WO2013085791A1 - Composition ignifugée à basse teneur d'antimoine de type polymère thermoplastique styrénique - Google Patents

Composition ignifugée à basse teneur d'antimoine de type polymère thermoplastique styrénique Download PDF

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Publication number
WO2013085791A1
WO2013085791A1 PCT/US2012/067043 US2012067043W WO2013085791A1 WO 2013085791 A1 WO2013085791 A1 WO 2013085791A1 US 2012067043 W US2012067043 W US 2012067043W WO 2013085791 A1 WO2013085791 A1 WO 2013085791A1
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Prior art keywords
retarded
flame
thermoplastic polymer
styrenic thermoplastic
polymer composition
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PCT/US2012/067043
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English (en)
Inventor
Sergei V. Levchik
Yankai YANG
Marc LEIFER
James Innes
Garrett SHAWHAN
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Icl-Ip America Inc.
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Publication of WO2013085791A1 publication Critical patent/WO2013085791A1/fr

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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
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/08—Organic materials containing halogen

Definitions

  • the present invention relates to flame-retarded thermoplastic compositions and more particularly to flame-retarded styrenic thermoplastic polymer compositions and articles containing the same.
  • Styrenic polymers and more specifically high impact polystyrene (HIPS) and
  • ABS acrylonitrile, butadiene, styrene polymers
  • flame retardancy is needed and is usually provided by flame retardant systems based on a combination of brominated flame retardants with antimony trioxide as a synergist.
  • antimony trioxide being a very efficient synergist, tends to significantly increase smoke yield, which impairs visibility which could create problems for evacuation of people in the case of a fire.
  • antimony trioxide has a very high bulk density which increases the specific gravity of molded parts containing the same. This is especially undesirable in transportation and aviation applications.
  • antimony trioxide has significantly increased in price in recent years. Still further, some recently introduced ecolabels require elimination of antimony trioxide from thermoplastic parts.
  • the present invention is directed to a low antimony trioxide flame-retarded styrenic thermoplastic polymer composition
  • a low antimony trioxide flame-retarded styrenic thermoplastic polymer composition comprising:
  • thermoplastic polymer (a) at least one styrenic thermoplastic polymer
  • the flame-retarded styrenic thermoplastic polymer composition can optionally further comprise antidripping agent, impact modifiers, heat stabilizers, antioxidants, processing aids, and other additives enhancing physical properties of the resin.
  • any reference to a flame-retarded styrenic thermoplastic polymer composition is such that the composition is low antimony trioxide styrenic
  • thermoplastic composition thermoplastic composition.
  • the present invention is directed to a flame retardant additive composition that comprises a unique and unexpected combination of a bromine compound, an antimony synergist, e.g. , antimony trioxide and calcium borate on an inorganic carrier.
  • a flame retardant additive composition can be used in styrenic thermoplastic polymers and compositions containing styrenic thermoplastic polymers, to provide flame retardancy at significantly reduced loading of antimony trioxide.
  • Styrenic thermoplastic polymer (a) refers to polymers, and specifically copolymers (including terpolymers), which contain (optionally substituted) a styrenic structural unit, however combined with one or more other structural units. More specific examples of styrenic thermoplastic polymer (a) are styrene-based copolymers belonging to the following classes:
  • HIPS high impact polystyrene
  • rubber-modified copolymers of styrenic monomers obtainable, for example, by mixing an elastomer (butadiene) with the (optionally substituted) styrenic monomer(s) prior to polymerization.
  • the styrenic thermoplastic polymer (a) generally comprise between 40 wt% and 85 wt%, more specifically between 50 wt% and 85 wt% HIPS resins having a melt flow index (MFI) between 1 and 50 g/lOmin (measured according to ISO 1 133; 200°C/5kg).
  • MFI melt flow index
  • ABS acrylonitrile butadiene styrene
  • copolymers and terpolymers that include the structural units corresponding to (optionally substituted) styrene, acrylonitrile and butadiene, regardless of the composition and method of production of said polymers.
  • the styrenic thermoplastic polymer (a) can comprise between 40 wt% and 85 wt%, more specifically between 50 wt% and 83 wt% ABS having an MFI between 1 and 50 g/lOmin (measured according to ISO 1 133 at 220°C/10 kg).
  • SAN styrene acrylonitrile: copolymer of acrylonitrile and styrene, and SMA (styrene maleic anhydride); copolymer of styrene with maleic anhydride.
  • the styrenic thermoplastic polymer (a) can in one embodiment comprise between 40 wt% and 85 wt% SAN, and in another embodiment can comprise between 40 wt% and 85 wt% SMA.
  • the flame-retarded styrenic thermoplastic polymer composition of the invention can contain as the styrenic thermoplastic polymer (a) an alloy of styrene-containing polymers, namely, a blend of a styrene-containing polymer as set forth above with a second polymer or copolymer (such blends are obtained by extruding pellets of the styrene-containing polymer (a) and pellets of the second polymer in desired proportions).
  • a an alloy of styrene-containing polymers
  • a blend of a styrene-containing polymer as set forth above with a second polymer or copolymer such blends are obtained by extruding pellets of the styrene-containing polymer (a) and pellets of the second polymer in desired proportions.
  • Some non-limiting examples of such blends include a blend of HIPS and polyphenylene oxide or a blend of ABS with polycarbonate.
  • HIPS/polyphenylene oxide alloy such can comprise the styrene- containing polymer (HIPS) at a concentration in the range between 20 wt% and 80 wt%.
  • HIPS styrene-containing polymer
  • ABS/polycarbonate alloy such can comprise the styrene-containing polymer (ABS) at a concentration in the range between 5 wt% and 85 wt%.
  • thermoplastic styrenic polymer (a) is different from any brominated polystyrene flame retardant (b) which is employed. In one embodiment the thermoplastic styrenic polymer (a) is non-halogenated.
  • Brominated flame retardant (b) includes any flame retardant which contains a bromine atom in its chemical structure.
  • the most specific brominated flame retardant compounds (b) have the following formulae.
  • the brominated flame retardant (b) is present in the flame-retarded styrenic thermoplastic polymer composition in the range of from about 2 wt% to about 40 wt% and specifically in the range from about 5 wt% to about 30 wt% based on the total weight of the flame-retarded styrenic thermoplastic polymer composition.
  • Antimony synergist (c) e.g., antimony trioxide
  • the proportion of antimony synergist (c) which is appropriate is when one antimony atom exists based on every two to five bromine atoms of the brominated flame retardant.
  • the proportion is smaller than one antimony atom for every five bromine atoms the effect of antimony synergist is negligible.
  • the proportion is larger than one antimony atom for every two bromine atoms, an increase in the effect can no longer be expected even by further increase of antimony synergist proportion and the obtained flame-retarded styrenic thermoplastic polymer composition is inferior in mechanical properties and moldability such as flowability.
  • antimony syngergist (c) can be antimony pentaoxide or sodium and combinations of any of the noted antimony synergists.
  • the average particle size of antimony synergist (c) is specifically from 0.5 ⁇ to 5 ⁇ .
  • Antimony synergist (c) may be surface-treated with an epoxy compound, silane compound, isocyanate compound, titanate compound, or the like as required.
  • Antimony synergist (c) can be used as a powder or as a masterbatch compounded in a carrier resin. Typically a masterbatch contains 50-80 wt. % pre-dispersed antimony syngerist (c) such as the non-limiting example of antimony trioxide.
  • Use of a masterbach impoves safety of the operation eliminating the handling of hazardous powder and improves dispersion of antimony synergist (c) in the flame-retarded styrenic thermoplastic polymer composition.
  • the antimony synergist (c) can be present in an amount of less than 5 weight percent based on the total weight of the flame-retarded styrenic
  • thermoplastic polymer composition and in a further embodiment can have a lower endpoint range amount of zero or a lower endpoint range amount of 0.001 weight percent, more specifically a lower endpoint range amount of 0.01 weight percent, even more specifically a lower endpoint range amount of 0.1 weight percent or a lower endpoint range amount of 0.5 weight percent with said a lower endpoint range amounts being based on the total weight of the flame-retarded styrenic thermoplastic polymer composition.
  • the calcium borate on an inorganic carrier (d), which is used herein, can in one embodiment be manufactured by the reaction of lime with boric acid in the presence of an inorganic carrier, in a water suspension, with subsequent drying, milling and sieving.
  • the calcium borate on an inorganic carrier can in addition to the calcium borate comprise any known inorganic filler material as the inorganic carrier.
  • inorganic filler material which may function as the inorganic carrier are aluminum hydroxide, boehmite, natural calcium carbonate, precipitated calcium carbonate, calcium sulphate, carbon black, carbon fibers, clay, cristobalite, diatomaceous earth, dolomite, feldspar, graphite, glass beads, glass fibers, kaolin, magnesium carbonate, magnesium hydroxide, metal powders or fibers, mica muscouite, mica phlogopite, natural silica, synthetic silica, nepheline-syenite, talc, whiskers, natural wollastonite or synthetic calcium silicate, and combinations thereof.
  • the inorganic carrier for the calcium borate on an inorganic carrier is wollastonite. More specifically, the calcium borate on an inorganic carrier (e.g. wherein the inorganic carrier is wollastonite) is such that the particles of calcium borate on the inorganic carrier (e.g wollastonite) have a mean particle size (d 5 o) of from about 1 micron to about 15 microns and 99 weight percent of the total amount of particles of calcium borate on an inorganic carrier have a diameter (d 99 ) of less than about 50 microns, and more specifically, a d 5 o of from about 2 microns to about 10 microns and a d 99 of less than about 25 microns.
  • the calcium borate on an inorganic carrier contains from about 20 to about 80 weight percent of wollastonite and from about 20 to about 80 weight percent of calcium borate, provided that the total weight percent of calcium borate and the total amount of inorganic carrier is equal to 100 weight percent.
  • the inorganic carrier is synthetic calcium silicate having a d 5 o of from about 0.5 microns to about 3 microns. Such calcium silicates are available for example from Evonik, Europe or Shreji, China.
  • the calcium borate on any inorganic carrier (d) herein can be present in an amount of from about 1 to about 10 weight percent based on the total weight of the flame-retarded styrenic thermoplastic polymer composition.
  • the antidripping agent is used in order to further improve efficiency of the flame-retarded styrenic thermoplastic polymer composition.
  • the antidripping agent is generally a fluoropolymer or copolymer containing a fluoro-ethylenic structure.
  • antidripping agent examples include difluoroethylene polymers, tetrafluoroethylene polymers, tetrafluoroethylene-hexafluoropropylene copolymers, and copolymers of
  • the antidripping agent (d) is polytetrafluoroethylene (PTFE). Any and every type of polytetrafluoroethylene known at present in the art is usable for antidripping agent.
  • polytetrafluoroethylene used herein is not specifically limited.
  • Specific examples of the polytetrafluoroethylene capable of forming fibrils include Teflon 6C (registered trademark of DuPont) or Hostaflon 2071 (registered trademark of Dynon).
  • the content of the antidripping agent in the flame-retarded styrenic thermoplastic polymer composition is generally from 0.05 percent by weight to 2 percent by weight, specifically between 0.1 percent by weight to 0.5 percent by weight.
  • the amount of the fluororesin may be suitably determined depending on the required flame retardancy of the article formed from the flame-retarded styrenic thermoplastic polymer composition, for example, based on V-0, V-l or V-2 in UL-94 in consideration with the amount of the other components.
  • ingredients that can be employed in amounts less than 10 percent by weight of the low antimony trioxide flame-retarded styrenic thermoplastic polymer composition, specifically less than 5 percent by weight include the non-limiting examples of lubricants, heat stabilizers, light stabilizers and other additives used to enhance the properties of the resin. Such other ingredients may be specifically utilized in amounts from 0.01 to 5 percent by weight of the total weight of the low antimony trioxide or antimony free flame-retarded styrenic thermoplastic polymer composition and include specific examples such as hindered phenols and phosphites.
  • the low antimony trioxide flame-retarded styrenic thermoplastic polymer composition comprises styrenic thermoplastic polymer (a), e.g., HIPS, ABS, SAN or SMA resin in an amount of from about 40 wt% to about 85 wt%; brominated flame retardant (b) in an amount of from about 2 wt% to about 40 wt%; antimony trioxide (c) in an amount of from about 0.001 wt% to about 5 wt% and an calcium borate on an inorganic carrier (d), in an amount of from about 1 wt% to about 10 wt% all based on the total weight of the low antimony trioxide flame-retarded styrenic thermoplastic polymer composition.
  • styrenic thermoplastic polymer e.g., HIPS, ABS, SAN or SMA resin in an amount of from about 40 wt% to about 85 wt%
  • brominated flame retardant b
  • the low antimony trioxide flame-retarded styrenic thermoplastic polymer composition comprises styrenic thermoplastic polymer (a), e.g., HIPS, ABS, SAN or SMA resin in an amount of from about 50 wt% to about 85 wt%; brominated flame retardant (b) in an amount of from about 5 wt% to about 30 wt%; antimony trioxide (c) in an amount of from about 0.5 wt% to about 5 wt% weight percent and calcium borate on a silicate carrier (d), in an amount of from about 1 wt% to about 10 wt% all based on the total weight of the low antimony trioxide flame retarded styrenic thermoplastic polymer composition.
  • styrenic thermoplastic polymer e.g., HIPS, ABS, SAN or SMA resin in an amount of from about 50 wt% to about 85 wt%
  • brominated flame retardant b
  • flame retardant additives (b), (c) and (d) in the low antimony trioxide flame-retarded styrenic thermoplastic polymer composition or articles made therefrom are flame- retardant effective amounts thereof.
  • the low antimony trioxide flame-retarded styrenic thermoplastic polymer composition or articles made therefrom herein can have a flame retardancy classification of one or more of HB, V-2, V-l, V-0 and 5VA according to UL-94 protocol.
  • the low antimony trioxide flame-retarded styrenic thermoplastic polymer composition can have a flame retardancy of at least V-l or V-0.
  • a method of making a low antimony flame-retarded styrenic thermoplastic polymer composition or articles made therefrom comprising blending the styrenic polymer (a) and other ingredients (b), (c) and (d) in powder or granular form, extruding the blend and comminuting the blend into pellets or other suitable shapes.
  • Blending and compounding of the low antimony flame-retarded styrenic thermoplastic polymer compositions of this invention can be carried out by any other conventional techniques. Although it is not essential, the best results are obtained if the ingredients (a), (b), (c) and (d) are compounded, pelletized and then molded into a desirable article.
  • Compounding can be carried out in conventional equipment.
  • the styrenic polymer (a), other ingredients (b), (c) and (d), and, optionally, other additives are fed into a twin screw extruder in the form of a dry blend of the composition, the screw employed having a long transition section to insure proper melting.
  • the low antimony trioxide flame-retarded styrenic thermoplastic polymer composition can be molded in any equipment conventionally used for thermoplastic compositions. If necessary, depending on the molding properties of the styrenic polymer (a), the amount of additives, resin flow and the rate of solidification of the styrenic polymer (a), those skilled in the art will be able to make the conventional adjustments in molding cycles to accommodate the composition.
  • the wet- milled product was pumped into a steam heated drum dryer operating at 190 - 240 degrees F and was then conveyed by a hot air line with the end temperature setup at about 310 degrees F. At the final stage the dried product went through a ACM60 grinding mill further decreasing the particle size to d 5 o ⁇ 7 micron and d 99 ⁇ 25 micron. The final product was packaged into bags. Examples 2-14.
  • the polymers pellets, brominated flame retardants, antimony trioxide, calcium borate on a silicate carrier, PTFE and stabilizers were weighted on semi analytical scales with consequent manual mixing in plastic bags.
  • the mixtures were introduced into the main feeding port of the extruder.
  • the obtained pellets of compounded mixtures were dried in a circulating air oven instruments at 80°C for overnight.
  • Test specimens were prepared by injection molding the pellets of compounded mixtures on Arburg All-Rounder Injection Molding machine at 220-250°C.
  • Comparative examples 2 and 5 show standard formulations recommended in technical literature for V-0 rated HIPS using FR-245 or FR-1410 respectively.
  • Replacement of about 1/2 of the antimony trioxide with FR-1120 in both example 3 which contains FR-245 and in example 6 which contains FR- 1410 allowed the preservation of the V-0 rating and the comparable physical properties to the standard formulation.
  • Replacement of about 2/3 of the antimony trioxide in C2 and C5 with FR- 1 120 resulted in decreasing UL-94 rating from V-0 to V-l, which is still acceptable for many parts of electronic equipment and keeping good physical properties.
  • examples 3,4,6 and 7 represent low antimony trioxide HIPS thermoplastic polymers.
  • Composition and tests results for ABS are presented in Table 4.
  • Comparative examples 8 and 1 1 show standard formulations recommended in technical literature for V-0 rated ABS using FR-245 or FR-1524 respectively.
  • Replacement of about 1/2 of the antimony trioxide with FR- 1 120 in example 9 which contains FR-245 allowed the preservation of the V-0 rating and comparable physical properties to the standard formulation.
  • Replacement of about 2/3 of the antimony trioxide with F-l 120 in example 10 resulted in a decrease in the UL-94 rating from V- 0 to V-1.
  • FR-1120 was able to replace only 1/3 of antimony trioxide in CI 1 and still preserve a V-0 rating in example 12. Replacement of 1/2 of the antimony trioxide in comparative example 11 (CI 1) with Fr-1120 lead to the failure of UL-94 vertical test in comparative example 13 (C I 3).
  • the formulations of examples 9,10 and 19 represent low antimony trioxide ABS thermoplastic polymers.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition ignifugée à basse teneur de trioxyde d'antimoine de type polymère thermoplastique styrénique comprenant : (a) au moins un polymère thermoplastique styrénique ; (b) au moins un agent ignifuge bromé ; (c) au moins un synergiste de type trioxyde d'antimoine en une quantité inférieure à 5 % en poids ; et (d) au moins un borate de calcium sur support inorganique. Un procédé de préparation de ladite composition ignifugée de type polymère thermoplastique styrénique et un article l'utilisant sont également décrits.
PCT/US2012/067043 2011-12-09 2012-11-29 Composition ignifugée à basse teneur d'antimoine de type polymère thermoplastique styrénique WO2013085791A1 (fr)

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US201161568968P 2011-12-09 2011-12-09
US61/568,968 2011-12-09

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014047322A (ja) * 2012-09-03 2014-03-17 Dai Ichi Kogyo Seiyaku Co Ltd 難燃化スチレン系樹脂組成物
WO2015123042A1 (fr) * 2014-02-12 2015-08-20 Icl-Ip America Inc. Composition polymère de polyoléfine ignifugée ayant une teneur réduite en trioxyde d'antimoine
CN106221102A (zh) * 2016-08-25 2016-12-14 桂林浩新科技服务有限公司 一种高效耐热阻燃组合物及其制备方法
CN106366551A (zh) * 2016-08-25 2017-02-01 桂林浩新科技服务有限公司 一种阻燃组合物及其制备方法
CN106398091A (zh) * 2016-08-25 2017-02-15 桂林浩新科技服务有限公司 一种高效耐热阻燃组合物及其制备方法
CN109627671A (zh) * 2018-11-27 2019-04-16 金发科技股份有限公司 一种abs复合材料
CN110964284A (zh) * 2019-12-12 2020-04-07 武汉金发科技有限公司 一种阻燃hips复合材料

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US20100076137A1 (en) * 2006-11-20 2010-03-25 Mitsui Chemcials Inc. Flame -retardant polyamide composition
US20110160362A1 (en) * 2008-07-22 2011-06-30 Bromine Compounds Ltd. Flame-retarded compositions of styrene-containing polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100076137A1 (en) * 2006-11-20 2010-03-25 Mitsui Chemcials Inc. Flame -retardant polyamide composition
US20110160362A1 (en) * 2008-07-22 2011-06-30 Bromine Compounds Ltd. Flame-retarded compositions of styrene-containing polymers

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014047322A (ja) * 2012-09-03 2014-03-17 Dai Ichi Kogyo Seiyaku Co Ltd 難燃化スチレン系樹脂組成物
WO2015123042A1 (fr) * 2014-02-12 2015-08-20 Icl-Ip America Inc. Composition polymère de polyoléfine ignifugée ayant une teneur réduite en trioxyde d'antimoine
US10119012B2 (en) 2014-02-12 2018-11-06 Icl-Ip America Inc. Flame-retarded polyolefin polymer composition with reduced antimony trioxide content
CN106221102A (zh) * 2016-08-25 2016-12-14 桂林浩新科技服务有限公司 一种高效耐热阻燃组合物及其制备方法
CN106366551A (zh) * 2016-08-25 2017-02-01 桂林浩新科技服务有限公司 一种阻燃组合物及其制备方法
CN106398091A (zh) * 2016-08-25 2017-02-15 桂林浩新科技服务有限公司 一种高效耐热阻燃组合物及其制备方法
CN109627671A (zh) * 2018-11-27 2019-04-16 金发科技股份有限公司 一种abs复合材料
CN109627671B (zh) * 2018-11-27 2022-01-14 金发科技股份有限公司 一种abs复合材料
CN110964284A (zh) * 2019-12-12 2020-04-07 武汉金发科技有限公司 一种阻燃hips复合材料

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