WO2001007511A2 - Compositions ignifuges stables exemptes d'efflorescences et procede permettant d'ignifuger des polyolefines - Google Patents

Compositions ignifuges stables exemptes d'efflorescences et procede permettant d'ignifuger des polyolefines Download PDF

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WO2001007511A2
WO2001007511A2 PCT/US2000/019140 US0019140W WO0107511A2 WO 2001007511 A2 WO2001007511 A2 WO 2001007511A2 US 0019140 W US0019140 W US 0019140W WO 0107511 A2 WO0107511 A2 WO 0107511A2
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flame retardant
composition
retardant compound
weight
polymer
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PCT/US2000/019140
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WO2001007511A3 (fr
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Louella Jane Likens
Nicolai A. Favstritsky
Olga I. Kuvshinnikova
David Asher Lee
Robert E. Lee
William Ray Fielding
Gurudas Zingde
Ray William Atwell
Jeffrey Scott Stults
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Great Lakes Chemical Corporation
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Priority to AU13247/01A priority Critical patent/AU1324701A/en
Publication of WO2001007511A2 publication Critical patent/WO2001007511A2/fr
Publication of WO2001007511A3 publication Critical patent/WO2001007511A3/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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the present invention is directed to stabilized flame retardant compositions for polymers, preferably polyolefms, and methods of flame retarding polymers, particularly aliphatic polyolefms, by adding thereto a combination of flame retardant compounds (a) and (b) wherein (a) is an aromatic oligomeric compound, preferably having a weight average molecular weight of at least 2,000 and including aromatic bromine, (b) is a monomer ic or dimeric aromatic compound, preferably having a molecular weight less than 2,000 and including aliphatic bromine, wherein the weight ratio of (a):(b) is in the range of about 1 : 10 to 10: 1, preferably at least 1 : 1, more preferably at least 1.1:1, most preferably at least 1.3: 1.
  • the composition also contains (c) an antioxidant process stabilizer; and (d) a UV degradation retardant selected from the group consisting of an ultraviolet (UV) stabilizer; a UV absorber; a UV screener; and a combination of any two or more of said UV degradation retarders.
  • UV ultraviolet
  • This combination of flame retardants, antioxidant process stabilizer and UV degradation retardant(s) shows low surface migration (bloom) characteristics in polymers, particularly aliphatic (non-aromatic) polyolefms; and good retention of physical properties and/or color in polyolefm fibers and films, particularly for polyethylene, polypropylene and copolymers thereof.
  • halogen-containing compounds together with antimony oxide, are frequently utilized with polymers, to impart flame retardant properties to the polymers.
  • Commercially available halogenated flame - retardants that have a high melting point tend to contain large amounts of aromatic halogens or are polymeric. These molecules tend to be inefficient flame retardants for polyolefms.
  • Lower molecular weight halogen compounds that are efficient flame retardants and that contain aliphatic bromine tend to undergo surface migration in polyolefms. This leads to marring of the surface appearance of the polyolefm.
  • antioxidant process stabilizers during the manufacture of polyolefms to prevent oxidation of olefins during the polymerization reaction, and to add one or more antioxidants to a polyolefm during processing, e.g., during fiber formation, to prevent oxidation of the polyolefm.
  • halogenated flame retardants also are generally reactive with UV light in polyolefms, e.g., polypropylene, causing degradation of the polyolefm, as demonstrated by decreasing tensile strength of the polyolefm-containing polymer composition.
  • the addition of one or more UV degradation retardants decreases the degradation rate.
  • GPP-39 ® a trademark of Great Lakes Chemical Corporation, is a graft copolymer of polypropylene with brominated polystyrene. It was developed as a flame retardant for polypropylene fiber. Attempts to UV stabilize the GPP-39 in polypropylene gave results similar to unstabilized polypropylene - the polypropylene degradation rate was still too high for use of the GPP-39 flame retardant in polypropylene fiber applications.
  • This invention accordingly, is directed to improvements in stabilized flame retarded polymer compositions, and in particular polyolefm compositions, more particularly, toward flame retarded and UV stabilized polyolefm fiber compositions, where there is a tendency for the flame retardant to bloom and a great tendency to degrade under exposure to UV light, and is directed towards inhibiting this bloom and degradation.
  • U.S. Patent No. 3,730,929 teaches that the use of a fatty acid or a metal salt of a fatty acid minimizes the tendency toward exudation. Dispersants have been disclosed to reduce blooming in U.S. Patent No. 4,006, 118.
  • U.S. Patent No. 4,699,734 discloses that an epoxy resin, e.g. , Epon 1031 , an epoxy having an epoxy equivalent of about 220, an elastomer ic resin, e.g. , a styrene-butadiene-styrene block copolymer, and a nucleating agent, such as a fire -dried fumed silica gel, are needed to minimize surface migration of the flame retardant in polypropylene. When any one or more of the ingredients were omitted, then the surface appearance was poor to fair after aging.
  • an epoxy resin e.g. , Epon 1031
  • an epoxy having an epoxy equivalent of about 220 an elastomer ic resin, e.g. , a styrene-butadiene-styrene block copolymer
  • a nucleating agent such as a fire -dried fumed silica gel
  • WO 98/17718 discloses the use of aliphatic-containing bromine molecules as synergists for tris(tribromoneopentyl) phosphate in polyolefm resins. Tris(tribromoneopentyl) phosphate may act as a bloom suppressant for PE-68 and Nonen-52.
  • U.S. Patent No. 5,559, 172 discloses the use of an oligomer based on tetrabromobisphenol A, ethylene dibromide, and end-capped with methyl bromide as a flame retardant for vinyl aromatic resins, such as ABS and HIPS, and blends with polycarbonate and polyphenylene oxide.
  • U.S. Patent No. 5,530,044 discloses a composition of an oligomer material where the end group is an unreactive alkyl group. Neither patent discloses that the oligomeric flame retardant is an effective flame retardant for polyolefms, nor does either patent disclose reduced exudation in polyolefms .
  • Hei 5-320439 discloses that tetrabromobisphenol S bis(2,3- dibromopropyl) ether in combination with brominated bisphenol A carbonate oligomers, or with brominated bisphenol ethyl ether oligomer s, gave less surface exudation than tetrabromobisphenol S bis(2,3-dibromopropyl) ether used alone in polypropylene.
  • the tetrabromobisphenol S bis(2,3- dibromopropyl) ether monomer to oligomer weight ratio is 99: 1 to 1 : 1 , with the range of 19: 1 to 3:2 being preferred.
  • Japanese Patent Application Kokai Sho 54-106557 discloses the use of a combination of tetrabromobisphenol A bis(2,3-dibromopropyl) ether and brominated bisphenol A carbonate oligomers as a low bloom, efficient flame retardant combination for polypropylene.
  • the preferred weight ratio range of ether to carbonate flame retardants is 9: 1 to 1: 1. Ratios of less than 1 : 1 are not disclosed as being useful, and many of the oligomeric species tested had a weight average molecular weight below 2,000.
  • Japanese Patent Application Kokai Hei 8-59902 discloses the use of brominated epoxy resins as bloom inhibitors for tetrabromobisphenol A bis(2,3-dibromopropyl) ether.
  • the weight ratio range of epoxy to tetrabromobisphenol A bis(2,3-dibromo ⁇ ropyl) ether is 1: 1 to 1:2.
  • An attempt to use bisphenol A carbonate oligomers or brominated bisphenol ethyl ether oligomers gave either poor flammability performance, high bleeding or both.
  • Japanese Patent Application Kokai Sho 57-192443 discloses a flame retardant composition obtained by combining polypropylene with a mixture comprising a brominated bisphenol A ethyl ether oligomer with a mixture of tetrabromobisphenol A bis(2,3-dibromopropyl) ether and tetrabromobisphenol S bis(2,3-dibromopropyl) ether and/or tris (2,3- dibromopropyl) isocyanurate.
  • Japanese Patent Application Hei 4-309542 discloses a flame- retardant resin composition formed by compounding 100 parts by weight polyolefin resin with 5-50 parts by weight organic halogen flame retardant having a bromoalkyl group in its structure, antimony trioxide at 3/1 - 1/6 antimony /halogen in the organic halogen flame retardant (molar ratio), 0.05-2.0 parts by weight alicyclic aliphatic epoxy compound, and 0.1 - 10.0 parts by weight pentaerythritol and/or pentaerythritol oligomer.
  • the present invention is directed to a unique blend of brominated flame retardants.
  • the composition also contains an antioxidant process stabilizer, and UV degradation retardant(s) combination including one or more UV degradation retardants selected from a UV stabilizer, a UV absorber, a UV blocker or screener, and any combination thereof that exhibits low surface migration (surface bleeding) even under accelerated oven testing while mamtaimng good flame retardancy despite the fact that one of the flame retardant components may show exudation when used by itself.
  • the brominated flame retardant composition includes two or more flame retardant components, and must contain at least one oligomeric flame retardant.
  • the oligomeric flame retardant component (component (a)) should contain aromatic bromine or a combination of aromatic bromine and aliphatic bromine while the monomeric or dimeric flame retardant component (component (b)) contains aliphatic bromine, and may contain a mixture of aliphatic bromine and aromatic bromine. Furthermore, the oligomeric flame retardant component should be compatible with the monomeric or dimeric flame retardant component, and should have a weight average molecular weight (M w ) of at least 2,000, as measured by GPC (Gel Permeation Chromatography) .
  • M w weight average molecular weight
  • the weight ratio of the oligomeric flame retardant component (a) to the monomeric or dimeric flame retardant component (b) should be in the range of about 1 : 10 to 10: 1 , preferably at least 1 : 1 , more preferably at least 1.1 : 1 , most preferably at least 1.2: 1 and to achieve the full advantage of the present invention, at least 1.3: 1. If the ratio of component (a) to component (b) is too low, then good flame retardancy will be exhibited but the final composite will show bloom after 24 hours of accelerated aging. Conversely, if the ratio of component (a) to component (b) is too high, then the composite will show low surface migration but poor flammability performance.
  • additional optional additives to the polymers include about 0.05% to about 2% , preferably about 0.1 % to about 1 % , based on the weight of the polymer, of an antioxidant acting as a process stabilizer, and about 0.1 % to about 3 % , preferably about 0.2% to about 2%, based on the weight of the polymer, of one or more UV degradation retardants selected from the group consisting of a UV stabilizer, a UV absorber, a UV blocker or screener, and any combination thereof.
  • Typical antioxidant process stabilizers include aromatic phosphites, aliphatic phosphites, aromatic phosphonites, aliphatic phosphonites or combinations of these.
  • UV degradation retarders include a hindered amine light stabilizer (HALS), UV absorber and/or a UV screener.
  • HALS hindered amine light stabilizer
  • Typical HALS include aliphatic hindered amines, dimeric hindered aliphatic amines, polymers containing the aliphatic amine in the backbone of the polymer or as a pendant group, or combinations of different HALS.
  • the amine may be secondary or ternary and may be either a liquid or a solid.
  • UV absorbers include alkoxy- or hydroxy-substituted benzophenones or hydroxyphenyl or substituted hydroxyphenyl benzotriazoles.
  • UV screeners may consist of inorganic or organic pigments, metal oxides such as titanium dioxide and carbon black.
  • Substituted phenols, especially hindered phenols and isocyanurate substituted cresols, may be used as antioxidants.
  • the stabilizer package may also contain acid scavengers such as metal salts of carboxylic acids and other basic or alkaline materials.
  • the present invention relates to a mixture of an oligomeric flame retardant component (a), preferably having a weight average molecular weight of at least 2,000, with a non-oligomeric (monomeric or dimeric) flame retardant component (b), preferably having a weight average molecular weight of less than 2,000.
  • a polymer stabilizer combination also is included in the composition comprising (c) an antioxidant process stabilizer and (d) a UV degradation retardant selected from the group consisting of (i) a UV stabilizer, (ii) a UV absorber, (iii) a UV blocker or UV screener; and (iv) any combination of two or more of the foregoing UV degradation retardants.
  • the oligomeric flame retardant component (a) can be represented by the following formula I:
  • G is a connecting group selected from the group consisting of a single bond, a branched or unbranched divalent aliphatic radical of from 1 to 10 carbons, oxygen, sulfur, sulfoxide, sulfone, or oxygen-silicon;
  • x is an integer from 1-4; and
  • R and R' are each (same or different) a branched or unbranched alkyl radical, A is a branched or unbranched alkyl diradical; and n is a positive integer greater or equal to 2.
  • G is a connecting group of the formula -CYY' where Y and Y' (same or different) are each an aliphatic hydrocarbon radical and, in particular, methyl radicals. In other preferred embodiments, G is an SO 2 connecting group.
  • A may be CH 2 CH 2 .
  • G is a C(CH 3 ) 2 connecting group; and A is a CH H connecting group, R and R' are CH 2 CH 2 Br groups.
  • the oligomeric flame retardant component (a) may consist of a bromine-containing epoxy oligomer with a weight average molecular weight of 1 ,000-50,000 of the following formula (II):
  • G is a connecting group selected from the group consisting of a single bond, a branched or unbranched divalent aliphatic radical of from 1 to 10 carbons, oxygen, sulfur, sulfoxide, sulfone, or oxygen-silicon
  • X is an integer from 1-4
  • R" and R"' are, independently, a branched or unbranched alkyl epoxy radical, branched or unbranched alkyl alcohol radical, branched or unbranched alkyl ether radical or branched or unbranched alkylhalide alcohol radical
  • C is a branched or unbranched alkyl diradical containing a hydroxy or ether group and n is a positive integer greater than or equal to 2.
  • G' is a (CH 3 ) 2 C group
  • C is a CH 2 CHOHCH 2 group
  • R"' is
  • the second, monomeric or dimeric flame retardant component (b) comprises a material having the following formula III:
  • G" is a connecting group selected from the group consisting of a single bond, a branched or unbranched divalent aliphatic radical of from 1 to 10 carbon atoms, oxygen, sulfur, sulfoxide, sulfone, or oxygen-silicon;
  • x" is an integer from 0-4; and
  • R"" and R'"" (same or different) each is selected from a branched or unbranched alkyl radical, branched or unbranched alkyl halide radical, and wherein at least of one R"" and R"'” contains bromine;
  • A' is a branched or unbranched alkyl diradical or halogenated dialkyl radical; and
  • n is a positive integer of 0 or 1.
  • G" is a connecting group of the formula
  • Y and Y' each is an aliphatic hydrocarbon radical and, in particular, methyl radicals.
  • G" is an SO 2 connecting group.
  • R"" and R""' are 2,3-dibromopropyl groups.
  • G" is a C(CH 3 ) 2 connecting group; n is 0; and both R"" and R""' are CH 2 CH 2 BrCH 2 Br groups.
  • the second, monomeric or dimeric flame retardant component (b) may also be selected from the following flame retardants: ethylene bis(5,6-dibromonorborane-2, 3-dicarboximide); hexabromocyclododecane; the Diels-Alder adduct of hexachlorocyclopentadiene with 1,5-cyclooctadiene; and tris(tribromoneopentyl)phosphate; bis(2,3-dibromopropyl)tetrabromophthalate, and the like.
  • flame retardants ethylene bis(5,6-dibromonorborane-2, 3-dicarboximide); hexabromocyclododecane; the Diels-Alder adduct of hexachlorocyclopentadiene with 1,5-cyclooctadiene; and tris(tribromoneopentyl)phosphate; bis(2,3-dibromopropy
  • the optional stabilizer package should contain an antioxidant, acting as a process stabilizer, and one or more UV degradation retardants.
  • Typical process stabilizers contain aromatic phosphites, aliphatic phosphites, aromatic phosphonites, aliphatic phosphonites, benzufuran(2) ones, especially
  • Examples are tris(2,4-di-tert-butyl-phenyl) phosphite, also known as Alkanox ® 240 (Alknox ® is a trademark of Great Lakes Chemical Corporation) or
  • Irgafos ® 168 (Irgafos ® is a trademark of Ciba Specialty Chemicals); bis(2,4-di- tert-butyl-phenyl)pentaerythritol diphosphite, also called Alkanox ® P-24 or
  • Ultranox ® 626 (Ultranox ® is a trademark of General Electric Corporation); tetrakis (2,4-di-tert-butyl-phenyl)4,4'-biphenylene-diphosphonite, also known as Alkanox ® 24-44 or Irgafos ® P-EPQ; bis(2,4-dicumylphenyl)pentaerythritol diphosphite, also called Alkonox ® 28 or Doverphos ® S-9228 (Doverphos ® is a registered trademark of Dover Corporation); and tris(p-nonyl- phenyl)phosphite, also called Alkanox ® TNPP or Doverphos ® 4-HR.
  • Substituted phenols especially hindered phenols and isocyanurate substituted methylene phenols, may be used as antioxidant process stabilizers.
  • antioxidants are 2-(2'-hydroxy-3',5'-di- tert-butylbenzyl)isocyanurate, also known as AnoxTM 1C-14 (AnoxTM is a trademark of Great Lakes Chemical Corporation) or IRGANOX ® 3114, a trademark of CIBA Specialty Chemicals; tetrakismethylene (3,5-di-t-butyl-4- hydroxyhydrocinnamate)methane, also called AnoxTM 20 or IRGANOX ® 1010; octadecyl 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, also called AnoxTM PP18 or IRGANOX ® 1076; and l,3,5-tris(2,6-dimethyl-3-hydroxy
  • the stabilizer package preferably also contains at least one of a
  • UV degradation retarder or UV stabilizer such as a hindered amine light stabilizer (HALS), UV absorber or a UV screener.
  • HALS hindered amine light stabilizer
  • Typical HALS include aliphatic hindered amines; dimeric hindered aliphatic amines; polymers containing the aliphatic amine in the backbone of the polymer or as a pendant group; or combinations of different HALS, and hydroxyl amines.
  • the amine may be secondary or ternary and may be either a liquid or a solid.
  • HALS include bis-(l,2,2,6,6-pentamethyl-4-piperidinyl)-sebacate, also known as Lowlite ® 76 (Lowlite ® is a trademark of Great Lakes Chemical Corporation) or Tinuvin ® 765 (Tinuvin ® is a trademark of Ciba Specialty Chemicals) or Tinuvin ® 292; bis-(2,2,6,6-tetramethyl-4-piperidinyl)-sebacate, also called Lowlite ® 77 or Tinuvin 770 ® ; butanedioic acid, dimethyl ester, polymer with 4-hydroxy-2,2,6,6-tetramethyl-l-piperidineethanol, also called Lowlite ® 62 or Tinuvin ® 622; poly-methylpropyl-3-oxy-[4(2, 2,6,6- tetramefhyl)piperdinyl] siloxane, also called Uvasil ® 299 (Uvasil ® is a trademark of
  • UV absorbers include alkoxy or hydroxy substituted benzophenones or hydroxyphenyl or substituted hydroxyphenyl benzotriazoles. Specific examples of UV absorbers are 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxy-benzophenone, also called Lowlite ® 22 or Chimassorb ® 81; 2-(2'-hydroxy-3',5'-ditert-butyl-phenyl)-5-chlorobenzotriazole, also known as Lowlite ® 27 or Tinuvin ® 327; 2-(2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl)- 5-chlorobenzotriazole, also called Lowlite ® 26 or Tinuvin ® 326; 2-(2'-hydroxy- 3',5'-di-t-amylphenyl)benzotriazole, also called Lowlite ® 28 or Tinuvin ® 328; and 2-(2'-hydroxy-5'-methyl-phenyl)benz
  • the stabilizer package may also contain acid scavengers such as metal salts of carboxylic acids. Typical examples include calcium stearate, zinc stearate, calcium lactate, aluminum-magnesium hydrotalcite and other basic or alkaline materials.
  • acid scavengers such as metal salts of carboxylic acids. Typical examples include calcium stearate, zinc stearate, calcium lactate, aluminum-magnesium hydrotalcite and other basic or alkaline materials.
  • the stabilizer package when added to the fibrous or non-fibrous polymer, may include a flame retardant synergist in an amount in a ratio of flame retardant: flame retardant synergist in the range of about 10: 1 to 3: 1 , preferably in the range of about 2-6: 1.
  • flame retardant synergists include antimony trioxide, zinc borate, and sodium antimonate.
  • the combination of the flame retardant components, optional antioxidant process stabilizer and optionally one or more UV degradation retarders are useful as flame retardants, particularly when compounded with other plastic compounds or polymer compositions, particularly polyolefms, preferably aliphatic polyolefms, such as polyethylene and polypropylene and copolymers thereof.
  • the combination of flame retardant compounds of the present invention is less prone to surface migration, while maintaining good flame retardancy.
  • the preferred addition of the antioxidant process stabilizer and one or more UV degradation retarders prevents the degradation of physical properties and/or color in the polymer, particularly in polyolefin fibers and film, particularly polypropylene.
  • the combination of flame retardants of the present invention is useful as a stabilized flame retardant in polymeric materials such as polystyrene; high impact polystyrene; copolymers of styrene; polycarbonates; polyurethanes; polyi ides; polyamides; polyethers; acrylics; polyesters; epoxies; phenolics; elastomers, such as butadiene/styrene copolymers and butadiene/acrylonitrile copolymers; te olymers of acrylonitrile, butadiene and styrene; natural rubber; butyl rubber; polysiloxanes, and particularly polyolefins, including fibers made from any of the foregoing.
  • polymeric materials such as polystyrene; high impact polystyrene; copolymers of styrene; polycarbonates; polyurethanes; polyi ides; polyamides; polyethers; acrylics
  • Preferred polymers include those of olefinically-saturated monomers, such as ethylene, propylene, butene, butadiene and copolymers of two or more of such alkylene monomers. Blends of polymers may also be flame retarded and stabilized with the combination of flame retardants and stabilizers/UV degradation retardants disclosed herein.
  • the most preferred polymers are aliphatic polyolefins, particularly polyethylene, polypropylene, and copolymers of propylene and ethylene, preferably where the polyolefm and polyolefm copolymers are in fiber form.
  • the oligomeric flame retardant component (a) of the present invention may be prepared by reacting a diphenol with a divalent reactant, for example carbonyl dichloride, in the presence of a base, in a solvent such as methylene chloride. A second phenol can be added to end cap the oligomer.
  • a divalent reactant for example carbonyl dichloride
  • the flame retarded polymer compositions of the present invention may be prepared by mixing the oligomeric flame retardant component
  • a premixing of the flame retardant components (a) and (b) with the optional process stabilizer component (c) and the optional UV degradation retarder(s) (d) is preferred.
  • the flame retardant components (a) and (b) , the optional stabilizer component (c), and the optional UV degradation retarder(s) (d) may be blended by mixing the powders; melting the components and then mixing; or one component may be melted or softened and the components then mixed.
  • Typical mixing apparatus includes, but is not limited to, high shear mixers, such as a Banbury mixer; tumble type blenders; and extruders. It is further preferred to mix the components (a) and (b) with the optional stabilizer and UV degradation retarder(s) (c) and (d) and then blend the complete package with the polymer.
  • the flame retardant stabilized mixtures of the present invention may be used as a fine powder, as a compacted material, or may be used with a small amount of a suitable binder as a master batch.
  • Suitable binders include, but are not limited to, calcium stearate, antimony trioxide, polyethylene, polypropylene, propylene/ethylene copolymers, and poly(brominated styrene).
  • Suitable forms of the compounds of this invention include powder, compacted, prilled, chilsinated, and the like.
  • compositions of this invention when including components (c) and (d), may also be added in a stepwise manner.
  • the antioxidant process stabilizer component (c) can be added to the polyolefm followed by addition of the flame retardant components (a) and (b) and then a UV degradation retardant (d), such as HALS; or followed by the flame retardant components (a) and (b) and then a UV degradation retarder, e.g. , HALS, and then an acid scavenger.
  • a UV degradation retardant such as HALS
  • a UV degradation retarder e.g. , HALS
  • the flame retardant combination when added to the fibrous or non- fibrous polymer, preferably a polyolefm used to make a polyolefm in fiber or film form, may include a flame retardant synergist in an amount in a weight ratio of flame retardant: flame retardant synergist in the range of about 10: 1 to 3: 1 , preferably in the range of about 2-6: 1.
  • flame retardant synergists include antimony trioxide, zinc borate, and sodium antimonate.
  • the oligomeric component (a), monomeric or dimeric component (b), antimony trioxide (5: 1 weight ratio of total flame retardant to antimony trioxide), are weighed into the polyolefm and the mixture is thoroughly hand mixed in a poly bag.
  • the oligomeric component (a) and monomeric or dimeric component (b) are mixed in a ribbon blender and then weighed, with antimony oxide, into the polyolefm and then thoroughly mixed.
  • the material is compounded on a Berstorff ZE-25 twin screw extruder at the conditions shown below (see Table 1). TABLE 1
  • a belt feeder was used to feed the formulation mixture to the throat (i.e. , barrel 1) of the twin screw.
  • the throat was cooled to 80-90°F.
  • the formulation strands were cooled in a 6 foot water bath (Ca. 75-80°F), then air dried and pelletized using a Conair/Jetro Model #304 pelletizer.
  • Bloom plaques (Gardner impact plaques) and 1/16 th inch UL-94 bars were molded on a Boy 50 Ton injection molder (Model #159-50 at the conditions shown below (See Table 2).
  • Nozzle Temperature (°C) 225 Typical Melt Temperature (°F) 440-450
  • Bloom plaques and UL-94 bars were conditioned at 70-75 °F for 24 hours prior to start of testing.
  • A tetrabromobisphenol A bis(2,3-dibromopropyl ether)
  • B methyl end-capped tetrabromobisphenol A/ethylene dibromide oligomer (M w ⁇ 2,000)
  • C methyl end-capped tetrabromobisphenol A/ethylene dibromide oligomer (M w > 2,000)
  • D molecular weight 1100, mixture of CH 2 CH 2 Br and H end groups*
  • E molecular weight 2340, mixture of CH 2 CH 2 Br and CH 3 end groups
  • F molecular weight 6110, CH 2 CH 2 Br end groups

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un mélange unique d'ignifugeants bromés, un stabilisateur de traitement antioxydant qui présente une faible migration en surface (surface bleeding) et qui empêche la dégradation des propriétés physiques et/ou de la couleur, y compris en cas d'essai en four accéléré, tout en conservant de bonnes propriétés d'ignifugation en dépit du fait qu'un des composants ignifugeants puisse présenter une exsudation lorsqu'il est utilisé seul. La composition ignifuge bromée comporte un ou plusieurs composants ignifugeants et doit contenir au moins un ignifugeant oligomère. Le composant ignifugeant oligomère (composant (a)) devrait contenir du brome aromatique ou une combinaison de brome aromatique et de brome aliphatique, tandis que le composant ignifugeant monomère ou dimère (composant (b)) devrait contenir du brome aliphatique et peut contenir un mélange de brome aliphatique et de brome aromatique.
PCT/US2000/019140 1999-07-23 2000-07-13 Compositions ignifuges stables exemptes d'efflorescences et procede permettant d'ignifuger des polyolefines WO2001007511A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU13247/01A AU1324701A (en) 1999-07-23 2000-07-13 Non-blooming, stabilized flame retardant compositions and method of flame retarding polyolefins

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US14548499P 1999-07-23 1999-07-23
US60/145,484 1999-07-23
US15884999P 1999-10-12 1999-10-12
US15882699P 1999-10-12 1999-10-12
US60/158,826 1999-10-12
US60/158,849 1999-10-12

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WO2001007511A2 true WO2001007511A2 (fr) 2001-02-01
WO2001007511A3 WO2001007511A3 (fr) 2001-08-30

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001062840A1 (fr) * 2000-02-25 2001-08-30 Clariant International Ltd Compositions stabilisantes synergiques pour polymeres thermoplastiques en contact prolonge avec l'eau
US6646035B2 (en) 2000-02-25 2003-11-11 Clariant Finance (Bvi) Limited Synergistic combinations of phenolic antioxidants
WO2012127463A1 (fr) 2011-03-20 2012-09-27 Bromine Compounds Ltd. Composition retardatrice de flamme et polypropylène à haute résistance au choc, à retard de flamme

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Publication number Priority date Publication date Assignee Title
US4699734A (en) * 1985-11-06 1987-10-13 A. Schulman, Inc. Flame-retardant polyolefin compositions containing exudation inhibitor and process for producing same
EP0462722A2 (fr) * 1990-06-04 1991-12-27 Illinois Tool Works Inc. Composition ignifugée
EP0633288A1 (fr) * 1993-07-06 1995-01-11 Hpg International, Inc. Composition polypropylène retardatrice de flammes
WO1996035747A1 (fr) * 1995-05-11 1996-11-14 Great Lakes Chemical Corporation Polyethers halogenes a coiffe terminale alkyle

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JPS5468854A (en) * 1977-11-10 1979-06-02 Dainippon Ink & Chem Inc Flame-retardant polystyrene resin composition
JP3030909B2 (ja) * 1991-04-04 2000-04-10 東ソー株式会社 難燃性樹脂組成物

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US4699734A (en) * 1985-11-06 1987-10-13 A. Schulman, Inc. Flame-retardant polyolefin compositions containing exudation inhibitor and process for producing same
EP0462722A2 (fr) * 1990-06-04 1991-12-27 Illinois Tool Works Inc. Composition ignifugée
EP0633288A1 (fr) * 1993-07-06 1995-01-11 Hpg International, Inc. Composition polypropylène retardatrice de flammes
WO1996035747A1 (fr) * 1995-05-11 1996-11-14 Great Lakes Chemical Corporation Polyethers halogenes a coiffe terminale alkyle

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Title
CHEMICAL ABSTRACTS, vol. 118, no. 13, 29 March 1993 (1993-03-29) Columbus, Ohio, US; abstract no. 118103897, TANAKA Y: "Fire-resistant polyolefin compositions" XP002159835 & JP 04 309542 A (TOSOH CORP) 2 November 1992 (1992-11-02) *
PATENT ABSTRACTS OF JAPAN vol. 003, no. 091 (C-054), 3 August 1979 (1979-08-03) & JP 54 068854 A (DAINIPPON INK & CHEM INC), 2 June 1979 (1979-06-02) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001062840A1 (fr) * 2000-02-25 2001-08-30 Clariant International Ltd Compositions stabilisantes synergiques pour polymeres thermoplastiques en contact prolonge avec l'eau
US6646035B2 (en) 2000-02-25 2003-11-11 Clariant Finance (Bvi) Limited Synergistic combinations of phenolic antioxidants
US6787591B2 (en) 2000-02-25 2004-09-07 Clariant Finance (Bvi) Limited Synergistic stabilizer compositions for themoplastic polymers in prolonged contact with water
WO2012127463A1 (fr) 2011-03-20 2012-09-27 Bromine Compounds Ltd. Composition retardatrice de flamme et polypropylène à haute résistance au choc, à retard de flamme

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AU1324701A (en) 2001-02-13
WO2001007511A3 (fr) 2001-08-30

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