CN106380770A - Flame-retardant styrene resin composition and preparation method thereof - Google Patents

Flame-retardant styrene resin composition and preparation method thereof Download PDF

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Publication number
CN106380770A
CN106380770A CN201610736995.7A CN201610736995A CN106380770A CN 106380770 A CN106380770 A CN 106380770A CN 201610736995 A CN201610736995 A CN 201610736995A CN 106380770 A CN106380770 A CN 106380770A
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flame retardant
styrene resin
retardant
flame
compositionss
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Inventor
王灿灿
郝雅珍
向以贵
赵光发
张秀文
谭伟宏
崔青涛
李伟
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Qingdao Haier New Material Research & Development Co Ltd
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Qingdao Haier New Material Research & Development Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The present invention relates to a flame-retardant styrene resin composition, which comprises the following components in weight part: 85-90 parts of styrene resin, 4-6 parts of halogen-based flame retardant, 1-2 parts of antimony-based flame retardant, 3-5 parts of phosphorus-based flame retardant, 0.1-0.2 part of antioxidant, and 0-2.0 parts of impact modifier. According to the technical scheme of the invention, under the synergistic effects of the antimony-based flame retardant, the phosphorus-based flame retardant and the halogen-based flame retardant, the flame-retardant efficiency of styrene resin is effectively improved. The flowability and the apparent quality of styrene resin are improved. Therefore, the problems in the prior art that styrene resin is difficult in injection molding and low in gloss can be solved. As a result, the flame-retardant styrene resin composition has a wide application prospect.

Description

A kind of flame retardant styrene resin compositionss and preparation method thereof
Technical field
The invention belongs to polymeric material field is and in particular to a kind of flame retardant styrene resin compositionss and its preparation side Method.
Background technology
Styrene resin is widely used in electronic apparatus, auto industry, office equipment, Communication Equipment, household electric at present The fields such as device, belong to inflammable macromolecular material, when having the product of flame-retardancy requirements for electronic apparatus etc., need it is carried out Flame-retardant modified, to meet its use requirement in terms of fire safety.At present, styrene resin is the most commonly used and using effect Best flame-retardant system is the synergistic system of halogenated flame retardant and antimony oxide, and this system is passed through the fire-retardant mechanism of gas phase and realized Anti-flammability.In styrene resin, the application of other based flame retardants is less, main reason is that other kind based flame retardant such as phosphorus systems The addition of fire retardant, can destroy the synergistic system of halogenated flame retardant and antimony oxide, affect flame retarding efficiency.There is documents below equal Halogen antimony flame retarded wall is studied：
Patent CN 102977490 A discloses a kind of interpolation 70-80 part polystyrene, and 1-3 part aoxidizes dibenzoyl, 4-6 Part TDE, 1.5-4 part antimony oxide, 1.5-7 part Firebrake ZB, 1-4 part lubrication dispersing agent, 2-3 part toughener system The method of standby flame-proof polystyrene composition.
Patent CN 103160036 A discloses a kind of interpolation 70-80 part high impact polystyrene, and 12-15 part bromine system is fire-retardant Agent, 2-10 part chlorinated polyethylene, 1-5 part antimony oxide, 0.1-1 part antioxidant, 0.1-0.5 part lubricant is prepared fire-retardant high anti- The method rushing modified polystyrene resin.
Patent CN 102391608 A discloses a kind of 100 parts of ABS resin of interpolation, 10-25 part TDE, or bromine Change epoxy, or mould assembly fire retardant FR-Emerald 1000, or their mixture, 2-8 part is by antimony oxide, inorganic particle With the fire retarding synergist of super high molecular weight polysiloxanes composition, 5-30 part heat-proof modifier, 0.1-2 part dispersant, 1-10 part increases Tough dose, 0.1-1 part antioxidant, 0.1-1 part light stabilizer, the method that 0.5-5 part processing aid prepares superelevation heat-proof combustion-resistant ABS.
Patent CN 102863734 A discloses a kind of interpolation 50-90 part ABS resin, 3-20 part brominated triazine, or bromination Epoxy, or TDE, or tetrabromobisphenol A, or their mixture, 1-6 part antimony oxide, 1-10 part MCA, 0.1- 1 part of PTFE, 2-15 part toughener, 0.2-2 part antioxidant, the method that flame-proof ABS prepared by 0.1-1 part lubricant.
Patent CN 103571151 A discloses a kind of interpolation 50-80 part ABS resin, 5-10 part toughener, 15-20 part four Bromine bisphenol-A, or TDE, or brominated epoxy, or brominated triazine, or their mixture, 1-10 part antimony oxide, Or antimony pentoxide, or Firebrake ZB, or Pulvis Talci, or their mixture, 0.1-05 part politef, 0.5-2.5 part heat Stabilizer, 0.3-1 part antioxidant, 0.2-1.2 part lubricant, 3-5 part stearic acid monoglyceride, 0.1-1.5 part zinc ion antibacterial The method that high antibacterial flame-retardant ABS resin is prepared in agent.
Although the halogen antimony synergistic flame-retardant system in the studies above has excellent flame retardant effect, due to most of halogen Antimony fire retardant is inorganic particle, and inorganic particle is poor with the compatibility of resin and dispersibility, a certain amount of inorganic with the addition of After powder body, the melt index of resin, surface gloss and mechanical property are all greatly reduced.Therefore halogen antimony flame-retardant system is modified Styrenics compositions, most mobility is poor, thus causing injection mo(u)lding difficult, affects apparent mass and the product table of product Face glossiness is low.
Content of the invention
The purpose of the present invention is exactly to be referred to due to melting to overcome that above-mentioned existing styrene resin flame-retarded technology exists The defect such as the low injection mo(u)ldings that cause of number are difficult, glossiness is low, apparent mass is poor, and a kind of height flowing, high glaze, apparent is provided Matter measured flame retardant styrene resin compositionss.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of flame retardant styrene resin compositionss, said composition includes following components and weight portion content：
Preferably, described styrene resin be selected from acrylonitrile-butadiene-styrene copolymer, general purpose polystyrene, Acrylonitrile-butadiene-acrylate copolymer, MBS, acrylonitrile-chloride gather One of ethylene-styrene copolymer, acrylonitritrile-styrene resin, copolymer of methyl methacrylatestyrene or several The mixing planted.
Preferably, described halogenated flame retardant is selected from chlorinated polyethylene, chlorinated paraffin, tetrabromobisphenol A, decabrominated dipheny second Alkane, brominated triazine, brominated epoxy resin, Brominated Polystyrene, bromination phenoxy resin, tribromo-benzene based phosphates, the poly- carbon of bromination The mixing of one or more of acid esters oligomer.
Preferably, described Sb system fire retardant is one or more of sodium antimonate, antimony oxide, antimony pentoxide Compositionss.
Preferably, described phosphorus flame retardant is phosphate ester flame retardants, further preferably from the double (diphenylphosphine of bisphenol-A Acid esters), resorcinol double (diphenyl phosphoester), triphenyl phosphate, trimethyl phosphate, triethyl phosphate, fire retardant PX220, The mixing of one or more of tricresyl phosphate.
Preferably, described antioxidant is Irganox 1010, Irganox 1076, Irganox 1098, Irganox The mixture of one of 168 or B215 or two kinds.
Preferably, described impact modifying agent is one of toughening polystyrene agent SBS, ABS toughener high glue powder.
Preferably, described styrene resin composite also comprises inorganic filler；Described inorganic filler be Pulvis Talci, The mixing of one or more of barium sulfate, Calcium Carbonate, montmorillonite, Kaolin, Muscovitum, glass microballoon, brucite, wollastonite.
Another object of the present invention is the preparation method providing above-mentioned flame retardant styrene resin compositionss, using such as Lower technical scheme：
A kind of preparation method of flame retardant styrene resin compositionss, comprises the following steps：
(1) batch mixing：By proportioning weighing, by 85-90 parts by weight of styrene resinoid, 4-8 weight portion halogenated flame retardant, 3-5 Weight portion phosphorus flame retardant, 1-2 weight portion Sb system fire retardant, 0-2.0 weight portion impact modifying agent, 0.1-0.2 weight portion antioxygen Agent mix homogeneously；
(2) mixture of step (1) is sent in double screw extruder, under the shearing of twin screw, conveying, kneading, fill Point melt, mixing, then through head extrusion, tie rod, fetch water, pelletizing, drying, be finally packaged into finished product；Double screw extruder leading portion Temperature is 180-200 DEG C, and stage casing temperature is 200-220 DEG C, and head extrusion temperature is 220 DEG C, screw speed turns for 480-700/ Minute.
Mixing in described step (1) is carried out in mixer, and the rotating speed of mixer is 200-2000rpm, and mixing time is 1-5 minute.
The present invention has advantages below：
(1) pass through to reduce the number of bromine antimony fire retardant, and add phosphate ester flame retardants, phosphate ester flame retardants are to halogen system Fire retardant shows good synergistic anti-flammability, under halogen, antimony system, the synergism of phosphorus flame retardant, effectively increases The flame retarding efficiency of styrene resin, flame retardant rating reaches V2 level.
(2) due to the addition of high fluidity phosphorus flame retardant, improve mobility and the apparent mass of styrene resin, Thus solving the problems, such as that flame retardant styrene resin injection mo(u)lding is difficult and glossiness is low, have broad application prospects.
(3) utilize cheap phosphorus flame retardant to substitute part bromine Sb system fire retardant, significantly reduce the production of material Cost.
(4) any lubricant, Simplified flowsheet, reduces cost need not be added during extruding pelletization.
(5) injection temperature, Simplified flowsheet, reduces cost can greatly be reduced.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area For personnel, without departing from the inventive concept of the premise, some deformation can also be made and improve.These broadly fall into the present invention Protection category.
According to the proportioning raw materials weighing of embodiment 1-6 and comparative example 1-2, will be fire-retardant to the styrene resin weighing up, halogen system Agent, phosphorus flame retardant, Sb system fire retardant, impact modifying agent, antioxidant divide through high-speed mixer stirring (200-2000rpm) 1-5 Said mixture, so as to mix homogeneously, is then sent in extruder, front-end temperature is 180-200 DEG C, stage casing temperature is by clock 200-220 DEG C, head extrusion temperature is 220 DEG C, and screw speed is 480-700 rev/min.In the shearing of twin screw, conveying, mixed Under refining, fully melt, mixing, then through head extrusion, tie rod, fetch water, pelletizing, drying, be finally packaged into finished product.
The flame retardant styrene resin of each embodiment and comparative example preparation is molded into various standard mechanical property by ASTM standard Mechanical performance and the fire resistance of resin can be tested, physical property and method of testing are as shown in table 1.
The quantitative measurement method of the resin that table 1 embodiment 1-5 and comparative example 1-2 prepare
Physical property Method of testing
Tensile strength (50mm/min) ASTM D638
Bending strength (2mm/min) ASTM D790
Melt index (200 DEG C, 5Kg) ASTM D1238
Heat distortion temperature (1.82MPa) ASTM D648
IZOD notch impact strength (3.2mm) ASTM D256
Flammability (vertical combustion 3.0mm/1.5mm) UL 94
Glossiness BG/T8007
Embodiment 1
The component of styrene resin composite and mass fraction are：
Wherein：
Styrene resin is high impact polystyrene 8250 resin of platform；
Halogenated flame retardant is brominated triazine；
Sb system fire retardant is antimony oxide；
Phosphorus flame retardant is the PX220 of ten thousand Shengs；
Antioxidant is Irganox 1010.
Embodiment 2
The component of styrene resin composite and mass fraction are：
Wherein：
Styrene resin is high impact polystyrene 8250 resin of platform；
Halogenated flame retardant is refined precious tetrabromobisphenol A；
Sb system fire retardant is the mixture of antimony oxide and sodium antimonate；
Phosphorus flame retardant is the PX220 of ten thousand Shengs；
Antioxidant is Irganox 1076.
Embodiment 3
The component of styrene resin composite and mass fraction are：
Wherein：
Styrene resin is the high impact polystyrene 425TVL resin of Jin Hu；
Halogenated flame retardant is refined precious TDE；
Sb system fire retardant is antimony oxide；
Phosphorus flame retardant is the triphenyl phosphate of ten thousand Shengs；
Antioxidant is Irganox 1098.
Embodiment 4
The component of styrene resin composite and mass fraction are：
Wherein：
Styrene resin is acrylonitrile-butadiene-styrene copolymer, LG 121H resin；
Halogenated flame retardant is brominated triazine；
Sb system fire retardant is the mixture of antimony oxide and antimony pentoxide；
Phosphorus flame retardant is that bisphenol-A is double (diphenyl phosphoester)；
Antioxidant is Irganox 1010；
Lubricant is fatty acid amide.
Embodiment 5
The component of styrene resin composite and mass fraction are：
Wherein：
Styrene resin is acrylonitrile-butadiene-styrene copolymer, LG 121H resin；
Halogenated flame retardant is brominated triazine；
Sb system fire retardant is antimony oxide；
Phosphorus flame retardant is that bisphenol-A is double (diphenyl phosphoester)；
Antioxidant is B215.
Comparative example 1
The component of styrene resin composite and mass fraction are：
Wherein：
Styrene resin is scape lake day beautiful 425TV resin；
Impact modifying agent is SBS；
Halogenated flame retardant is the compound of TDE and brominated triazine；
Sb system fire retardant is antimony oxide；
Antioxidant is 0.1kg Irganox 1010 and 0.2kg Irganox 168；
Lubricant is the compound of calcium stearate and aliphatic amide.
Comparative example 2
The component of styrene resin composite and mass fraction are：
Wherein：
Styrene resin is acrylonitrile-butadiene-styrene copolymer, LG 121H resin；
Halogenated flame retardant is tetrabromobisphenol A；
Sb system fire retardant is antimony oxide；
Antioxidant is 0.1kg Irganox 1010 and 0.2kg Irganox 168；
Lubricant is the compound of calcium stearate and aliphatic amide.
The physical function parameter table 2 of the resin that table 2 embodiment 1-5 and comparative example 1-2 prepare
As shown in table 2, test result shows the physical property measurement result of embodiment 1-5 and comparative example 1-2, bromine system, phosphorus system, antimony The cooperative flame retardant system of system's composition has efficient flame retarding efficiency, and this system resin has good mobility and processing is special Property, it is favorably improved the apparent mass of material.Therefore this flame-retardant system can greatly improve mobility and the table of resin combination Appearance quality, under the present situation of Market competition, improves the market competitiveness to modified enterprise and is significant.In addition, phosphorus system Fire retardant has also played plasticization, though as do not added impact modifying agent in embodiment 1, its notch impact strength is still better than adding The comparative example 1 of impact modifying agent, on the one hand because comparative example 1 employs larger amount of powdery halogen antimony flame-retardant system impact mechanical property Can, on the other hand embody the plasticization that phosphorus flame retardant plays in styrene resin lipid composite.Additionally, due to phosphorus Flame retardant high temperature becomes oily after dissolving, and serves lubrication, scattered effect, from embodiment 1-5, even if not adding Plus in the case of lubricant, its melt index is higher than still comparative example 1-2 that with the addition of lubricant.

Claims (10)

1. a kind of flame retardant styrene resin compositionss are it is characterised in that said composition includes following components and weight portion content：
2. flame retardant styrene resin compositionss according to claim 1 are it is characterised in that described styrene resin Selected from acrylonitrile-butadiene-styrene copolymer, general purpose polystyrene, acrylonitrile-butadiene-acrylate copolymer, methyl Methylacrylate-butadiene-styrol copolymer, acrylonitrile-chlorianted polyethylene-styrene terpolymer, acrylonitrile-styrene are common The mixing of one or more of polymers, copolymer of methyl methacrylatestyrene.
3. flame retardant styrene resin compositionss according to claim 1 are it is characterised in that described halogenated flame retardant selects From chlorinated polyethylene, chlorinated paraffin, tetrabromobisphenol A, TDE, brominated triazine, brominated epoxy resin, bromo polyphenyl second The mixing of one or more of alkene, bromination phenoxy resin, tribromo-benzene based phosphates, brominated polycarbonate oligomer.
4. flame retardant styrene resin compositionss according to claim 1 are it is characterised in that described Sb system fire retardant is The compositionss of one or more of sodium antimonate, antimony oxide, antimony pentoxide.
5. flame retardant styrene resin compositionss according to claim 1 are it is characterised in that described phosphorus flame retardant is Phosphate ester flame retardants.
6. flame retardant styrene resin compositionss according to claim 1 are it is characterised in that described phosphorus flame retardant selects From bisphenol-A double (diphenyl phosphoester), resorcinol double (diphenyl phosphoester), triphenyl phosphate, trimethyl phosphate, tricresyl phosphate The mixing of one or more of ethyl ester, fire retardant PX220, tricresyl phosphate.
7. flame retardant styrene resin compositionss according to claim 1 are it is characterised in that described antioxidant is The mixing of one of Irganox 1010, Irganox 1076, Irganox 1098, Irganox 168 or B215 or two kinds Thing.
8. flame retardant styrene resin compositionss according to claim 1 are it is characterised in that described impact modifying agent is One of toughening polystyrene agent SBS, ABS toughener high glue powder.
9. flame retardant styrene resin compositionss according to claim 1 are it is characterised in that described styrene resin Compositionss also comprise inorganic filler；Described inorganic filler be Pulvis Talci, barium sulfate, Calcium Carbonate, montmorillonite, Kaolin, Muscovitum, The mixing of one or more of glass microballoon, brucite, wollastonite.
10. a kind of preparation method of flame retardant styrene resin compositionss is it is characterised in that comprise the following steps：
(1) batch mixing：By proportioning weighing, by 85-90 parts by weight of styrene resinoid, 4-8 weight portion halogenated flame retardant, 3-5 weight Part phosphorus flame retardant, 1-2 weight portion Sb system fire retardant, 0-2.0 weight portion impact modifying agent, 0.1-0.2 weight portion antioxidant mix Close uniformly；
(2) mixture of step (1) is sent in double screw extruder, under the shearing of twin screw, conveying, kneading, fully melt Change, mixing, then through head extrusion, tie rod, fetch water, pelletizing, drying, be finally packaged into finished product；Double screw extruder front-end temperature For 180-200 DEG C, stage casing temperature is 200-220 DEG C, and head extrusion temperature is 220 DEG C, and screw speed is 480-700 rev/min.
CN201610736995.7A 2016-08-26 2016-08-26 Flame-retardant styrene resin composition and preparation method thereof Pending CN106380770A (en)

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CN109503970A (en) * 2018-11-27 2019-03-22 金发科技股份有限公司 A kind of high fire-retardance grade HIPS composite
CN109721922A (en) * 2018-12-26 2019-05-07 金旸（厦门）新材料科技有限公司 A kind of bathroom high glaze antibacterial flame-retardant AS/MS composite material and preparation method
CN110317421A (en) * 2019-07-15 2019-10-11 莱法特防火材料河北有限公司 A kind of Novel fireproof sealing material and preparation method thereof
CN110951207A (en) * 2019-12-12 2020-04-03 武汉金发科技有限公司 Flame-retardant ABS composite material
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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