 ℃, 230 ℃, 240 ℃; Screw speed is 300rpm; Screw slenderness ratio is 40, extrudes cooling granulation through conveying, fusion, shearing, obtains contrast material.
Table 1
| Material component kg | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| HIPS-1 | phr | 52 | 51 | 50 | 50 | 50 | 80 |
| HIPS-2 | / | 30 | 30 | 30 | 30 | 30 | / |
| SBS | / | 3 | 3 | 3 | 3 | 3 | 3 |
| Sb2O3 | / | 4 | 4 | 4 | 4 | 4 | 4 |
| DBDPE | / | 10 | 10 | 10 | 10 | 10 | 10 |
| BEO | / | / | / | / | 2 | 2 | 2 |
| BDP | / | 1 | 1 | 2 | / | / | / |
| Oxidation inhibitor 168 | / | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Antioxidant 1010 | / | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| EBS | / | 0.7 | 0.7 | 0.7 | 0.7 | 2.0 | 0.7 |
Method of evaluating performance and standard
The performance of the sample that embodiment and Comparative Examples are prepared is tested, and test condition is following:
Tensile strength: ASTM D638, single cast gate of difference moulding and two ends cast gate tensile bars, batten size: 170*127*3.2mm, speed is 50mm/min, the record tensile strength is respectively TS
1, TS
2Loss of tensile strength rate=(TS
1-TS
2)/TS
1* 100%; Shock strength: ASTM D256, batten size 64*12.7*3.2mm; Flame retardant resistance: UL94, batten size 125*13.0*1.6mm; Glossiness: ASTM, size 150*90*3mm; Vicat softening point: ASTM D1525, batten size 64*12.7*3.2mm, condition be 5kg/ (50 ℃/h); Melt flow rate(MFR): ASTM D1238,230 ℃ of * 5kg of test condition; Thermostability: 240 ℃ stop injection moulding 10min, press ASTM D test xanthochromia index YI.Test result is as shown in table 2.
Table 2
Annotating: represent weld bond not obvious more zero more; * the weld bonds of representing obvious more more
Comparative example 1～3 can find that BDP has played the effect of synergistic flame retardant, and the while is along with the increase of BDP content; Melt flow rate(MFR) obviously improves, and the loss of tensile strength rate descends, to the weld bond effect of having clear improvement; Comparative Examples 2 shows through increasing lubricant and can improve liquidity; But the weld bond degree to goods is not improved, and glossiness descends simultaneously, and this is owing to the relatively poor reason of lubricant thermostability under the high temperature.
Embodiment 4
A kind of preparation method who is used for the flame-retardant styrene resin composition of large-scale thin wall parts, this method may further comprise the steps:
(1) prepares raw material according to following component: the styron of 60kg modified rubber, 5kg impact modifying agent, 1kg P contained compound, 8kg fire retardant, 7kg fire retarding synergist; Wherein the styron of modified rubber is that its melt flow rate(MFR) of high-impact polystyrene is 8g/10min; Rubber is dispersed in the styron with particulate forms, is sea-island structure through transmission electron microscope observing; Impact modifying agent is vinylbenzene-ethylene propylene rubber segmented copolymer, and the content of rubber is 50wt%, and P contained compound is an aromatic phosphate acid ester, and structural formula is as follows:
Wherein, R
1, R
2, R
4, R
5Be C
6, C
10, C
12, C
16, C
20The substituted aromatic group of aromatic base, R
3Be Resorcinol, polymkeric substance n is 4; Fire retardant is 2,4,6-tribromo triple phenoxyl-1,3,5-triazines, ethylidene-(two tetrabromo phthalimide); Fire retarding synergist is a colloidal antimony pentoxide.
(2) said components is placed high-speed mixer premix 20min, temperature is controlled at 40 ℃, obtains pre-composition;
(3) pre-composition that obtains is joined in the twin screw extruder that has accurate temperature regulating device and gas barrier; The temperature in each section of control twin screw extruder district is 180 ℃, 200 ℃, 210 ℃, 230 ℃, 240 ℃; Screw speed is 400rpm; Screw slenderness ratio 30 is extruded cooling granulation through conveying, fusion, shearing, obtains product.
Embodiment 5
A kind of preparation method who is used for the flame-retardant styrene resin composition of large-scale thin wall parts, this method may further comprise the steps:
(1) prepares raw material according to following component: the styron of 70kg modified rubber, 1kg impact modifying agent, 5kg P contained compound, 17kg fire retardant, 3kg fire retarding synergist; Wherein the styron of modified rubber is that its melt flow rate(MFR) of high-impact polystyrene is 12g/10min; Rubber is dispersed in the styron with particulate forms, is sea-island structure through transmission electron microscope observing; Impact modifying agent be vinylbenzene-ethylene propylene rubber segmented copolymer and styrene-butadiene block copolymer by weight the compound that is 1: 2, the content of rubber is 80wt%, P contained compound is dihydroxyphenyl propane-diphenyl phosphate; Fire retardant is a tetrabromo-bisphenol; Fire retarding synergist is particle diameter 2000 purpose Antimony Trioxide: 99.5Mins; Comprise also that in addition 2kg anti-dripping agent tetrafluoroethylene, 2kg photostabilizer benzotriazole, 1kg carbon black are as pigment;
(2) said components is placed high-speed mixer premix 20min, temperature is controlled at 60 ℃, obtains pre-composition;
(3) pre-composition that obtains is joined in the twin screw extruder that has accurate temperature regulating device and gas barrier; The temperature in each section of control twin screw extruder district is 180 ℃, 200 ℃, 210 ℃, 230 ℃, 240 ℃; Screw speed is 200rpm; Screw slenderness ratio 50 is extruded cooling granulation through conveying, fusion, shearing, obtains product.
Embodiment 6
A kind of preparation method who is used for the flame-retardant styrene resin composition of large-scale thin wall parts, this method may further comprise the steps:
(1) prepares raw material according to following component: the styron of 75kg modified rubber, 2kg impact modifying agent, 3kg P contained compound, 10kg fire retardant, 5kg fire retarding synergist; Wherein the styron of modified rubber is styrene butadiene-acrylonitrile copolymer; Its melt flow rate(MFR) is 15g/10min; Rubber is dispersed in the styron with particulate forms, is sea-island structure through transmission electron microscope observing; Impact modifying agent is that vinylbenzene-ethylene propylene rubber segmented copolymer and styrene butadiene graft copolymer are by weight the compound that is 1: 1; The content of rubber is 60wt%, and P contained compound is that triphenylphosphate and dihydroxyphenyl propane-diphenyl phosphate are by weight the compound that is 1: 2; Fire retardant is that tetrabromo-bisphenol and tetrabromophthalate-(2-ethylhexyl) ester are by weight the compound that is 1: 2; Fire retarding synergist is particle diameter 4000 purpose Antimony Trioxide: 99.5Mins; Comprise also that in addition 1kg oxidation inhibitor 168,2kg photostabilizer benzotriazole, 1kg iron oxide red are as pigment;
(2) said components is placed high-speed mixer premix 20min, temperature is controlled at 70 ℃, obtains pre-composition;
(3) pre-composition that obtains is joined in the twin screw extruder that has accurate temperature regulating device and gas barrier; The temperature in each section of control twin screw extruder district is 180 ℃, 200 ℃, 220 ℃, 230 ℃, 240 ℃; Screw speed is 300rpm; Screw slenderness ratio 40 is extruded cooling granulation through conveying, fusion, shearing, obtains product.
Claims (7)
1. a flame-retardant styrene resin composition that is used for large-scale thin wall parts is characterized in that, said composition comprises following component and weight part content:
The styron 60～82 of modified rubber;
Impact modifying agent 1～5;
P contained compound 1～5;
Fire retardant 8～17;
Fire retarding synergist 3～7;
Described P contained compound is selected from the aromatic phosphate acid ester that following formula is represented:
Wherein, R
1, R
2, R
4, R
5Be selected from aromatic base or the substituted aromatic group of alkyl of C6～C20 respectively, R
3Be selected from a kind of in Resorcinol, bisphenol-A, the quinhydrones, polymkeric substance n is 0～6; Described aromatic phosphate acid ester is selected from one or more in triphenylphosphate, dihydroxyphenyl propane-diphenyl phosphate or the Resorcinol-diphenyl phosphate.
2. a kind of flame-retardant styrene resin composition that is used for large-scale thin wall parts according to claim 1; It is characterized in that; The styron of described modified rubber is that rubber is dispersed in the styron with particulate forms; Through transmission electron microscope observing is sea-island structure, is selected from high-impact polystyrene, styrene butadiene-acrylonitrile copolymer or cinnamic acrylic ester-acrylonitrile copolymer, and the styron melt flow rate(MFR) of this modified rubber is 4～15g/10min.
3. a kind of flame-retardant styrene resin composition that is used for large-scale thin wall parts according to claim 1; It is characterized in that; Described impact modifying agent is selected from one or more in styrene-butadiene block copolymer, vinylbenzene-ethylene propylene rubber segmented copolymer or the styrene butadiene graft copolymer, and the content of rubber is 50～80wt% in this impact modifying agent.
4. a kind of flame-retardant styrene resin composition that is used for large-scale thin wall parts according to claim 1; It is characterized in that described fire retardant is selected from tetrabromo-bisphenol, TDE, 2; 4; In 6-tribromo triple phenoxyl-1,3,5-triazines, ethylidene-(two tetrabromo phthalimide), brominated epoxy oligomer or tetrabromophthalate-(2-ethylhexyl) ester one or more.
5. a kind of flame-retardant styrene resin composition that is used for large-scale thin wall parts according to claim 1; It is characterized in that; Described fire retarding synergist is for containing sb oxide, and this contains sb oxide and is selected from Antimony Trioxide: 99.5Min, stibnate or the colloidal antimony pentoxide one or more.
6. a kind of flame-retardant styrene resin composition that is used for large-scale thin wall parts according to claim 1; It is characterized in that; Described flame-retardant styrene resin composition also comprises other auxiliary agent, is selected from lubricant, oxidation inhibitor, thermo-stabilizer, anti-dripping agent, photostabilizer, the pigment one or more.
7. a preparation method who is used for the flame-retardant styrene resin composition of large-scale thin wall parts is characterized in that, this method may further comprise the steps:
(1) get the raw materials ready according to following component and weight part content:
The styron 60～82 of modified rubber,
Impact modifying agent 1～5,
P contained compound 1～5,
Fire retardant 8～17,
Fire retarding synergist 3～7,
Described P contained compound is selected from the aromatic phosphate acid ester that following formula is represented:
Wherein, R
1, R
2, R
4, R
5Be selected from aromatic base or the substituted aromatic group of alkyl of C6～C20 respectively, R
3Be selected from a kind of in Resorcinol, bisphenol-A, the quinhydrones, polymkeric substance n is 0～6; Described aromatic phosphate acid ester is selected from one or more in triphenylphosphate, dihydroxyphenyl propane-diphenyl phosphate or the Resorcinol-diphenyl phosphate;
(2) said components is placed high-speed mixer premix 20min, temperature is controlled at 40～60 ℃, obtains pre-composition;
(3) pre-composition that obtains is joined in the twin screw extruder that has accurate temperature regulating device and gas barrier; The control extrusion temperature is 180～240 ℃, and screw speed is 200～400rpm, and screw slenderness ratio is not less than 30; Extrude cooling granulation through conveying, fusion, shearing, obtain product.
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| CN102408641B (en) * | 2011-08-05 | 2015-10-21 | 大连瑞贤达塑胶有限公司 | A kind of moulding process of plastic material |
| JP2015000892A (en) * | 2013-06-13 | 2015-01-05 | 株式会社リコー | Regenerated resin composition |
| CN106366555A (en) * | 2016-08-29 | 2017-02-01 | 合肥会通新材料有限公司 | Flame-retardant ABS modified material with high toughness, high thermal stability and ultra-high fluidity and preparation method thereof |
| CN106189034A (en) * | 2016-08-29 | 2016-12-07 | 合肥会通新材料有限公司 | One is applicable to thin-gage goods without the highly anti-flush polyphenylacetylene composition and preparation method thereof that glows |
| CN106784527A (en) * | 2016-12-22 | 2017-05-31 | 陈申申 | A kind of lead-acid accumulator dividing plate and preparation method thereof |
| JP7280133B2 (en) * | 2019-07-17 | 2023-05-23 | 旭化成株式会社 | Polyphenylene ether resin composition |
| CN110964284A (en) * | 2019-12-12 | 2020-04-07 | 武汉金发科技有限公司 | Flame-retardant HIPS composite material |
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| CN1299846A (en) * | 2000-09-28 | 2001-06-20 | 广州金发科技发展有限公司 | Weather-resistant high-flowbility fireproof shock-resistant polystyrene composite with less environment pollution |
| WO2003027180A1 (en) * | 2001-09-27 | 2003-04-03 | Lg Chem, Ltd. | Styrenic thermoplastic resin composition |
| CN101184806A (en) * | 2006-06-29 | 2008-05-21 | Lg化学株式会社 | Flame retardant rubber-modified styrene resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299846A (en) * | 2000-09-28 | 2001-06-20 | 广州金发科技发展有限公司 | Weather-resistant high-flowbility fireproof shock-resistant polystyrene composite with less environment pollution |
| WO2003027180A1 (en) * | 2001-09-27 | 2003-04-03 | Lg Chem, Ltd. | Styrenic thermoplastic resin composition |
| CN101184806A (en) * | 2006-06-29 | 2008-05-21 | Lg化学株式会社 | Flame retardant rubber-modified styrene resin composition |
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