WO2001007510A2 - Compositions ignifuges stabilisees non efflorescentes et procede d'elaboration de polyolefines ignifuges - Google Patents

Compositions ignifuges stabilisees non efflorescentes et procede d'elaboration de polyolefines ignifuges Download PDF

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WO2001007510A2
WO2001007510A2 PCT/US2000/019084 US0019084W WO0107510A2 WO 2001007510 A2 WO2001007510 A2 WO 2001007510A2 US 0019084 W US0019084 W US 0019084W WO 0107510 A2 WO0107510 A2 WO 0107510A2
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flame retardant
composition
retardant compound
weight
polymer
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PCT/US2000/019084
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English (en)
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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 AU14296/01A priority Critical patent/AU1429601A/en
Publication of WO2001007510A2 publication Critical patent/WO2001007510A2/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
    • C08K5/13—Phenols; Phenolates
    • C08K5/136—Phenols containing halogens

Definitions

  • the present invention is directed to stabilized flame retardant compositions for polymers, preferably polyolefins, and methods of flame retarding polymers, particularly aliphatic polyolefins, 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 monomeric 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) polyolefins; and good retention of physical properties and/or color in polyolefin 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 polyolefins.
  • Lower molecular weight halogen compounds that are efficient flame retardants and that contain aliphatic bromine tend to undergo surface migration in polyolefins. This leads to marring of the surface appearance of the polyolefin.
  • antioxidant process stabilizers during the manufacture of polyolefins to prevent oxidation of olefins during the polymerization reaction
  • antioxidants to a polyolefin during processing, e.g., during fiber formation, to prevent oxidation of the polyolefin.
  • halogenated flame retardants also are generally reactive with UV light in polyolefins, e.g. , polypropylene, causing degradation of the polyolefin, as demonstrated by decreasing tensile strength of the polyolefin-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 polyolefin compositions, more particularly, toward flame retarded and UV stabilized polyolefin 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 elastomeric 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 elastomeric 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 polyolefin 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 polyolefins, nor does either patent disclose reduced exudation in polyolefins.
  • 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 oligomers, 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-dibromopropyl) ether is 1 : 1 to 1 :2.
  • 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 maintaining 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).
  • 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 phenyl or a halogen substituted aromatic group of from 6 to 12 carbon atoms;
  • A is a carbonyl group or a dicarboxy-containing connecting group containing from 2-12 carbon atoms; and
  • n is a positive integer greater than or equal to 2.
  • G is a connecting group of the formula
  • Y and Y' are each an aliphatic hydrocarbon radical and, in particular, methyl radicals.
  • G is an SO 2 connecting group.
  • R and R' same or different, each may be a phenyl or tribromophenyl group.
  • A may be CO or OCCH 2 CH 2 CH 2 CH 2 CO.
  • G is a C(CH 3 ) 2 connecting group; A is a CO connecting group; and R and R' are phenyl 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-dibromo
  • 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-
  • 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- tetramethyl)piperdinyl] siloxane, also called Uvasil ® 299 (Uvasil ® is a trademark of Great Lakes Chemical
  • 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 polyolefins, preferably aliphatic polyolefins, 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; pol imides; poly amides; poly ethers; acrylics; polyesters; epoxies; phenolics; elastomers, such as butadiene/styrene copolymers and butadiene/acrylonitrile copolymers; terpolymers 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; pol imides; poly amides; poly ethers;
  • 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 polyolefin and polyolefin 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 containing components (c) and (d), may also be added in a stepwise manner.
  • the antioxidant process stabilizer component (c) can be added to the polyolefin 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 oligomeric component (a), monomeric or dimeric component (b), and antimony trioxide (5:1 weight ratio of total flame retardant to antimony trioxide), are weighed into the polyolefin 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 polyolefin and then thoroughly mixed.
  • the material is compounded on a Berstorff ZE-25 twin screw extruder at the conditions shown below (see Table 1).
  • 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 Mold Temperature (°F) 90 Typical Inject Pressure (psi) 450-475
  • Bloom plaques and UL-94 bars were conditioned at 70-75 °F for 24 hours prior to start of testing.
  • the monomeric or dimeric flame retardant component (b), used alone, has good flame retardancy (examples 1 and 2) but unacceptable exudation.
  • the oligomeric component has poor flammability when used alone (example 3).
  • Good flame retardancy as measured by the UL 94 V-0 rating, can be achieved at relatively low loading levels but at weight load ratios of 1 : 1 (example 8) of the oligomeric flame retardant component (a) to the monomeric or dimeric flame retardant component (b), bloom becomes unacceptable.
  • oligomeric flame retardant (a) to monomeric or dimeric flame retardant (b) is 1.1 : 1 to 5 : 1 ; more preferred in the range of 1.2: 1 to 5: 1, and most preferred in the range of 1.5: 1 to 3: 1 for V-0 flame rating applications.
  • Samples were first formulated with a stabilizer package and then compounded using a Killion KL-100 single screw extruder to minimize shear and eliminate cross contamination between formulations.
  • the following temperature profile was used: 200 - 210 - 230 - 230°C with a screw speed of 115-1 16 RPM.
  • the stabilized samples were compounded using a Bersdorff 25 mm twin screw extruder.
  • the following temperature profile was used: (Second extrusion) 195 - 200 - 200 - 200 - 200 - 200 - 200 - 200 - 205 °C with a melt pressure of 200-220 PSI and a screw speed of 270 RPM.
  • Fiber from each formula was wrapped on the card using a winder.
  • the samples and the test control fabric were mounted on a rotating carousel in gas fade chamber and were exposed simultaneously to oxides of nitrogen from burnt gas fumes @ 140°F.
  • Al 28 Alkanox ® 28
  • GPP 39 ® Great Lakes GPP 39 CN2525
  • CN 2525 is a 2: 1 mixture of an oligomeric brominated carbonate flame retardant having formula I and a monomeric brominated carbonate flame retardant of formula III
  • Uvasil ® 2000LMPE 70% Uvasil ® 299 in 30% polypropylene as a binder to bind the Uvasil ® 299 powder.
  • Each formulation contains Alkanox ® 28 @ 0.3 % as processing stabilizer and calcium stearate as an acid scavenger.
  • Uvasil ® 2000 was used for compounding. Uvasil ® 2000 @ 0.42% load level is equal to Uvasil ® 299 @ 0.25 % .

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Abstract

L'invention concerne un mélange unique d'ignifuges bromés présentant une faible migration de surface (épanchement de surface) et empêchant la dégradation des propriétés physiques et/ou de la couleur, y compris lors d'un essai en four accéléré, tout en maintenant une bonne capacité ignifugeante même si l'un des composés ignifuges peut présenter une exsudation lors de sa détérioration. Cette composition ignifuge bromée comprend deux ou plusieurs composés ignifuges et doit contenir au moins un composé ignifuge oligomérique. Ce composé ignifuge oligomérique (composé (a)) contient normalement du brome aromatique ou une combinaison de brome aromatique et de brome aliphatique, alors que le composé ignifuge dimérique ou monomérique (composé (b)) contient habituellement du brome aliphatique et parfois un mélange de brome aliphatique et de brome aromatique.
PCT/US2000/019084 1999-07-23 2000-07-13 Compositions ignifuges stabilisees non efflorescentes et procede d'elaboration de polyolefines ignifuges WO2001007510A2 (fr)

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AU14296/01A AU1429601A (en) 1999-07-23 2000-07-13 Non-blooming, stabilized flame retardant compositions and method of flame retarding polyolefins

Applications Claiming Priority (6)

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US14548399P 1999-07-23 1999-07-23
US60/145,483 1999-07-23
US15882599P 1999-10-12 1999-10-12
US15882799P 1999-10-12 1999-10-12
US60/158,827 1999-10-12
US60/158,825 1999-10-12

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US09/980,799 A-371-Of-International US6660711B1 (en) 1999-07-16 2000-07-13 Laundry detergent compositions comprising zwitterionic polyamines and mid-chain branched surfactants
US10/679,917 Continuation US6914041B2 (en) 1999-07-16 2003-10-06 Laundry detergent compositions comprising zwitterionic polyamines and mid-chain branched surfactants

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1284121A2 (fr) 2001-08-06 2003-02-19 Lifescan, Inc. Dispositifs et méthodes de prélèvement d'un échantillon
CN115322488A (zh) * 2022-08-11 2022-11-11 金发科技股份有限公司 一种阻燃聚丙烯复合材料及其制备方法和应用

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1284121A2 (fr) 2001-08-06 2003-02-19 Lifescan, Inc. Dispositifs et méthodes de prélèvement d'un échantillon
CN115322488A (zh) * 2022-08-11 2022-11-11 金发科技股份有限公司 一种阻燃聚丙烯复合材料及其制备方法和应用
CN115322488B (zh) * 2022-08-11 2023-10-31 金发科技股份有限公司 一种阻燃聚丙烯复合材料及其制备方法和应用

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