WO2011120225A1 - Compositions de polyuréthane thermoplastique ignifugeant sans migration et sans halogène - Google Patents

Compositions de polyuréthane thermoplastique ignifugeant sans migration et sans halogène Download PDF

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Publication number
WO2011120225A1
WO2011120225A1 PCT/CN2010/071473 CN2010071473W WO2011120225A1 WO 2011120225 A1 WO2011120225 A1 WO 2011120225A1 CN 2010071473 W CN2010071473 W CN 2010071473W WO 2011120225 A1 WO2011120225 A1 WO 2011120225A1
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composition
flame retardant
compositions
melting point
total weight
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PCT/CN2010/071473
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English (en)
Inventor
Lu Journey Zu
Bin Li
Lan Lu
Jing Given Chen
Qin Deng
Hong Fei David Guo
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Dow Global Technologies Llc
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Priority to PCT/CN2010/071473 priority Critical patent/WO2011120225A1/fr
Priority to TW100109107A priority patent/TW201134925A/zh
Publication of WO2011120225A1 publication Critical patent/WO2011120225A1/fr

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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
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds

Definitions

  • MIGRATION-FREE MIGRATION-FREE, HALOGEN-FREE, FLAME RETARDANT THERMOPLASTIC
  • Thermoplastic polyurethane (TPU) elastomers have a broad range of flexibility and can be fabricated by a variety of methods, from injection molding to extrusion and blow molding. They also offer the performance benefits of clarity, abrasion resistance, chemical and hydrocarbon resistance, load-bearing capabilities and high tensile strengths. Accordingly, they find use in many applications which require flame resistance.
  • Traditional flame retardants used in TPU compositions contain halogens (the so-called halogenated flame retardants).
  • HFFR non- halogenated flame retardant
  • Liquid organic phosphates e.g. resorcinol bis(diphenyl phosphate) (RDP), or bisphenol-A bis(diphenyl phosphate) (BDP)
  • RDP resorcinol bis(diphenyl phosphate)
  • BDP bisphenol-A bis(diphenyl phosphate)
  • One aspect of the invention provides halogen-free flame-retardant compositions comprising at least 20 weight percent, based on the total weight of the composition, of a continuous resin phase comprising a thermoplastic polyurethane; at least 5 weight percent, based on the total weight of the composition, of an aromatic organic phosphate flame retardant having a melting point of at least 50 °C; and at least 20 weight percent, based on the total weight of the composition, of an inorganic hydrate flame retardant.
  • These compositions comprise no greater than 10 weight percent, based on the total weight of the composition, of organic flame retardants having a melting point of 25 °C or lower.
  • the compositions comprise at least 30 weight percent, based on the total weight of the composition, of a continuous resin phase comprising a thermoplastic polyurethane; at least 5 weight percent, based on the total weight of the composition, of an aromatic organic phosphate flame retardant having a melting point of at least 50 °C, wherein the aromatic organic flame retardant is an aromatic polyphosphate; and at least 30 weight percent, based on the total weight of the composition, of an inorganic hydrate flame retardant.
  • the compositions comprise an organic flame retardant having a melting point of 25 °C or lower, in which the weight percent of organic flame retardants having a melting point of 25 °C or lower is equal to, or lower than the weight percent of the aromatic organic phosphate flame retardant having a melting point of at least 50 °C. In some such embodiments, the compositions are free of organic flame retardant having a melting point of 25 °C or lower.
  • compositions are characterized in that a cable consisting of a composition in accordance with this invention does not exhibit migration after 48 hours at 50 °C and 80% relative humidity.
  • the compositions have a heat deformation ratio, as measured by UL 1581 -2001 , of no greater than 20 %.
  • compositions further comprise an epoxidized novolac resin.
  • compositions further comprise a polar polyolefin dispersed in, or co-continuous with, the continuous resin phase.
  • the aromatic organic phosphate flame retardant having a melting point of at least 50 °C is high molecular weight resorcinol bis(diphenyl phosphate), resorcinol bis(dixylenyl phosphate), or a combination thereof.
  • Another aspect of the invention provides jacketing or insulation for a wire or cable comprising a composition in accordance with the present invention.
  • FIG. 1 is a schematic diagram of the set-up for the non -migration testing of the present compositions.
  • One aspect of the present invention provides a halogen-free, thermoplastic polyurethane-based composition having good mechanical and flame-retardant properties.
  • the compositions include flame-retardant organic phosphorus compounds that do not exhibit migration in molded products, such as cable and wire jacketing.
  • the compositions include a continuous resin phase comprising a thermoplastic polyurethane elastomer, at least one aromatic organic phosphate flame retardant having a melting point of at least 50 °C and an inorganic hydrate flame retardant.
  • the aromatic organic phosphate flame retardant is a solid at room temperature in molded articles made from the present compositions and, as a result, these compositions provide improved non-migration properties relative to comparable flame-retardant compositions that use liquid organic phosphate flame retardants.
  • Halogen-free and like terms mean that the compositions are without or substantially without halogen content, i.e., contain less than 2000 mg/kg of halogen as measured by ion chromatography (IC) or a similar analytical method. Halogen content of less than this amount is considered inconsequential to the efficacy of the blend as, for example, a wire or cable covering.
  • IC ion chromatography
  • compositions are suited for use in a variety of molded thermoplastic articles, including jacketing and insulation for wires and cables, automobile parts, building and construction materials, toys, artificial leather, and electronic appliances and devices.
  • a "thermoplastic polyurethane” refers to the reaction product of a di-isocyanate, one or more polymeric diol(s), and optionally one or more difunctional chain extender(s).
  • the TPU may be prepared by the prepolymer, quasi-prepolymer, or one-shot methods.
  • the di-isocyanate forms a hard segment in the TPU and may be an aromatic, an aliphatic, or a cycloaliphatic di-isocyanate and combinations of two or more of these compounds.
  • a nonlimiting example of a structural unit derived from di-isocyanate (OCN- R-NCO) is represented by formula (I) below: o o
  • R is an alkylene, cycloalkylene, or arylene group.
  • diisocyanates can be found in U.S. Patent Nos. 4,385,133, 4,522,975 and 5,167,899.
  • suitable diisocyanates include 4,4'-di-isocyanatodiphenyl-methane, p-phenylene di-isocyanate, 1 ,3 -bis(isocyanatomethyl)-cyclohexane, 1 ,4-di-isocyanato-cyclohexane, hexamethylene di-isocyanate, 1 ,5 -naphthalene di-isocyanate, 3,3'-dimethyl-4,4'-biphenyl di-isocyanate, 4,4'-di-isocyanato-dicyclohexylmethane, and 2,4-toluene di-isocyanate.
  • the polymeric diol forms soft segments in the resulting TPU.
  • the polymeric diol can have a molecular weight (number average) in the range, for example, from 200 to 10,000 g/mole. More than one polymeric diol can be employed.
  • Nonlimiting examples of suitable polymeric diols include polyether diols (yielding a "polyether TPU”); polyester diols (yielding a "polyester TPU”); hydroxy-terminated polycarbonates (yielding a "polycarbonate TPU”); hydroxy- terminated polybutadienes; hydroxy-terminated polybutadiene-acrylonitrile copolymers; hydroxy-terminated copolymers of dialkyl siloxane and alkylene oxides, such as ethylene oxide, propylene oxide; natural oil diols, and any combination thereof.
  • One or more of the foregoing polymeric diols may be mixed with an amine-terminated polyether and/or an amino-terminated polybutadiene-acrylonitrile copolymer.
  • the difunctional chain extender can be aliphatic straight and branched chain diols having from 2 to 10 carbon atoms, inclusive, in the chain.
  • diols ethylene glycol, 1,3 -propanediol, 1 ,4-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, neopentyl glycol, and the like; 1,4-cyclohexanedimethanol; hydroquinonebis-(hydroxyethyl)ether; cyclohexylenediols (1,4-, 1,3-, and 1,2-isomers), isopropylidenebis(cyclohexanols); diethylene glycol, dipropylene glycol, ethanolamine, N-methyl-diethanolamine, and the like; and mixtures of any of the above.
  • difunctional extender may be replaced by trifunctional extenders, without detracting from the thermoplasticity of the resulting TPU; illustrative of such extenders are glycerol, trimethylolpropane, and the like.
  • the chain extender is incorporated into the polyurethane in amounts determined by the selection of the specific reactant components, the desired amounts of the hard and soft segments, and the index sufficient to provide good mechanical properties, such as modulus and tear strength.
  • chain stoppers small amounts of monohydroxyl functional or monoamino functional compounds, often termed “chain stoppers,” may be used to control molecular weight.
  • chain stoppers are the propanols, butanols, pentanols, and hexanols.
  • TPUs include the PELLETHANETM, ESTANETM, TECOFLEXTM, TECOPHILICTM, TECOTHANETM, and TECOPLASTTM thermoplastic polyurethanes all available from the Lubrizol Corporation; ELASTOLLANTM thermoplastic polyurethanes and other thermoplastic polyurethanes available from BASF; and additional thermoplastic polyurethane materials available from Bayer, Huntsman, Merquinsa and other suppliers.
  • the polyurethane component of the continuous resin phase used in the practice of the invention may contain a combination of two or more TPUs as described above.
  • the TPUs are typically present in an amount of at least 20 weight percent (wt.%), based on the total weight of the composition. This includes compositions that contain at least 30 wt.% TPU, based on the total weight of the composition. For example, in some embodiments, the compositions include about 20 to 70 wt.% TPU, about 30 to 50 wt.% TPU, or about 30 to 40 wt.% TPU.
  • the halogen-free, TPU-based compositions can optionally include one or more additional polymers, such as polar polyolefins. These can be dispersed in, or co-continuous with, the continuous resin phase of the composition.
  • Olefin polymer means a polymer containing, in polymerized form, a majority weight percent of an olefin, for example ethylene or propylene, based on the total weight of the polymer.
  • Thermoplastic polyolefins include both olefin homopolymers and interpolymers.
  • Interpolymer means a polymer prepared by the polymerization of at least two different monomers.
  • the interpolymers can be random, block, homogeneous, heterogeneous, etc.
  • This generic term includes copolymers, usually employed to refer to polymers prepared from two different monomers, and polymers prepared from more than two different monomers, e.g., terpolymers, tetrapolymers, etc.
  • a "polar olefin polymer,” is an olefin polymer containing one or more polar groups (sometimes referred to as polar functionalities).
  • a "polar group,” as used herein, is any group that imparts a bond dipole moment to an otherwise essentially nonpolar olefin molecule.
  • Exemplary polar groups include carbonyls, carboxylic acid groups, carboxylic acid anhydrate groups, carboxylic ester groups, epoxy groups, sulfonyl groups, nitrile groups, amide groups, silane groups and the like. These groups can be introduced into the olefin-based polymer either through grafting or copolymerization.
  • Nonlimiting examples of polar olefin-based polymers include ethyl ene/acrylic acid (EAA), ethyl ene/methacrylic acid (EMA), ethylene/acrylate or methacrylate, ethylene/vinyl acetate (EVA), poly(ethylene-co-vinyltrimethoxysilane) copolymer, maleic anhydrate- or silane-grafted olefin polymers, poly(tetrafluoroethylene-alt-ethylene) (ETFE), poly(tetrafluoroethylene-co-hexafluoro-propylene) (FEP), poly(ethylene-co- tetrafluoroethylene-co-hexafluoropropylene (EFEP), poly(vinylidene fluoride) (PVDF), poly(vinyl fluoride) (PVF), and the like.
  • EAA ethyl ene/acrylic acid
  • EMA ethyl ene/methacryl
  • Preferred polar olefin polymers include DuPont EL VAXTM ethylene vinyl acetate (EVA) resins, AMPLIFYTM ethylene ethyl acrylate (EEA) copolymer from The Dow Chemical Company, PRFMACORTM ethylene/acrylic acid copolymers from The Dow Chemical Company, and SI-LINKTM poly(ethylene-co-vinyltrimethoxysilane) copolymer from The Dow Chemical Company.
  • EVA is a preferred polar olefin polymer. This includes copolymers of EVA with one or more comonomers selected from Ci to C 6 alkyl acrylates, Ci to C 6 alkyl methacrylates, acrylic acid and methacrylic acid.
  • the polar olefin polymers are typically used in amounts ranging from 1 to 40 wt.% based on the total weight of the composition.
  • the halogen-free, flame-retardant compositions include at least one aromatic organic phosphate-based flame retardant compound, such as a phosphoric acid ester, having a melting point that is low enough that it melts under melt processing and extrusion temperatures (e.g., >150 °C), but high enough that it exists as a solid in the final molded product at room temperature (23 °C) and passes the non-migration test laid out in the example, below. It is advantageous for the non-migrating aromatic organic phosphate-based flame retardant to exist as a liquid during extrusion so that it will operate as a lubricant.
  • the non-migrating aromatic organic phosphate-based flame retardant compound has a melting point of at least 50 °C, at least 70 °C, at least 80 °C, or at least 100 °C.
  • aromatic polyphosphates such as high molecular weight resorcinol bis(diphenyl phosphate) (P-RDP) and resorcinol bis(dixylenyl phosphate) (XDP), the structures of which are shown below.
  • P-RDP high molecular weight resorcinol bis(diphenyl phosphate)
  • XDP resorcinol bis(dixylenyl phosphate)
  • n can be, for example 1.7 to 1.8 and the molecular weight, Mw, can be 650 to 700.
  • the non-migrating, aromatic organic phosphate flame retardants are typically present in an amount of at least 5 wt.%, based on the total weight of the composition. This includes compositions that contain at least 10 wt.%, based on the total weight of the composition, of non- migrating, aromatic organic phosphate flame retardant.
  • the compositions include about 5 to 20 wt.% non-migrating, aromatic organic phosphate flame retardant or about 10 to 15 wt.% non-migrating, aromatic organic phosphate flame retardant.
  • the present composition can optionally include one or more liquid (at room temperature) organic phosphate flame retardants.
  • liquid organic phosphate flame retardants exist as liquids in molded articles made from the compositions at room temperature and/or have relatively low melting points such that they contribute to the flame-retardant migration in the molded articles.
  • these liquid organic phosphate flame retardants can be characterized by melting points of 25 °C, or lower.
  • the concentration of these liquid organic phosphate flame retardants in the compositions should be low, preferably lower than the concentration of the non-migrating aromatic phosphate flame retardants.
  • liquid organic phosphate flame retardants that can optionally be included in the present compositions are aromatic polyphosphates, such as liquid RDP and bisphenol A diphosphate (BPADP) and monophosphate, such as tributoxy ethyl phosphate (TBEP), trimethyl phosphate (TMP) and triethyl phosphate (TEP).
  • aromatic polyphosphates such as liquid RDP and bisphenol A diphosphate (BPADP) and monophosphate, such as tributoxy ethyl phosphate (TBEP), trimethyl phosphate (TMP) and triethyl phosphate (TEP).
  • organic flame retardants that can be included in the present compositions include, phosphorus-based and nitrogen-based flame retardants. These include, but are not limited to, phosphoric acid salts, phosphonic acid salts, and nitrogen-containing flame retardants.
  • the compositions are free of liquid (at room temperature) organic flame retardants.
  • the compositions include no greater than 10 wt.%, no greater than 8 wt.%, or no greater than 5 wt.%, based on the total weight of the composition, of liquid (at room temperature) organic flame retardants.
  • the compositions can include 0.1 to 10 wt.%, based on the total weight of the composition, of liquid (at room temperature) organic flame retardants. This includes embodiments in which the compositions include 2 to 8 wt.%, based on the total weight of the composition, of liquid (at room temperature) organic flame retardants.
  • the compositions are free of all organic flame retardants, other than the non-migrating aromatic organic phosphate flame retardants.
  • the compositions include no greater than 10 wt.%, no greater than 8 wt.%, or no greater than 5 wt.%, based on the total weight of the composition, of organic flame retardants, other than the non- migrating aromatic organic phosphate flame retardants.
  • the compositions can include 0.1 to 10 wt.%, based on the total weight of the composition, of organic flame retardants, other than the non-migrating aromatic organic phosphate flame retardants. This includes embodiments in which the compositions include 2 to 8 wt.%, based on the total weight of the composition, of organic flame retardants, other than the non-migrating aromatic organic phosphate flame retardants.
  • the inorganic hydrates in the present compositions impart flame retardant properties to the compositions.
  • suitable examples include, but are not limited to, metal hydroxides, such as aluminum trihydroxide (also known as ATH or aluminum trihydrate) and magnesium hydroxide (also known as magnesium dihydroxide).
  • metal hydroxides such as aluminum trihydroxide (also known as ATH or aluminum trihydrate) and magnesium hydroxide (also known as magnesium dihydroxide).
  • Other examples include calcium hydroxide, basic calcium carbonate, basic magnesium carbonate, hydrotalcite, huntite, and hydromagnesite.
  • the inorganic hydrates are typically used in amounts of at least 20 wt.%, based on the total weight of the composition. This includes embodiments in which inorganic hydrates are used in amounts of at least 30 wt.%, based on the total weight of the composition. For example, in some embodiments, the inorganic hydrates are used in amounts of 20 to 50 wt.%, based on the total weight of the composition. This includes embodiments in which the inorganic hydrates are used in amounts of 30 to 40 wt.%, based on the total weight of the composition.
  • compositions can optionally include one or more char forming agents to prevent or minimize dripping during combustion.
  • some embodiments of the compositions include an epoxidized novolac resin as a char forming agent.
  • An "epoxidized novolac resin,” is the reaction product of epichlorohydrin and phenol novolac polymer in an organic solvent.
  • suitable organic solvents include acetone, methyl ethyl ketone, methyl amyl ketone, and xylene.
  • the epoxidized novolac resin may be a liquid, a semi-solid, a solid, and combinations thereof.
  • the epoxidized novolac resins are typically used in amounts ranging from 0.1 to 5 wt.%, based on the total weight of the composition. This includes embodiments in which the epoxidized novolac resins are used in amounts ranging from 1 to 3 wt.%, based on the total weight of the composition and further includes embodiments in which the epoxidized novolac resins are used in amounts ranging from 1.5 to 2.5 wt.%, based on the total weight of the composition.
  • compositions of this invention can, optionally, also contain additives and/or fillers.
  • additives include, but are not limited to, antioxidants, processing aids, colorants, ultraviolet stabilizers (including UV absorbers), antistatic agents, nucleating agents, slip agents, plasticizers, lubricants, viscosity control agents, tackifiers, anti-blocking agents, surfactants, extender oils, acid scavengers, and metal deactivators.
  • additives are typically used in a conventional manner and in conventional amounts, e.g., from 0.01 wt.% or less to 10 wt.% or more, based on the total weight of the composition.
  • Representative fillers include but are not limited to the various metal oxides, e.g., titanium dioxide; metal carbonates such as magnesium carbonate and calcium carbonate; metal sulfides and sulfates such as molybdenum disulfide and barium sulfate; metal borates such as barium borate, meta-barium borate, zinc borate and meta-zinc borate; metal anhydride such as aluminum anhydride; clay such as diatomite, kaolin and montmoriUonite; huntite; celite; asbestos; ground minerals; and lithopone.
  • These fillers are typically used a conventional manner and in conventional amounts, e.g., from 5 wt.% or less to 50 wt.% or more based on the weight of the composition.
  • Suitable UV light stabilizers include hindered amine light stabilizers (HALS) and UV light absorber (UVA) additives.
  • HALS hindered amine light stabilizers
  • UVA UV light absorber
  • antioxidants include, but are not limited to, hindered phenols such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydro-cinnamate)]methane; bis[(beta-(3,5-ditert- butyl-4-hydroxybenzyl)-methylcarboxyethyl)]sulphide, 4,4'-thiobis(2-methyl-6-tert-butylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol),and thiodiethylene bis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate; phosphites and phosphonites such as tris(2,4-di-tert-butylphenyl)phosphite and di-tert-butylphenyl-phosphonite; thio compounds such as d
  • processing aids include, but are not limited to, metal salts of carboxylic acids such as zinc stearate or calcium stearate; fatty acids such as stearic acid, oleic acid, or erucic acid; fatty amides such as stearamide, oleamide, erucamide, or ⁇ , ⁇ '-ethylene bis- stearamide; polyethylene wax; oxidized polyethylene wax; polymers of ethylene oxide; copolymers of ethylene oxide and propylene oxide; vegetable waxes; petroleum waxes; non ionic surfactants; silicone fluids and polysiloxanes.
  • carboxylic acids such as zinc stearate or calcium stearate
  • fatty acids such as stearic acid, oleic acid, or erucic acid
  • fatty amides such as stearamide, oleamide, erucamide, or ⁇ , ⁇ '-ethylene bis- stearamide
  • polyethylene wax oxidized polyethylene wax
  • compositions can be characterized by their resistance to migration, as well as their good mechanical and flame-retardant properties.
  • Wires coated with some embodiments of the present compositions generally exhibit a heat deformation ratio of less than 30% at 150 °C with a 350 gram load (3.5 ⁇ 0.2 N) according to UL 1581-2001. In some embodiments, the coated wires exhibit a heat deformation of no greater than 25 percent or even no greater than 20 percent, measured at 150 °C with a 350 gram load (3.5 ⁇ 0.2 N) according to UL 1581-2001.
  • VW-1 is an Underwriters' Laboratory (UL) flame rating for wire and sleeving. It denotes "Vertical Wire, Class 1 ", which is the highest flame rating a wire or sleeve can be given under the UL 1441 specification.
  • the test is performed by placing the wire or sleeve in a vertical position. A flame is set underneath it for a period of time, and then removed. The characteristics of the sleeve are then noted.
  • the VW-1 flame test is determined in accordance with method 1080 ofUL-1581.
  • the present compositions can be characterized by their tensile strength at break (in MPa) and elongation at break (%). Tensile strength and elongation can be measured in accordance with the ASTM D-638 testing procedure on compression molded samples prepared according to ASTM D4703. Elongation at break, or elongation to break, is the strain on a sample when it breaks. It usually is expressed as a percent.
  • compositions having tensile strengths at break of at least 10 MPa This includes compositions having tensile strength at break of at least 12 MPa and further includes compositions having a tensile strength at break of at least 15 MPa.
  • compositions having an elongation at break of at least 200% This includes compositions having an elongation at break of at least 300%, and further includes compositions having an elongation at break of at least 320%.
  • Melt Flow Rate is measured according to ASTM D 1238-04, Procedure C, Condition 190 °C/2.16 kg.
  • Some embodiments of the compositions have an MFR of at least 10 g/10 min. This includes compositions having an MFR of at least 12 g/10 min.
  • compositions can be formed by mixing the TPU, any additional polymers, the inorganic hydrate, the non-migrating phosphate flame retardant and any additional organic flame retardants, epoxidized novolac resins, additives and fillers.
  • the mixing can take place in a stepwise fashion or in a single step and can be carried out in a conventional tumbling device.
  • the compositions can be compounded at a temperature above the melting point of the non-migrating phosphate flame retardants.
  • Compounding of the compositions can be effected by standard compounding equipment.
  • compounding equipment are internal batch mixers, such as a BanburyTM or BoilingTM internal mixer.
  • continuous single, or twin screw, mixers can be used, such as a FarrelTM continuous mixer, a Werner and PfleidererTM twin screw mixer, or a BussTM kneading continuous extruder.
  • the type of mixer utilized, and the operating conditions of the mixer will affect properties of the composition such as viscosity, volume resistivity, and extruded surface smoothness.
  • the resulting compositions are desirably capable of being molded and shaped into an article, such as a wire jacket, profile, sheet or pellet for further processing.
  • Another aspect of the invention provides articles, such as molded or extruded articles, comprising one or more compositions of the present invention.
  • Articles include wire and cable jackets and insulation.
  • the article includes a metal conductor and a coating on the metal conductor to provide an "insulated" wire capable of electrical transmission.
  • a "metal conductor,” as used herein, is at least one metal component used to transmit either electrical power and/or electrical signals. Flexibility of wire and cables is often desired, so the metal conductor can have either a solid cross-section or preferentially can be composed of smaller wire strands that provide increased flexibility for the given overall conductor diameter. Cables are often composed of several components such as multiple insulated wires formed into an inner core, and then surrounded by a cable sheathing system providing protection and cosmetic appearance.
  • the cable sheathing system can incorporate metallic layers such as foils or armors, and typically has a polymer layer on the surface.
  • the one or more polymer layers incorporated into the protective/cosmetic cable sheathing are often referred to as cable "jacketing".
  • the sheathing is only a polymeric jacketing layer surrounding a cable core.
  • cables having a single layer of polymer surrounding the conductors performing both the roles of insulation and jacketing.
  • the present compositions may be used as, or in, the polymeric components in a full range of wire and cable products, including power cables and both metallic and fiber optic communication applications.
  • a cable containing an insulation layer comprising a composition of this invention can be prepared with various types of extruders, e.g., single or twin screw types.
  • thermoplastic compositions in accordance with the present invention.
  • the TPUs used in this example are polytetramethylene glycol ether TPU (PELLETHANETM 2103 -90 AE from Lubrizol Advanced Materials) and an ether based TPU (ESTANE® 58219 from Lubrizol Advanced Materials). Before using, the TPU samples are pre- dried at 90 °C for at least 6 hrs under vacuum.
  • Aluminum hydroxide (ATH) is used as the inorganic hydrate (grade H42M, from Showa Chemical).
  • Resorcinol bis(diphenyl phosphate) (RDP) (grade Fyrolflex® RDP from Supresta) is used in comparative example 1 and bis(diphenyl phosphate) (BDP) (obtained from Adeka with grade name FP600) is used as received in comparative example 2 and inventive examples 3-5.
  • RDP Resorcinol bis(diphenyl phosphate)
  • BDP bis(diphenyl phosphate)
  • the non-migrating aromatic organic phosphate flame retardants used in the inventive examples are resorcinol bis(dixylenyl phosphate) (PX-200 XPD from Daihachi Chemical) and high molecular weight powder RDP (p-RDP from Yoke Chemical) which is a solid at room temperature, having a melting point of 55-60 °C and an Mw of 670-680.
  • the examples include an epoxy novolac (DEN438 from Dow Chemical Company) and the following additives/fillers: (1) tetrafluroethylene-co-styrene-co-acrylonitrile (grade AD001 from Daikin); (2) Ti0 2 (R350 from DuPont); (3) an anti-oxidants (Irganox 1010 from Ciba Specialty Chemicals; Irgafosl26 from Ciba Specialty Chemicals; and Irgafos MD1024 from Ciba Specialty Chemicals); (4) a processing stabilizer (Irgafos 168 from Ciba Specialty Chemicals; (5) a UV stabilizer (Tinuvin 866 from Ciba Specialty Chemicals); and a color match additive (Clariant MB from Clariant).
  • tetrafluroethylene-co-styrene-co-acrylonitrile grade AD001 from Daikin
  • Ti0 2 R350 from DuPont
  • an anti-oxidants
  • compositions shown in Table A are prepared on a twin screw extruder and evaluated for extrusion characteristics and key properties. Both Comparative Examples (CEs) and Inventive Examples ( Es) are shown. The following steps are used in the material preparation and evaluation. In a 50L high speed mixer, all of the TPU resin and a portion of the aluminum oxide trihydrate filler is added and mixed for 10 seconds. The remaining aluminum oxide trihydrate is then added to the mixture, together with the solid phosphates (XDP or p-RDP) and, if present, the liquid phosphates (BDP and RDP). Pre-heated epoxidized novolac is gradually spooned into the mixer. Then the Irganox 1010 and Irgafos 168 additives are added.
  • CEs Comparative Examples
  • Es Inventive Examples
  • the tensile strength at break and the elongation at break are measured according to ASTM D-638 at room temperature and a speed of 50 mm/min.
  • the tensile testing is performed on a INSTRON 5565 Tensile Tester.
  • the specimen for the tensile tests are compression molded plaques prepared at a 185 °C molding temperature, using a low pressure cycle to facilitate melting, followed by exposure to high pressure to shape the 1.4x200x200mm plaques.
  • the mold is held at high pressure (15 MPa) and cooled to room temperature over a period of 8 min to solidify the plaques.
  • Mimic VW-1 testing is conducted in a UL-94 chamber.
  • the test specimens have dimensions of 200*2.7*1.9 mm.
  • the specimen is hanged on a clamp, with its longitudinal axis vertical by applying a 50 g load on to its lower end.
  • a paper flag (2 * 0.5 cm) is placed on the top of the wire.
  • the distance between the flame bottom (highest point of the burner oracle) and the bottom of flag is 18 cm.
  • the flame is applied continuously for 45 sec.
  • After flame time (AFT), uncharred wire length (UCL) and uncharred flag area percentage (flag uncharred) are recorded during and after combustion.
  • Four or five specimen are tested for each sample. Any of the following phenomena will result in a rating of "not pass”: (1) the cotton under the specimen is ignited; (2) the flag is burned out; or (3) dripping with flame is observed.
  • Heat deformation testing is conducted according to UL 1581-2001.
  • two parallel sample plaques are placed into an oven and preheated at 150 °C for one hour.
  • the preheated samples are then pressed with the same loading at 150 °C for one hour.
  • the pressed samples without removal of the weights, are placed in an ASTM room with setting temperature at 23 °C for an additional hour.
  • Non-migration tests are conducted with an assembly shoe shown in FIG. 1.
  • Two cables 102 composed of a composition in accordance with this invention are sandwiched between two plastic panels 104, which are further sandwiched between two glass panels 106 with a loading of 500g 108 on top of the assembly.
  • the plastic panels employed are PC, ABS, and PC/ ABS.
  • the cables are tested on each type of the three panels (i.e., three times— once each with each type of panel).
  • the diameters of the cables are not critical. Cables having diameters of about 0.5 mm to about 10 mm can be used.
  • the dimensions of each panel are 9 cm x 6 cm.
  • the two cables protrude past the pressing plate (width 60 mm).
  • a composition passes the non-migration test if no residue or etching is observed on the PC, ABS, and PC/ ABS panels after the test, as determined by visual inspection.
  • Comparative example 1 uses RDP as the phosphate-based flame retardant and Comparative example 2 uses BDP as the phosphate-based flame retardant. These two comparative examples, which are made with liquid phosphate flame retardants, fail the non- migration test, resulting in heavy etching on all the plastic panels.
  • Inventive examples 3 and 4 employ 2% BDP and 11.04% solid phosphate (PX-200 or P-RDP) as the phosphate-based flame retardant.
  • the two compositions also pass the non- migration test. At least equivalent burning performance and mechanical properties, relative to the comparative examples, are obtained.
  • Inventive example 5 employs 6.5% BDP and 6.5% solid phosphate (PX-200) as the phosphate-based flame retardant. This composition also passes the non-migration test. At least equivalent burning performance and mechanical properties, relative to the comparative examples, are obtained. The results of these examples show that with BDP loading as low as 2% or 6.5%, the final cable can pass the non-migration test.
  • the presence of BDP in the formulation can help pre-mixing of DEN438 in the formulation, which is a high viscosity liquid.

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

Abstract

L'invention concerne des compositions à base de polyuréthane thermoplastique sans halogène présentant de bonnes propriétés mécaniques et ignifugeantes. Les compositions comprennent des composés de phosphate organique aromatique ignifugeants qui ne présentent pas de migration dans les produits moulés, comme des produits de gainage et d'isolation de câbles et de fils. Les compositions comprennent une phase de résine continue comprenant un élastomère de polyuréthane thermoplastique, au moins un ignifugeant de type phosphate organique aromatique ayant un point de fusion d'au moins 50 °C et un ignifugeant de type hydrate inorganique.
PCT/CN2010/071473 2010-03-31 2010-03-31 Compositions de polyuréthane thermoplastique ignifugeant sans migration et sans halogène WO2011120225A1 (fr)

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PCT/CN2010/071473 WO2011120225A1 (fr) 2010-03-31 2010-03-31 Compositions de polyuréthane thermoplastique ignifugeant sans migration et sans halogène
TW100109107A TW201134925A (en) 2010-03-31 2011-03-17 Migration-free, halogen-free, flame retardant thermoplastic polyurethane compositions

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WO2013029250A1 (fr) * 2011-08-31 2013-03-07 Dow Global Technologies Llc Compositions de polyuréthane thermoplastique ignifuges exemptes d'halogène et exemptes de migration
US20130146330A1 (en) * 2011-12-07 2013-06-13 E I Du Pont De Nemours And Company Flame-retardant copolyetherester composition and articles comprising the same
WO2013085724A1 (fr) 2011-12-07 2013-06-13 E. I. Du Pont De Nemours And Company Composition de copolyétherester ignifuge et articles comprenant ladite composition
WO2013191902A1 (fr) * 2012-06-18 2013-12-27 Lubrizol Advanced Materials, Inc. Compositions de tpu ignifuges sans halogène à loi très élevé
WO2024017214A1 (fr) * 2022-07-21 2024-01-25 华为技术有限公司 Composition de résine thermoplastique, matériau de protection et câble à fibres optiques

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JP6789248B2 (ja) 2015-06-09 2020-11-25 ブローミン コンパウンズ リミテッド 織物のためのアンチモンフリー臭素化難燃剤システム

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EP1491580A1 (fr) * 2003-06-02 2004-12-29 Nexans Composition pour gaines de câble électrique ou optique
CN101570632A (zh) * 2009-06-16 2009-11-04 中纺投资发展股份有限公司 一种无卤阻燃热塑性聚氨酯塑料及其制备方法
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EP1491580A1 (fr) * 2003-06-02 2004-12-29 Nexans Composition pour gaines de câble électrique ou optique
WO2010012136A1 (fr) * 2008-07-30 2010-02-04 Dow Global Technologies Inc. Composition de polyuréthane ignifuge
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WO2013029250A1 (fr) * 2011-08-31 2013-03-07 Dow Global Technologies Llc Compositions de polyuréthane thermoplastique ignifuges exemptes d'halogène et exemptes de migration
US20140228490A1 (en) * 2011-08-31 2014-08-14 Journey Lu Zhu Migration-Free, Halogen-Free, Flame Retardant Thermoplastic Polyurethane Compositions
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US20130146330A1 (en) * 2011-12-07 2013-06-13 E I Du Pont De Nemours And Company Flame-retardant copolyetherester composition and articles comprising the same
WO2013085724A1 (fr) 2011-12-07 2013-06-13 E. I. Du Pont De Nemours And Company Composition de copolyétherester ignifuge et articles comprenant ladite composition
WO2013085725A1 (fr) 2011-12-07 2013-06-13 E. I. Du Pont De Nemours And Company Composition de copolyétherester retardant la flamme et articles comprenant ladite composition
US8759429B2 (en) * 2011-12-07 2014-06-24 E I Du Pont De Nemours And Company Flame-retardant copolyetherester composition and articles comprising the same
WO2013191902A1 (fr) * 2012-06-18 2013-12-27 Lubrizol Advanced Materials, Inc. Compositions de tpu ignifuges sans halogène à loi très élevé
CN104540924A (zh) * 2012-06-18 2015-04-22 路博润先进材料公司 具有非常高loi的无卤素阻燃tpu
US9920166B2 (en) 2012-06-18 2018-03-20 Lubrizol Advanced Materials, Inc. Halogen-free flame retardant TPU with very high LOI
CN104540924B (zh) * 2012-06-18 2019-11-12 路博润先进材料公司 具有非常高loi的无卤素阻燃tpu
WO2024017214A1 (fr) * 2022-07-21 2024-01-25 华为技术有限公司 Composition de résine thermoplastique, matériau de protection et câble à fibres optiques

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