WO2006019414A1 - Compositions ignifuges et leur utilisation - Google Patents

Compositions ignifuges et leur utilisation Download PDF

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WO2006019414A1
WO2006019414A1 PCT/US2005/006558 US2005006558W WO2006019414A1 WO 2006019414 A1 WO2006019414 A1 WO 2006019414A1 US 2005006558 W US2005006558 W US 2005006558W WO 2006019414 A1 WO2006019414 A1 WO 2006019414A1
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composition
brominated
range
bromine
per molecule
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PCT/US2005/006558
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English (en)
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Samuel G. Thomas, Jr.
Troy E. Desoto
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Albemarle Corporation
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    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • 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
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

Definitions

  • This invention relates to new, highly effective flame retardant compositions and thermoplastic polymers that are effectively flame retarded by inclusion therein of a flame retardant composition of this invention.
  • the flame retardant additive compositions of this invention are comprised of (a) brominated anionic styrenic polymer, and (b) at least one polybrominated organic flame retardant (i.e., an organic compound, or a mixture of organic compounds, which contains a plurality of bromine atoms per molecule irrespective of how it was prepared) selected from the following:
  • G) (i) at least one ring-brominated bisphenol A having an average of at least about 3 bromine atoms per molecule, or (ii) at least one ring-brominated bisphenol sulfone having an average of at least about 3 bromine atoms per molecule, or (iii) at least one ring-brominated bisphenol A bis(brominated alkylether) having an average of at least about 3 bromine atoms per molecule, or (iv) at least one ring-brominated bisphenol sulfone bis(brominated alkylether) having an average of at least about 3 bromine atoms per molecule, or a mixture of any two or more of (i)-(iv).
  • the styrenic polymer reactant used in the production of the brominated anionic styrenic polymer used as component (a) in the practice of this invention are produced by anionically-initiated polymerization.
  • Such brominated anionic styrenic polymers when used in conjunction with at least one component (b) compound enable the advantageous results of this invention to be achieved.
  • Component (a) of the compositions of this invention ' is at least one brominated anionic styrenic polymer, i. e. , component (a) is (i) at least one anionically-produced styrenic homopolymer that has been brominated or (ii) at least one anionically-produced copolymer of two or more styrenic monomers that has been brominated, or (iii) both of (i) and (ii).
  • the bromine content of such polymer should be at least about 50 percent by weight.
  • Preferred brominated anionic styrenic polymers especially brominated anionic polystyrene, have a bromine content of at least about 60 wt%, and more preferred brominated anionic styrenic polymers, especially brominated anionic polystyrene, have a bromine content of at least about 64 wt%.
  • Particularly preferred brominated anionic styrenic polymers, especially brominated anionic polystyrene have a bromine content in the range of about 67 to about 69 wt%. The bromine content of brominated styrenic polymers such as brominated polystyrene will seldom exceed about 71 wt%.
  • the brominated anionic styrenic polymer will have a melt flow index by the ASTM D 1238-99 test procedure, conducted at 22O 0 C and 2.16 kg, in the range of about 3 to about 40, and preferably such melt flow index is in the range of about 5 to about 35.
  • Most preferred brominated anionic styrenic polymers used in the practice of this invention have a melt flow index under these test conditions in the range of about 6 to about 30.
  • component (a) substances may not "melt" in the sense of reaching a melting point temperature at which they suddenly become transformed from a solid to a liquid.
  • Anionic styrenic polymers which are brominated to form the brominated anionic styrenic polymers used pursuant to this invention are one or more anionic homopolymers and/or anionic copolymers of at least one vinyl aromatic monomer.
  • Examples of such monomers are styrene, ⁇ /p ⁇ -methylstyrene, ort/zo-methylstyrene, /r ⁇ et ⁇ -methylstyrene, p ⁇ r ⁇ -methyl styrene, p ⁇ ra-ethylstyrene, isopropenyltoluene, vinylnaphthalene, isopropenylnaphthalene, vinylbiphenyl, vinylanthracene, the dimethylstyrenes, and tert-butylstyrene.
  • Polystyrene is the preferred reactant.
  • the brominated styrenic polymer is made by bromination of an anionic copolymer of two or more vinyl aromatic monomers
  • styrene be one of the monomers and that styrene comprise at least 50 weight percent and preferably at least about 80 weight percent of the copolymerizable vinyl aromatic monomers.
  • brominated anionic styrenic polymer and “brominated anionic polystyrene” as used herein refer to a brominated anionic polymer produced by bromination of a pre-existing anionic styrenic polymer such as anionic polystyrene or an anionic copolymer of styrene and at least one other vinyl aromatic monomer, as distinguished from an oligomer or polymer produced by oligomerization or polymerization of one or more brominated styrenic monomers, the properties of the latter oligomers or polymers being considerably different from brominated anionic polystyrene in a number of respects.
  • the terms "vinylaromatic” and “styrenic” in connection with monomer(s) or polymer(s) are used interchangeably herein.
  • the aromatic pendant constituents of the anionic styrenic polymer can be alkyl substituted or substituted by bromine or chlorine atoms, but in most cases, will not be so substituted.
  • the anionic styrenic polymers used to produce the brominated anionic styrenic polymers used in the practice of this invention will have a weight average molecular weight (M w ) in the range of about 2000 to about 50,000 and a polydispersity in the range of 1 to about 10.
  • Preferred brominated anionic styrenic polymers used in the practice of this invention are produced from anionic styrenic polymers having a weight average molecular weight (M w ) in the range of about 3000 to about 10,000 and a polydispersity in the range of 1 to about 4, and most preferably these ranges are, respectively, about 3500 to about 4500 and 1 to about 4.
  • M w and polydispersity values are both based on gel permeation chromatography (GPC) techniques which are hereinafter described.
  • GPC gel permeation chromatography
  • brominated anionic styrenic polymers have good, or at least satisfactory, solubility in solvents such as tetrahydrofuran (THF)
  • THF tetrahydrofuran
  • the determination of the total bromine content for a brominated anionic styrenic polymer is easily accomplished by using conventional X-Ray Fluorescence techniques.
  • the sample analyzed is a dilute sample, say O.l ⁇ 0.05 g brominated anionic polystyrene in 60 mL THF.
  • the XRF spectrometer can be a Phillips PW1480 Spectrometer. A standardized solution of bromobenzene in THF is used as the calibration standard.
  • the columns are Waters, ⁇ Styragel, 500A, 10,00OA and 100,000 A.
  • the autosampler is a Shimadzu, Model SiI 9A.
  • the solvent used is tetrahydrofuran, HPLC grade.
  • the test procedure used entails dissolving 0.015-0.020 g of sample in 10 niL of THF. An aliquot of this solution is filtered and 50 ⁇ L is injected on the columns.
  • the separation is analyzed using software provided by Precision Detectors for the PD 2000 Light Scattering Detector.
  • the instrument provides results in terms of weight average molecular weight and also in terms of number average molecular weight. Thus, to obtain a value for polydispersity, the value for weight average molecular weight is divided by the value for number average molecular weight.
  • polybrominated organic flame retardants can be used as component (b). These types are selected from at least one of the following: [0021] Type A) which is (1) at least one polybrominated l,l 5 3-trimethyl-3-phenylindane having three or more bromine atoms per molecule, or (2) at least one polybrominated 1- methyl-3-phenylindane having three or more bromine atoms per molecule, or (3) both of (1) and (2) hereof. These compounds preferably have bromine atoms on one, or more preferably, on both of the aromatic rings. Desirably the compound has 3 to 8 bromine atoms per molecule, and most preferably these are on the aromatic rings.
  • Type B which is at least one polybrominated epoxy oligomer having a bromine content of at least about 30 wt%, and preferably about 45 wt% or more.
  • These flame retardants are brominated bisphenol-A type epoxy resins which have an average degree of polymerization in the range of 0.1 to 100, typically in the range of 0.5 to 100, preferably in the range of 0.5 to 50.
  • Such products include "F-2300”, “F-2300H”, “F-2400”, “F-2400E” and “F-2400H” from The Dead Sea Bromine Group or Bromokem (Far East) Ltd.; “PRATHERM EC-14”, “PRATHERM EP-16”, “PRATHERM EC-20”, “PRATHERM EP-30”, “PRATHERM EC- 30”, “PRATHERM EP-100”, “PRATHERM EP-500”, and “PRATHERM EPC-15F", from
  • Type C which is at least one brominated diphenyl oxide having at least 6 bromine atoms per molecule or if a mixture, an average of at least 6 bromine atoms per molecule.
  • These flame retardants can also be referred to as brominated diphenyl ethers.
  • These compounds comprise one or more of hexabromodiphenyl oxide, heptabromodiphenyl oxide, octabromodiphenyl oxide, nonabromodiphenyl oxide, and decabromodiphenyl oxide, or mixtures containing one or more brominated diphenyl oxides having an average of at least 6 bromine atoms per molecule.
  • Preferred are one or a mixture of brominated diphenyl oxides that has in the range of 8 to 10 bromine atoms per molecule. Most preferred is decabromodiphenyl oxide. Products of this type are available commercially, such as for
  • Type D which is at least one brominated phenoxytriazine having two or preferably three brominated phenoxy groups bonded to a triazine ring, with the total number of bromine atoms on the two or three phenoxy groups being at least 6, or if a mixture of brominated phenoxytriazine compounds, an average of at least 6, bromine atoms per molecule.
  • Preferred compounds of this type are one or more 2,4,6-tri(bromophenoxy)-l,3,5-triazines having at least 6 bromine atoms per molecule or if a mixture, an average of at least 6 bromine atoms per molecule. Most preferred is 2,4,6-tris(tribromophenoxy)-l,3,5-triazine. This product is available commercially from The Dead Sea Bromine Group as FR-245 and from Daiichi
  • Type E which is at least one brominated diphenoxybenzene having at least 9 bromine atoms per molecule or if a mixture, an average of at least 9 bromine atoms per molecule.
  • a preferred flame retardant of this type is tetradecabromodiphenoxybenzene.
  • Type F which is at least one ring-brominated alkylenebisphthalimide having at least 6 and preferably 8 bromine atoms per molecule or if a mixture, an average of at least 6 and more preferably at least 7 bromine atoms per molecule.
  • the alkylene group is an ethylene group (-CH 2 CH 2 -), but can be a straight or branched chain alkylene group containing up to about 6 carbon atoms.
  • a preferred flame retardant of this type is ethylenebistetrabromophthalimide. Such compound is available commercially from
  • Type G which is (i) at least one ring-brominated bisphenol A having an average of at least about 3 bromine atoms per molecule, or (ii) at least one ring-brominated bisphenol sulfone having an average of at least about 3 bromine atoms per molecule, or (iii) at least one ring-brominated bisphenol A bis(brominated alkylether) having an average of at least about
  • These compounds comprise one or more of tribromobisphenol A, tetrabromobisphenol A, pentabromobisphenol A, hexabromobisphenol A, octabromobisphenol A, tetrabromobisphenol A bis(2-bromoethylether), tetrabromobisphenol A bis(l ,2-dibromoethylether), tetrabromobisphenol A bis(propylether), tetrabromobisphenol A bis(3-bromopropylether), tetrabromobisphenol A bis(2,3- dibromopropylether), tribromobisphenol sulfone, tetrabromobisphenol sulfone, pentabromobisphenol sulfone, hexabromobisphenol sulfone, octabromobisphenol sulfone, tetrabromobisphenol sulfone bis(2-brom
  • these compounds have at least about four bromine atoms per molecule.
  • Preferred flame retardants of this type include tetrabromobisphenol A and tetrabromobisphenol sulfone-bis-(dibromopropylether).
  • Commercially available compounds of this type include "Saytex® CP-2000" and “Saytex® HP-800 AG” from Albemarle Corporation, “Non-Nen 52" from Nyacol Nano Technologies, Inc., “FR-1524", from Bromokem (Far East) Ltd., and "Great Lakes BA-59P” from Great Lakes Chemical Corporation.
  • the proportions between components (a) and (b) can be varied and in all cases effective flame retardancy will be obtained with any and all proportions thereof as long as the total amount of these two components present in the substrate or host polymer is a flame retardant amount as described below.
  • the proportions as between components (a) and (b) can thus vary, for example from an (a)/(b) weight ratio of about 2/98 up to an (a)/(b) weight ratio of about 98/2 depending on whether the mixture is a powder blend, or in the form of aggregates or pellets, and also whether a supplemental binder is employed to form aggregates or pellets. Considering such factors as cost and effectiveness, the following guidelines may be used:
  • component (b) when component (b) is Type A), i.e., (1) at least one polybrominated 1,1,3- trimethyl-3-phenylindane having three or more bromine atoms per molecule, or (2) at least one polybrominated l-methyl-3-phenylindane having three or more bromine atoms per molecule, or (3) both of (1) and (2) hereof, the (a)/(b) weight ratio will typically be in the range of about 15/85 to about 95/5, preferably in the range of about 15/85 to about 50/50, and most preferably in the range of about 40/60 to about 50/50;
  • component (b) when component (b) is Type B), i.e., at least one polybrominated epoxy oligomer having a bromine content of at least about 30 wt%, the (a)/(b) weight ratio will typically be in the range of about 5/95 to about 95/5, preferably in the range of about 25/75 to about 50/50, and most preferably in the range of about 40/60 to about 50/50;
  • component (b) when component (b) is Type C), i.e., at least one brominated diphenyloxide having at least 6 bromine atoms per molecule or if a mixture, an average of at least 6 bromine atoms per molecule, the (a)/(b) weight ratio will typically be in the range of about 25/75 to about 95/5, preferably in the range 30/70 to about 75/25, more preferably in the range of about 40/60 to about 60/40, and most preferably in the range of about 40/60 to about 50/50;
  • component (b) when component (b) is Type D) i.e., at least one brominated phenoxytriazine having two or preferably three brominated phenoxy groups bonded to a triazine ring, with the total number of bromine atoms on the two or three phenoxy groups being at least 6, or if a mixture of brominated phenoxytriazine compounds, an average of at least 6, bromine atoms per molecule, the (a)/(b) weight ratio will typically be in the range of about 15/85 to about 95/5, preferably in the range of about 15/85 to about 50/50, and most preferably in the range of about 20/80 to about 30/70; [0034] E) when component (b) is Type E), i.e., at least one brominated diphenoxybenzene having at least 9 bromine atoms per molecule or if a mixture, an average of at least 9 bromine atoms per molecule, the (a)/(b) weight ratio will typically
  • component (b) when component (b) is Type G), i.e., (i) at least one ring-brominated bisphenol A, or (ii) at least one ring-brominated bisphenol sulfone, or (iii) at least one ring-brominated bisphenol A bis(brominated alkylether), or (iv) at least one ring-brominated bisphenol sulfone bis(brominated alkylether), or a mixture of any two or more of (i)-(iv), the (a)/(b) weight ratio will typically be in the range of about 25/75 to about 95/5, preferably in the range of about 30/70 to about 75/25, more preferably in the range of about 40/60 to about 60/40, and most preferably in the range of about 40/60 to about 50/50.
  • Other embodiments of this invention are flame retardant polymer compositions comprising a polymer comprised of one or more polymerized monomers having a polymerizable olefmic double bond in the molecule with which has been blended a flame retardant quantity of a flame retardant additive composition of the above components (a) and (b).
  • polymers There are three groups of such polymers, namely (i) one or more vinylaromatic homopolymers or copolymers, preferably high-impact polystyrene, (ii) one or more acyclic olefinic hydrocarbon homopolymers or copolymers, such as polyethylene, polypropylene, and copolymers of ethylene or propylene with at least one higher olefin and with or without a diene monomer, and (iii) one or more copolymers of at least one vinylaromatic monomer and at least one non- vinylaromatic monomer containing a functional group, such as acrylonitrile, an acrylate monomer, or a methacrylate monomer with or without a diene monomer.
  • a functional group such as acrylonitrile, an acrylate monomer, or a methacrylate monomer with or without a diene monomer.
  • group (iii) examples include ABS, MBS, SAN, and ASA.
  • components (a) and (b) can be blended with the polymer individually and/or in any sub- combination ⁇ ) or partial blend(s) of components (a) and (b) and any other selected optional additives.
  • a preformed blend comprised of components (a) and (b) in which the components are already in suitable proportions.
  • Vinylaromatic polymers that can be flame retarded in the practice of this invention can be homopolymers, copolymers or block polymers and such polymers can be formed from such vinylaromatic monomers as styrene, ring-substituted s ⁇ yrenes in which the substituents are one or more C 1-6 alkyl groups, alpha-methylstyrene, ring-substituted alpha-methylstyrenes in which the substituents are one or more C 1-6 alkyl groups, vinylnaphthalene, and similar polymerizable styrenic monomers ⁇ /. e.
  • styrenic compounds capable of being polymerized, e.g., by means of peroxide or like catalysts, into thermoplastic resins.
  • Homopolymers and copolymers of simple styrenic monomers e.g. , styrene, p-methyl-styrene, 2,4-dimethylstyrene, alpha-methyl-styrene, p-chloro-styrene, etc. are preferred from the standpoints of cost and availability.
  • the vinylaromatic polymers that are flame retarded pursuant to this invention can be homopolymers or copolymers can be produced by free-radical polymerization, cationically-initiated polymerization, or anionically-initiated polymerization.
  • the vinylaromatic polymers that are flame retarded in the practice of this invention can be foamable, expanded, or foamed vinylaromatic polymer compositions.
  • the vinylaromatic polymers can have various structural configurations. For example they can be isotactic polymers, syndiotactic polymers, or mixtures of isotactic and syndiotactic polymers.
  • the vinylaromatic polymers can be in the form of blends or alloys with other thermoplastic polymers, such as polyphenylene ether-styrenic polymer blends and polycarbonate-styrenic polymer blends.
  • the vinylaromatic polymers can be impact-modified or rubber-modified polymers.
  • Impact-modified polystyrenes (IPS) that are preferably used may be medium-impact polystyrene (MIPS), high-impact polystyrene (HIPS), or blends of HIPS and GPPS (sometimes referred to as crystal polystyrene). These are all conventional materials.
  • MIPS medium-impact polystyrene
  • HIPS high-impact polystyrene
  • GPPS sometimes referred to as crystal polystyrene
  • High-impact polystyrene or blends containing a major amount (greater than 50 wt%) of high-impact polystyrene together with a minor amount (less than 50 wt%) of crystal polystyrene are particularly preferred as the substrate or host polymer.
  • suitable vinyl aromatic monomers used in forming the vinylaromatic polymers are those which have the formula:
  • H 2 C CR-Ar wherein R is a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms and Ar is an aromatic group (including alkyl-ring substituted aromatic groups) of from 6 to 10 carbon atoms.
  • R is a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms and Ar is an aromatic group (including alkyl-ring substituted aromatic groups) of from 6 to 10 carbon atoms.
  • monomers are styrene, ⁇ /p/z ⁇ -methylstyrene, ⁇ rt/zo-methylstyrene, r ⁇ ef ⁇ -methylstyrene, p ⁇ r ⁇ -methylstyrene, p ⁇ z' ⁇ -ethylstyrene, isopropenyltoluene, vinylnaphthalene, isopropenylnaphthalene, vinylbiphenyl, vinylanthracene, the dimethylstyrenes, and ter
  • Polystyrene is the preferred reactant.
  • the weight average molecular weights of the vinylaromatic polymers that are flame retarded pursuant to this invention can vary widely, from low molecular weight polymers to very high molecular weight polymers.
  • Methods for producing styrenic polymers such as general purpose polystyrenes, impact-modified polystyrenes, foamed or expandable polystyrenes, syndiotactic polystyrenes, and blends or alloys of styrenic polymers with other thermoplastic polymers are reported in the literature. See for example Encyclopedia of Polymer Science and Technology, copyright 1970 by John Wiley & Sons, Inc., Volume 13, especially the section entitled Styrene
  • Preferred high-impact polystyrene compositions of this invention have the capability of forming molded specimens of 1.6 and 3.2 millimeter thickness (1/16 and 1/8-inch thickness) that pass at least the UL 94 V2 test.
  • Another group of thermoplastic polymers which may be effectively flame retarded by inclusion of components (a) and (b) with or without conjoint use of other suitable additives pursuant to this invention is polyolefins.
  • Non-limiting examples of suitable polyolefins include polyethylene; polypropylene; poly-(l-butene); copolymers of ethylene with one or more higher vinyl olefins such as propylene, 1-butene, 1-pentene, 3-methyl-l-butene, 1- hexene, 4-methyl- 1 -pentene, 1 -heptene, 1 -octene; copolymers of propylene with one or more higher vinyl olefins; copolymers of ethylene, propylene and one or more diene monomers; and blends or mixtures of any of the foregoing.
  • Methods for preparing such polymers are known and reported in the literature. See for example, Encyclopedia of Polymer Science and Technology, Interscience Publishers, a division of John Wiley & Sons, Inc. New York, especially sections entitled Ethylene Polymers; Propylene Polymers; Butylene Polymers; and
  • the flame retardant combinations of components (a) and (b) with or without conj oint use of other suitable additives pursuant to this invention may also be used for imparting flame retardancyto such polymers or resins as ABS (acrylonitrile-butadiene-styrene polymer), SAN (styrene-acrylonitrile polymer), ASA (acrylonitrile-styrene-butyl acrylate copolymer), MBS (methacrylonitrile-butadiene-styrene polymer), and similar polymers, resins, and polyblends. Of these polymers ABS is preferred. Methods for the production of polymeric substances of this type are reported in the literature.
  • One method for forming a molded article or shape comprises molding or extruding a flame retardant polymer composition of this invention at one or more temperatures at which the thermoplastic polymer is melted or at least softened sufficiently to enable the molding or extrusion to take place, ..
  • Yet another aspect, of this invention is . a . method of producing a flame-retarded vinylaromatic polymer article which comprises molding or extruding at a temperature of up to 250 0 C, a melt blend of a vinylaromatic composition of this invention.
  • components (a) and (b) can be used in conjunction with components (a) and (b), provided no such other component materially detracts from the performance of the overall flame retardant composition.
  • These other components may be included in the flame retardant additive compositions of this invention or in the flame retardant polymer compositions of this invention, or both.
  • One optional type of additive which can be used, and preferably is used, are flame retardant aids or synergists, especially one or more antimony oxides such as antimony pentoxide, and most especially antimony trioxide.
  • Alkali metal antimonates such as sodium antimonate can also be used either together with or in place of an antimony oxide. Amounts of one or more antimony oxides and/or one or more alkali antimonates used can vary, but typically such synergists will be used in amounts such that the brominated flame retardant(s): antimony synergist(s) weight ratio is in the range of about 0.5:1 to about 10:1.
  • this weight ratio will be in the range of about 2 : 1 to about 5:1, and most preferably is about 3:1.
  • other flame retardant aids or synergists include one or more zinc borates (including mixed oxides of boron and zinc), calcium borate (including mixed oxides of boron and calcium), barium sulfate, zinc stannate and similar known flame retardant aids or synergists. These materials can be used in the same proportions as those given above.
  • these synergists will be used in amounts such that the brominated flame retardant(s):synergist(s) weight rut 0.5 : 1 to about 10:1.
  • this weight ratio will be in the range of about 2:1 to about 5:1, and most preferably is about 3:1.
  • Antioxidants that can be used include phenolic antioxidants, many of which are available as articles of commerce, and organic phosphite esters, a number of which are also commercially available.
  • flame halogen-containing and/or phosphorus-containing flame retardants it is also possible to use other flame halogen-containing and/or phosphorus-containing flame retardants as long as the flame retardancy effectiveness and desirable performance characteristics provided by use of the combination of components (a) and (b) is not materially harmed. If another flame retardant is used and it contains bromine, the amount of bromine provided thereby should be taken into consideration in connection with the total amount of bromine provided to the substrate polymer as discussed below. While the amount of any such other flame retardant, whether halogen-containing or phosphorus-containing, if used, can vary, it is preferable that at least about 50 wt% and more preferably at least 75 wt% of the total bromine from flame retardant additives in the substrate polymer be provided by components (a) and (b).
  • the most preferred flame retardant additive compositions and the most preferred flame retardant polymer compositions of this invention are devoid of any other halogen-containing flame retardant additive and any phosphorus-containing flame.retardant.
  • additives such as other metal deactivators, UV stabilizers, pigments and dyes, processing aids, fillers, acid scavengers, thermal stabilizers, blowing agents, lubricants, nucleating agents, anti-static agents, plasticizers, impact modifiers, and related materials, can be included in the compositions of this invention as is appropriate.
  • the amounts of these additives used, if used, will typically be as recommended by the manufacturer for obtaining the particular property enhancement for which the additive is employed.
  • components (a) and (b) are blended with the substrate polymer, separately or preferably in combination, in a flame retardant amount, i. e. , in an amount which yields a composition that satisfies at least the minimum requirements for the test procedure(s) applicable to the particular end use to which the polymer composition is intended to be put.
  • the flame retardant polymer compositions of this invention should provide test specimens that at least pass the V2 UL 94 test procedure.
  • the finished blend of polymer and flame retardant components (a) and (b) proportioned relative to each other as described above should provide a total bromine content in the range of about
  • amounts of total bromine in the range of about 10 to about 30 wt% of bromine are desirable with amounts in the range of about 15 to about 25 wt% being especially desirable.
  • styrenic copolymers with functionalized monomers and with or without diene ABS, SAN, MBS, ASA, etc.
  • amounts of total bromine in the range of about 9 to about 15 wt% of bromine are desirable with amounts in the range of about 10 to about 13 wt% being especially desirable.
  • the flame retardant additive compositions of this invention can be formed as powder blends comprised of components (a) and (b) and other selected optional components. Because component (a) is itself a polymeric material, blends of components (a) and (b) can be formed by intimately mixing component (b) and if desired, other selected components, with heat- softened component (a). During at least a portion of the blending, the blend of (a) and (b) can be exposed to a temperature at which (a) is melted or at least softened sufficiently to facilitate the blending.
  • One way of preparing flame retardant polymer compositions of this invention is to form a blend or masterbatch of components (a) and (b) in a substrate or host polymer such as polystyrene, polyethylene, polypropylene, or the like, where the components (a) and (b) are suitably proportioned relative to each other but are in a higher concentration than the flame retardant level to be used in the finished flame retardant polymer.
  • the masterbatch can then be blended with additional thermoplastic polymer to form a less concentrated blend and/or the finished flame retardant polymer.
  • the flame retardant additive composition comprised of components (a) and (b), with or without one or more other optional components, thereby providing the additive in a dust-free, readily- handleable form.
  • the flame retardant additive composition comprised of components (a) and (b), with or without one or more other optional components, thereby providing the additive in a dust-free, readily- handleable form.
  • use can be made of commercially-available pellet mills and associated apparatus which will extrude molten strands of a flame retardant polymer composition of this invention and cut the strands into pellets.
  • the flame retardant polymer compositions of this invention can be prepared by use of conventional blending equipment such as a twin-screw extruder, a Brabender mixer, or similar apparatus. As noted above, it is possible to add the several components of the flame retardant compositions of this invention to the base polymer individually or in any combinations. Preferably, however, a preformed additive composition or a masterbatch of this invention is blended with the base thermoplastic resin.
  • thermoplastic polymer blends of this invention in producing finished articles therefrom.
  • the articles so formed should not show significant color and viscosity degradation often experienced when using such techniques on GPPS or
  • IPS which has been flame retarded with a brominated cycloaliphatic flame retardant.
  • thermal degradation of polyolefins such as polypropylene should be reduced, if not eliminated, when maintaining the flame retarded polyolefm composition of this invention at elevated temperatures during processing.
  • a flame retardant combination of this invention can be included before, during, and in some cases after, the foamed or expandable product has been formed.
  • a flame retardant extruded styrenic polymer such as XPS
  • at least (i) a vinylaromatic polymer, (ii) a preformed flame retardant additive composition of this invention or at least separate amounts of components (a) and (b) suitably proportioned relative to each other plus any other optional components all pursuant to this invention, and (iii) a blowing agent are mixed in an extruder, and the resultant mixture is extruded through a die providing the desired dimensions of the product, such as boards with various thicknesses and widths.
  • Another method for forming a foamed article or shape involves heating a composition comprised of (i) a flame retardant polymer composition of this invention and (ii) at least one foaming agent, at one or more temperatures at which the thermoplastic polymer is melted or at least softened sufficiently to enable the foaming to take place.
  • a typical method of producing flame retardant expandable styrenic polymers of this invention involves suspension polymerization in water of a mixture of at least (i) styrene monomer(s) and (ii) a preformed flame retardant additive composition of this invention or at least separate amounts of components (a) and (b) suitably proportioned relative to each other plus any other optional components all pursuant to this invention, to thereby form beads of styrenic polymer.
  • the small beads e.g. , about 1 mm in diameter
  • so formed are then pre-expanded with steam and then molded again with steam to produce large blocks which can be several meters high, and 2-3 meters wide, that will be cut in the desired dimensions.
  • the flame retardant polymer composition has high-impact polystyrene as the substrate polymer, and component (b) is a brominated trimethylphenylindane, tris(tribromophenoxy)triazine, ethylene-bis-tetrabromophthalimide, or at least one bisphenol-A type polybrominated epoxy oligomer having a bromine content of at least about 45 wt%.
  • More preferred flame retardant polymer compositions with high- impact polystyrene have ethylene-bis-tetrabromophthalimide, or at least one bisphenol-A type polybrominated epoxy oligomer having a bromine content of at least about 45 wt% as component (b); particularly preferred as component (b) with high-impact polystyrene is ethylene-bis-tetrabromophthalimide.
  • component (b) is tetrabromobisphenol A- bis(dibromopropylether) .
  • Preferred embodiments of the invention in which the substrate polymer in the flame retardant polymer composition is polypropylene have as component (b) decabromodiphenyl oxide, ethylene-bis-tetrabromophthalimide, tetrabromobisphenol A, or tetrabromobisphenol sulfone-bis(dibromopropylether). More preferably, component (b) is decabromodiphenyl oxide or ethylene-bis-tetrabromophthalimide when polypropylene is the substrate polymer.
  • component (b) is decabromodiphenyl oxide, ethylene- bis-tetrabromophthalimide, or at least one bisphenol-A type polybrominated epoxy oligomer having a bromine content of at least about 45 wt%.
  • Ethylene-bis-tetrabromophthalimide is especially preferred as component (b) in flame retardant polymer compositions of the invention where the substrate polymer is a copolymer of at least one vinylaromatic monomer and at least one methacrylate monomer.
  • Ethanox 310 penterythritol tetrakis(3 -(3,5 -di-t-butyl-4-hydroxyphenyl)propionate), and
  • EthaphosTM 368 tris-(2,4-di-t-butylphenyl)phosphite.
  • EC- 14 brominated aromatic epoxy oligomer (both ends capped with a brominated phenyl group), 59% bromine, polydispersity 1.14, Dainippon Ink & Chemical),
  • EP- 16 brominated aromatic epoxy oligomer (not end-capped), 51% bromine, average molecular weight 1600, polydispersity 2.18, Dainippon Ink & Chemical), FR-245 (tris(tribromophenoxy)triazine, 67% bromine, Dead Sea Bromine Group), FRl 808 (brominated trimethylphenylindane, 73% bromine, Dead Sea Bromine Group), Non-Nen 52 (tetrabromobisphenol sulfone-bis(2,3-dibromopropyl ether); Nyacol Nano
  • White Star N antimony trioxide, Campine N. V., Beerse, Belgium
  • TiO 2 masterbatch of 25% TiO 2 (TiPure Rl 03, DuPont) in substrate polymer, used as white pigment
  • Yellow masterbatch of 1% iron oxide (Akrochem E6980, Akrochem Corporation) in substrate polymer, used as yellow pigment
  • Tinuvin 622 poly(4-hydroxy-2,2,6,6-tetramethyl- 1 -piperidine ethanol- ⁇ /t- 1 ,4-butanedioic acid), Ciba Specialty Chemicals
  • Tinuvin 328 (2-(2'-Hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, Ciba Specialty
  • Example 1 flame retardant polymer compositions of this invention, where the polymer was ABS (Magnum PG-914, Dow Chemical Company) were formed, and various properties of these compositions were tested. In forming these compositions, the powders and ABS pellets were hand-mixed in a plastic bag prior to extrusion. The white, yellow, and black pigments used in the runs of this Example were prepared with ABS as the substrate polymer. The ABS and other components of the flame retardant polymer compositions were dried at
  • Example 1 AU of the formulations in Example 1 were prepared on a Werner & Pfleiderer ZSK 30mm, 32/1 length to diameter twin-screw extruder. Extrusion was carried out at lOkg/hr feed rate, 22O 0 C barrel temperatures, 150rpm screw speed. Injection molding was performed on a 38-ton reciprocating screw injection molding machine (Battenfeld) at 200-220 0 C.
  • Example 2 flame retardant polymer compositions of this invention, where the polymer was HIPS (StyronTM 801, Dow Chemical Company) were formed, and various properties of these compositions were tested.
  • HIPS StyronTM 801, Dow Chemical Company
  • the powders and HIPS pellets were hand-mixed in a plastic bag prior to extrusion.
  • the white, yellow, and black pigments used in the runs of this Example were prepared with HIPS as the substrate polymer.
  • the HIPS and other composition components were dried at 90°C for 2 hours prior to extrusion and molding. All of the compositions in Example 2 were prepared on a Werner &Pfleiderer ZSK 30mm, 32/1 length to diameter twin-screw extruder.
  • Extrusion was carried out at lOkg/hr feed rate, 200-210°C barrel temperatures, 150 rpm screw speed. Injection molding was performed on a 38-ton reciprocating screw injection molding machine (Battenfeld) at 190-210 0 C.
  • Run 7 shows an unexpectedly high volume resistivity, and such a flame retardant polymer composition of this invention would be useful in an application where volume resistivity is important.
  • Example 3 flame retardant polymer compositions of this invention, where the polymer was polypropylene (Moplen EP 440N, Basell) were formed, and various properties of these compositions were tested.
  • the powders and polypropylene pellets were hand-mixed prior to extrusion.
  • the polypropylene and other components of the flame retardant polymer compositions were dried at 90°C for 2 hours prior to extrusion and molding.
  • AU of the compositions in Example 3 were prepared on a Werner & Pfieiderer ZSK 25mm, twin-screw extruder. Extrusion was carried out at 1 Okg/hr feed rate, 200-210°C barrel temperatures, 150 rpm screw speed.
  • Injection molding was performed on a 38-ton reciprocating screw injection molding machine (Battenfeld) at 190-210 0 C.
  • the following ASTM test procedures were performed on the samples: Tensile Strength (D638) specimen type 1 ; Tensile Modulus (D638); Elongation at yield (D638); Elongation at break (D638); Notched IZOD Impact Strength (D256) method A; Melt Flow Index (D1238) procedure A, 230°C/2.16 kg; and the UL-94 flammability test.
  • Table 6 lists the amounts of the components in the compositions that were tested; amounts listed therein are in weight percent.
  • Table 7 lists various properties of the tested compositions.
  • compositions of Runs 3 and 4 (component (b) in Run 3 was tetrabromobisphenol sulfone-bis-(dibromopropylether); component (b) in Run 4 was tetrabromobisphenol A) are thus useful in applications where any one or a combination of these properties is particularly desirable.
  • Example 4 a flame retardant polymer composition of this invention, where the polymer was polyethylene (PE Lupolen 2426, Basell) was formed, and various properties of this composition were tested.
  • the powders and polyethylene pellets were hand-mixed prior to extrusion.
  • the polyethylene and other components of the flame retardant polymer composition were dried at 90°C for 2 hours prior to extrusion and molding.
  • the composition was prepared on a Werner & Pfleiderer ZSK 25mm, twin-screw extruder. Extrusion was carried out at 1 Okg/hr feed rate, 200-210°C barrel temperatures, 150 rpm screw speed.
  • Inj ection molding was performed on a 38 -ton reciprocating screw inj ection molding machine (Battenfeld) at 190-210°C.
  • the following ASTM test procedures were performed on the sample: Tensile Strength (D638) specimen type 1 ; Tensile Modulus (D638); Elongation at yield (D638); Elongation at break (D638); Notched IZOD Impact Strength
  • Table 8 lists he amounts of the components in the composition that was tested; amounts listed therein are in weight percent. Table 9 lists various properties of the tested composition.

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Abstract

La présente invention a trait à une composition additive ignifuge comportant un mélange de (a) du polymère styrénique anionique bromé, et (b) au moins un ignifuge organique polybromé. L'ignifuge organique polybromé (b) est choisi parmi le groupe constitué de: A) (1) au moins un 1,1,3-triméthyl-3-phénylindane polybromé ayant au moins trois atomes de brome par molécule, ou (2) au moins un 1-triméthyl-3-phénylindane polybromé ayant au moins trois atomes de brome par molécule, ou (3) (1) et (2) à la fois; B) au moins un oligomère époxyde polybromé ayant une teneur en brome d'au moins 30 % en poids; C) au moins un diphényloxyde bromé ayant au moins 6 atomes de brome par molécule, ou dans le cas d'un mélange, une moyenne d'au moins 6 atomes de brome par molécule; D) au moins une phénoxytriazine bromée ayant deux ou trois groupes phénoxy liés à un noyau triazine, le total d'atomes de brome sur les deux ou trois groupes phénoxy étant au moins au nombre de 6, ou dans le cas d'un mélange de composés de phénoxytriazine bromés, une moyenne d'au moins 6 atomes de brome par molécule; E) au moins un diphénoxybenzène bromé ayant au moins 9 atomes de brome par molécule, et dans le cas d'un mélange, une moyenne d'au moins 9 atomes de brome par molécule; F) au moins un alkylènebisphtalimide à noyau bromé ayant au moins 6 atomes de brome par molécule ou, dans le cas d'un mélange, une moyenne d'au moins 6 atomes de brome par molécule; et G) (i) au moins un bisphénol A à noyau bromé ayant une moyenne d'au moins 3 atomes de brome par molécule, ou (ii) au moins un bisphénol sulfone ayant une moyenne d'au moins 3 atomes de brome par molécule, ou (iii) au moins un bisphénol A bis(alkyléther bromé) ayant une moyenne d'au moins 3 atomes de brome par molécule, ou (iv) au moins un bisphénol sulfone bis(alkyléther bromé) à noyau bromé ayant une moyenne d'au moins 3 atomes de brome par molécule, ou un mélange d'au moins deux quelconque de (i) à (iv).
PCT/US2005/006558 2004-03-01 2005-03-01 Compositions ignifuges et leur utilisation WO2006019414A1 (fr)

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US8067088B2 (en) 2004-05-20 2011-11-29 Albemarle Corporation Pelletized brominated anionic styrenic polymers and their preparation and use
US8071688B2 (en) 2005-12-21 2011-12-06 Albemarle Corporation Brominated anionic styrenic polymers and their preparation
US8168723B2 (en) 2005-06-30 2012-05-01 Albemarle Corporation Brominated styrenic polymers and their preparation
WO2012116314A1 (fr) 2011-02-25 2012-08-30 Donaldson Company, Inc. Cartouches de filtre à air et ses composants, et ensembles épurateurs d'air
US8273831B2 (en) 2006-07-20 2012-09-25 Albemarle Corporation Process technology for recovering brominated styrenic polymers from reaction mixtures in which they are formed and/or converting such mixtures into pellets or into granules or pastilles
CN108164916A (zh) * 2017-12-28 2018-06-15 合肥永健工贸有限公司 一种abs黑色阻燃改性料
CN109265906A (zh) * 2018-09-14 2019-01-25 蚌埠星烁新材料科技有限公司 一种耐温、抗紫外的abs塑料色母粒的制备方法
WO2022015523A1 (fr) * 2020-07-13 2022-01-20 Dow Global Technologies Llc Procédés de mélange à l'état fondu de compositions ignifuges et polymères
WO2022031932A1 (fr) * 2020-08-07 2022-02-10 Albemarle Corporation Additifs pour polyoléfines ignifugées

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8067088B2 (en) 2004-05-20 2011-11-29 Albemarle Corporation Pelletized brominated anionic styrenic polymers and their preparation and use
US8168723B2 (en) 2005-06-30 2012-05-01 Albemarle Corporation Brominated styrenic polymers and their preparation
US8071688B2 (en) 2005-12-21 2011-12-06 Albemarle Corporation Brominated anionic styrenic polymers and their preparation
US8273831B2 (en) 2006-07-20 2012-09-25 Albemarle Corporation Process technology for recovering brominated styrenic polymers from reaction mixtures in which they are formed and/or converting such mixtures into pellets or into granules or pastilles
US8450429B2 (en) 2006-07-20 2013-05-28 Ablemarle Corporation Process technology for recovering brominated styrenic polymers from reaction mixtures in which they are formed and/or converting such mixtures into pellets or into granules or pastilles
WO2012116314A1 (fr) 2011-02-25 2012-08-30 Donaldson Company, Inc. Cartouches de filtre à air et ses composants, et ensembles épurateurs d'air
CN108164916A (zh) * 2017-12-28 2018-06-15 合肥永健工贸有限公司 一种abs黑色阻燃改性料
CN109265906A (zh) * 2018-09-14 2019-01-25 蚌埠星烁新材料科技有限公司 一种耐温、抗紫外的abs塑料色母粒的制备方法
WO2022015523A1 (fr) * 2020-07-13 2022-01-20 Dow Global Technologies Llc Procédés de mélange à l'état fondu de compositions ignifuges et polymères
WO2022031932A1 (fr) * 2020-08-07 2022-02-10 Albemarle Corporation Additifs pour polyoléfines ignifugées

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