EP2788365A1 - Composition de copolyétherester ignifuge et articles comprenant ladite composition - Google Patents

Composition de copolyétherester ignifuge et articles comprenant ladite composition

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Publication number
EP2788365A1
EP2788365A1 EP12795297.6A EP12795297A EP2788365A1 EP 2788365 A1 EP2788365 A1 EP 2788365A1 EP 12795297 A EP12795297 A EP 12795297A EP 2788365 A1 EP2788365 A1 EP 2788365A1
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EP
European Patent Office
Prior art keywords
ions
flame
phosphate
retardant
copolyetherester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP12795297.6A
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German (de)
English (en)
Inventor
Yong Ni
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of EP2788365A1 publication Critical patent/EP2788365A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • 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
    • 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
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • H01B3/427—Polyethers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the disclosure is related to flame-retardant copolyetherester compositions and articles comprising the same.
  • polymeric compositions based on copolyetherester elastomers Due to its excellent mechanical properties (e.g., tear strength, tensile strength, flex life, and abrasion resistance), polymeric compositions based on copolyetherester elastomers have been used in forming components for motorized vehicles and
  • copolyetherester based compositions also have low flammability and high thermal stability.
  • U.S. Patent No. 6,716,899 discloses the use of organic phosphorus-containing compounds as flame retardant synergists
  • U.S. Patent No. 6,365,071 discloses the use of nitrogen-containing compounds (e.g., melamine cyanurate, melamine phosphate, melamine pyrophosphate, or melamine diborate) as flame retardant synergists
  • U.S. Patent No. 6,255,371 discloses the use of reaction products of phosphoric acids with melamine or condensed product of melamine (e.g., melamine polyphosphate (MPP)) as flame retardant synergists.
  • MPP melamine polyphosphate
  • WO2009/047353 and WO2010/094560 each discloses flame retardant elastomeric compositions useful in forming the insulating layers and/or jackets of wires and cables.
  • combinations of i) a metal salt of a phosphinic acid and/or a diphosphinic acid, (ii) a nitrogen containing compound (e.g., melamine polyphosphate), and (iii) an inorganic compound (e.g., zinc borate) are taught as preferred flame retardant packages.
  • KR 2010038701 discloses a flame retardant package useful in copolyetherester, which comprises an organic phosphinate metal salt, a melamine cyanurate, and an aromatic phosphate.
  • a flame retardant package useful in copolyetherester which comprises an organic phosphinate metal salt, a melamine cyanurate, and an aromatic phosphate.
  • the present Applicant discovered that when such prior art flame retardant packages are used in copolyetherester compositions, the flame retardants tend to migrate to the surface over time and cause blooming.
  • a flame-retardant copolyetherester composition comprising: (a) at least one copolyetherester; (b) 5-35 wt% of at least one halogen-free flame retardant; (c) 0.1 -20 wt% of at least one nitrogen-containing compound; (d) 0.1 -10 wt% of at least one aromatic phosphate; and (e) 0.1 -10 wt% of at least at least one phenoxy resin, with the total wt% of all components of the copolyetherester composition totaling to 100 wt%, and wherein the at least one halogen-free flame retardant comprises at least one selected from the group consisting of phosphinates of the formula (I), disphosphinates of the formula (II), and combinations or polymers thereof
  • Ri and R2 being identical or different and each of Ri and R2 being hydrogen, a linear, branched, or cyclic Ci -C 6 alkyl group, or a C 6 -Ci 0 aryl;
  • R 3 being a linear or branched C C10 alkylene group, a C6-C10 arylene group, a C6-C12 alkyl-arylene group, or a C6-C12 aryl- alkylene group;
  • M being selected from calcium ions, aluminum ions, magnesium ions, zinc ions, antimony ions, tin ions, germanium ions, titanium ions, iron ions, zirconium ions, cerium ions, bismuth ions, strontium ions, manganese ions, lithium ions, sodium ions, potassium ions and combinations thereof; and m, n, and x each being a same or different integer of 1 -4.
  • the at least one copolyetherester is present at a level of 15-95 wt%, or 40-95 wt%, or 40-90 wt%, with the total wt% of all components of the copolyetherester composition totaling to 100 wt%.
  • the at least one halogen-free flame retardant, each of Ri and R2 is hydrogen, or the at least one halogen-free flame retardant is aluminum hypophosphite.
  • the at least one halogen-free flame retardant is present at a level of 5-30 wt% or 7.5-30 wt%, with the total wt% of all components of the copolyetherester composition totaling to 100 wt%.
  • the at least one nitrogen-containing compound is selected from the group consisting of (i) melamine cyanurate, (ii) condensation products of melamine, (iii) reaction products of phosphoric acid with melamine, and (iv) reaction products of phosphoric acid with condensation products of melamine, or the at least one nitrogen-containing compound is melamine cyanurate.
  • the at least one nitrogen-containing compound is present at a level of 1 -15 wt% or 2-15 wt%, with the total wt% of all components of the copolyetherester composition totaling to 100 wt%.
  • the at least one aromatic phosphate is selected from the group consisting of trialkyi phosphates, triaryl phosphates, trialkylaryl phosphates, and combinations of two or more thereof, or the at least one aromatic phosphate is selected from the group consisting of triphenyl
  • phosphate tri(4-methylphenyl)phosphate; tri(2,6-dimethylphenyl)phosphate; tri(2,4,6- trimethylphenyl)phosphate; tri(2,4-ditertiary butylphenyl)phosphate; tri(2,6-ditertiary butylphenyl)phosphate; resorcinol bis(diphenyl phosphate) (RDP); bisphenol A bis(diphenyl phosphate) (BDP); resorcinol bis(dixylenyl phosphate) (XDP); hydroquinol bis(diphenyl phosphate); resorcinol bis-(di-2,6-dimethylphenyl phosphate); 4,4'-biphenyl bis-(di-2,6- dimethylphenyl phosphate); and combinations of two or more thereof.
  • RDP bisphenol A bis(diphenyl phosphate)
  • BDP bisphenol A bis(diphenyl phosphate)
  • the at least one phenoxy resin has a structure of the formula (IV):
  • n an integer of 30-100 or 50-90.
  • the at least one phenoxy resin is present at a level of 0.1 -7.5 wt% or 0.1 -5 wt%, with the total wt% of all components of the copolyetherester composition totaling to 100 wt%.
  • an article comprising at least one component part formed of the flame-retardant copolyetherester composition described above, preferably the article is selected from motorized vehicle parts and electrical/electronic devices.
  • the article is selected from insulated wires and cables, and preferably, the insulated wires and cables comprise one or more insulating layers and/or insulating jackets that are formed of the flame-retardant copolyetherester composition described above.
  • the range includes any value that is within the two particular end points and any value that is equal to or about equal to any of the two end points.
  • a flame-retardant copolyetherester composition comprising,
  • copolyetheresters suitable for use in the compositions disclosed herein may be copolymers having a multiplicity of recurring long-chain ester units and recurring short- chain ester units joined head-to-tail through ester linkages, the long-chain ester units being represented by formula (I):
  • G is a divalent radical remaining after the removal of terminal hydroxyl groups from poly(alkylene oxide) glycols having a number average molecular weight of about 400-6000;
  • R is a divalent radical remaining after the removal of carboxyl groups from a dicarboxylic acid having a number average molecular weight of about 300 or less;
  • D is a divalent radical remaining after the removal of hydroxyl groups from a glycol having a number average molecular weight of about 250 or less
  • the at least one copolyetherester contains about 1 -85 wt% of the recurring long- chain ester units and about 15-99 wt% of the recurring short-chain ester units.
  • the copolyetherester used in the composition disclosed herein contains about 5-80 wt% of the recurring long-chain ester units and about 20-95 wt% of the recurring short-chain ester units.
  • the copolyetherester used in the composition disclosed herein contains about 10-75 wt% of the recurring long-chain ester units and about 25-90 wt% of the recurring short-chain ester units.
  • the copolyetherester used in the composition disclosed herein contains about 40-75 wt% of the recurring long-chain ester units and about 25-60 wt% of the recurring short-chain ester units.
  • long-chain ester units refers to reaction products of a long-chain glycol with a dicarboxylic acid.
  • Suitable long-chain glycols are poly(alkylene oxide) glycols having terminal hydroxyl groups and a number average molecular weight of about 400-6000, or about 600-3000, which include, without limitation, poly(tetramethylene oxide) glycol, poly(trimethylene oxide) glycol, polypropylene oxide) glycol, poly(ethylene oxide) glycol, copolymer glycols of these alkylene oxides, and block copolymers such as ethylene oxide-capped polypropylene oxide) glycol.
  • the long-chain glycols used herein may also be combinations of two or more of the above glycols.
  • the poly(alkylene oxide) glycols used herein are poly(tetramethylene oxide) glycols.
  • short-chain ester units refers to reaction products of a low molecular weight glycol or an ester-forming derivative thereof with a dicarboxylic acid.
  • Suitable low molecular weight glycols are those having a number average molecular weight of about 250 or lower, or about 10-250, or about 20-150, or about 50-100, which include, without limitation, aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, and aromatic dihydroxy compounds (including bisphenols).
  • the low molecular weight glycol used herein is a dihydroxy compound having 2-15 carbon atoms, such as ethylene glycol; propylene glycol; isobutylene glycol; 1 ,4-tetramethylene glycol; pentamethylene glycol; 2,2-dimethyltrimethylene glycol; hexamethylene glycol;
  • decamethylene glycol dihydroxycyclohexane; cyclohexanedimethanol; resorcinol;
  • the low molecular weight glycol used herein is a dihydroxy compound having 2-8 carbon atoms. In a yet further embodiment, the low molecular weight glycol used herein is 1 ,4- tetramethylene glycol.
  • Bisphenols that are useful herein include, without limitation, bis(p- hydroxy)diphenyl, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)propane, and mixtures of two or more thereof.
  • ester-forming derivatives of low molecular weight glycols useful herein include those derived from the low molecular weight glycols described above, such as ester- forming derivatives of ethylene glycol (e.g., ethylene oxide or ethylene carbonate) or ester- forming derivatives of resorcinol (e.g., resorcinol diacetate).
  • ester-forming derivatives of ethylene glycol e.g., ethylene oxide or ethylene carbonate
  • ester- forming derivatives of resorcinol e.g., resorcinol diacetate
  • the number average molecular weight limitations pertain to the low molecular weight glycols only. Therefore, a compound that is an ester-forming derivative of a glycol and has a number average molecular weight more than 250 can also be used herein, provided that the corresponding glycol has a number average molecular weight of about 250 or lower.
  • the "dicarboxylic acids" useful for reaction with the above described long-chain glycols or low molecular weight glycols are those low molecular weight (i.e., number average molecular weight of about 300 or lower, or about 10-300, or about 30-200, or about 50-100) aliphatic, alicyclic, or aromatic dicarboxylic acids.
  • aliphatic dicarboxylic acids used herein refers to those carboxylic acids having two carboxyl groups each attached to a saturated carbon atom. If the carbon atom to which the carboxyl group is attached to is saturated and is in a ring, the acid is referred to as an "alicyclic dicarboxylic acid".
  • aromatic dicarboxylic acids used herein refers to those dicarboxylic acids having two carboxyl groups each attached to a carbon atom in an aromatic ring structure. It is not necessary that both functional carboxyl groups in the aromatic dicarboxylic acid be attached to the same aromatic ring. Where more than one aromatic ring are present, they can be joined by aliphatic or aromatic divalent radicals or divalent radical such as -O- or -SO2-.
  • the aliphatic or alicyclic dicarboxylic acids useful herein include, without limitation, sebacic acid; 1 ,3-cyclohexane dicarboxylic acid; 1 ,4-cyclohexane dicarboxylic acid; adipic acid; glutaric acid; 4-cyclohexane-1 ,2-dicarboxylic acid; 2-ethyl suberic acid; cyclopentane dicarboxylic acid; decahydro-1 ,5-naphthylene dicarboxylic acid; 4,4'-bicyclohexyl
  • dicarboxylic acid decahydro-2,6-naphthylene dicarboxylic acid; 4,4'- methylenebis(cyclohexyl) carboxylic acid; 3,4-furan dicarboxylic acid; and combinations of two or more thereof.
  • the dicarboxylic acids used herein are selected from cyclohexane dicarboxylic acids, adipic acids, and combinations of two or more thereof.
  • aromatic dicarboxylic acids useful herein include, without limitation, phthalic acids; terephthalic acids; isophthalic acids; dibenzoic acids; dicarboxylic compounds with two benzene nuclei (such as bis(p-carboxyphenyl)methane; p-oxy-1 ,5-naphthalene dicarboxylic acid; 2,6-naphthalene dicarboxylic acid; 2,7-naphthalene dicarboxylic acid; or 4,4'-sulfonyl dibenzoic acid); and C1-C12 alkyl and ring substitution derivatives of the aromatic dicarboxylic acids described above (such as halo, alkoxy, and aryl derivatives thereof).
  • the aromatic dicarboxylic acids useful herein may also be, for example, hydroxyl acids such as p-( -hydroxyethoxy)benzoic acid.
  • the dicarboxylic acids used to form the copolyetheresters component may be selected from aromatic dicarboxylic acids.
  • the dicarboxylic acids may be selected from aromatic dicarboxylic acids having about 8-16 carbon atoms.
  • the dicarboxylic acids may be terephthalic acid alone or a mixture of terephthalic acid with phthalic acid and/or isophthalic acid.
  • dicarboxylic acids useful herein may also include functional
  • dicarboxylic acids reacts with the above described long-chain and low molecular weight glycols substantially the same way as dicarboxylic acids.
  • useful functional equivalents of dicarboxylic acids include ester and ester-forming derivatives of dicarboxylic acids, such as acid halides and anhydrides.
  • the number average molecular weight limitations pertain only to the corresponding dicarboxylic acids, not the functional equivalents thereof (such as the ester or ester-forming derivatives thereof).
  • a compound that is a functional equivalent of a dicarboxylic acid and has a number average molecular weight more than 300 can also be used herein, provided that the corresponding dicarboxylic acid has a number average molecular weight of about 300 or lower.
  • the dicarboxylic acids may also contain any substituent groups or combinations thereof that do not substantially interfere with the copolyetherester formation and the use of the copolyetherester in the compositions disclosed herein.
  • the long-chain glycols used in forming the copolyetherester component of the composition disclosed herein may also be mixtures of two or more long-chain glycols.
  • the low molecular weight glycols and dicarboxylic acids used in forming the copolyetherester component may also be mixtures of two or more low molecular weight glycols and mixtures of two or more dicarboxylic acids, respectively.
  • at least about 70 mol% of the groups represented by R in Formulas (I) and (II) above are 1 ,4-phenolene radicals, and at least 70 mol% of the groups represented by D in Formula (II) above are 1 ,4-butylene radicals.
  • the copolyetherester When two or more dicarboxylic acids are used in forming the copolyetherester, it is preferred to use a mixture of terephthalic acid and isophthalic acid, while when two or more low molecular weight glycols are used, it is preferred to use a mixture of 1 ,4-tetramethylene glycol and hexamethylene glycol.
  • the at least one copolyetherester comprised in the flame-retardant copolyetherester composition disclosed herein may also be a blend of two or more copolyetheresters. It is not required that the copolyetheresters comprised in the blend, individually meet the weight percentages requirements disclosed hereinbefore for the short-chain and long-chain ester units. However, the blend of two or more copolyetheresters must conform to the values described hereinbefore for the copolyetheresters on a weighted average basis.
  • one copolyetherester may contain about 10 wt% of the short-chain ester units and the other copolyetherester may contain about 80 wt% of the short-chain ester units for a weighted average of about 45 wt% of the short-chain ester units in the blend.
  • the at least one copolyetherester component comprised in the flame-retardant copolyetherester composition disclosed herein is obtained by the
  • the at least one copolyetherester is obtained by the copolymerization of an ester of terephthalic acid (e.g., dimethylterephthalate) with 1 ,4-tetramethylene glycol and poly(tetramethylene ether) glycol.
  • a dicarboxylic acid ester selected from esters of terephthalic acid, esters of isophthalic acid, and mixtures thereof, with a lower molecular weight glycol that is 1 ,4-tetramethylene glycol and a long-chain glycol that is poly(tetramethylene ether) glycol or ethylene oxide-capped polypropylene oxide glycol.
  • the at least one copolyetherester is obtained by the copolymerization of an ester of terephthalic acid (e.g., dimethylterephthalate) with 1 ,4-tetramethylene glycol and poly(tetramethylene ether) glycol.
  • copolyetheresters useful in the compositions disclosed herein may be made by any suitable methods known to those skilled in the art, such as by using a conventional ester interchange reaction.
  • the method involves heating an dicarboxylic acid ester (e.g., dimethylterephthalate) with a poly(alkylene oxide) glycol and a molar excess of a low molecular weight glycol (e.g., 1 ,4-tetramethylene glycol) in the presence of a catalyst, followed by distilling off methanol formed by the interchange reaction and continuing the heat until methanol evolution is complete.
  • a dicarboxylic acid ester e.g., dimethylterephthalate
  • a poly(alkylene oxide) glycol e.g., 1 ,4-tetramethylene glycol
  • the polymerization may be completed within a few minutes to a few hours and results in formation of a low molecular weight pre-polymer.
  • Such pre-polymers can also be prepared by a number of alternate esterification or ester interchange processes, for example, by reacting a long- chain glycol with a short-chain ester homopolymer or copolymer in the presence of catalyst until randomization occurs.
  • the short-chain ester homopolymer or copolymer can be prepared by the ester interchange either between a dimethyl ester (e.g.,
  • the short-chain ester homopolymer or copolymer can be prepared by direct esterification from appropriate acids (e.g., terephthalic acid), anhydrides (e.g., phthalic anhydride), or acid chlorides (e.g., terephthaloyl chloride) with glycols (e.g., 1 ,4-tetramethylene glycol).
  • the short-chain ester homopolymer or copolymer may be prepared by any other suitable processes, such as the reaction of dicarboxylic acids with cyclic ethers or carbonates.
  • the pre-polymers obtained as described above can be converted to high molecular weight copolyetheresters by the distillation of the excess low molecular weight glycols. Such process is known as "polycondensation". Additional ester interchange occurs during the polycondensation process to increase the molecular weight and to randomize the arrangement of the copolyetherester units.
  • the polycondensation may be run at a pressure of less than about 1 mmHg and a temperature of about 240-260°C, in the presence of antioxidants (such as 1 ,6-bis-(3,5-di- tert-butyl-4-hydroxyphenol)propionamido]-hexane or 1 ,3,5-trimethyl-2,4,6-tris[3,5-di-tert- butyl-4-hydroxybenzyl]benzene ), and for less than about 2 hours.
  • antioxidants such as 1 ,6-bis-(3,5-di- tert-butyl-4-hydroxyphenol)propionamido]-hexane or 1 ,3,5-trimethyl-2,4,6-tris[3,5-di-tert- butyl-4-hydroxybenzyl]benzene
  • catalysts can be used herein, which include, without limitation, organic titanates (such as tetrabutyl titanate alone or in combination with magnesium or calcium acetates), complex titanates (such as those derived from alkali or alkaline earth metal alkoxides and titanate esters), inorganic titanates (such as lanthanum titanate), calcium acetate/antimony trioxide mixtures, lithium and magnesium alkoxides, stannous catalysts, and mixtures of two or more thereof.
  • organic titanates such as tetrabutyl titanate alone or in combination with magnesium or calcium acetates
  • complex titanates such as those derived from alkali or alkaline earth metal alkoxides and titanate esters
  • inorganic titanates such as lanthanum titanate
  • calcium acetate/antimony trioxide mixtures lithium and magnesium alkoxides
  • stannous catalysts and mixtures of two or more thereof.
  • copolyetheresters useful in the compositions disclosed herein can also be obtained commercially from E.I. du Pont de Nemours and Company (U.S.A.) (hereafter "DuPont") under the trade name Hytrel®.
  • the at least one copolyetherester may be present at a level of about 25-95 wt%, or about 40-95 wt%, or about 40-90 wt%.
  • Halogen-free flame retardants suitable for use in the compositions disclosed herein may be selected from phosphinates of the formula (I), disphosphinates of the formula (II), and combinations or polymers thereof
  • Ri and R2 may be identical or different and each of Ri and R2 is hydrogen, a linear, branched, or cyclic Ci -Ce alkyl group, or a C6-C10 aryl group;
  • R3 is a linear or branched Ci- C10 alkylene group, a C6-C10 arylene group, a C6-C12 alkyl-arylene group, or a C6-C12 aryl- alkylene group;
  • M is selected from calcium ions, aluminum ions, magnesium ions, zinc ions, antimony ions, tin ions, germanium ions, titanium ions, iron ions, zirconium ions, cerium ions, bismuth ions, strontium ions, manganese ions, lithium ions, sodium ions, potassium ions and combinations thereof; each of m, n, and x is a same or different integer of 1 -4.
  • methylene ethylene, n-propylene, isopropylene, n-butylene, te/t-butylene, n-pentylene, n- octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, tert- butylphenylene, methylnaphthylene, ethylnaphthylene, terf-butylnaphthylene,
  • phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene; and M may be selected from aluminum and zinc ions. More preferably, the phosphinates used here may be selected from aluminum methylethylphosphinate, aluminum diethylphosphinate, and combinations thereof.
  • the halogen-free flame retardants useful herein may also be obtained commercially from Clariant (Switzerland) under the trade name ExolitTM OP.
  • the halogen-free flame retardant used herein is a aluminum hypophosphite, which may be obtained commercially from Italmatch Chemicals (Italy) under the trade name PhosliteTM IP-A.
  • the at least one halogen-free flame retardant may be present at a level of about 5-35 wt%, or about 5-30 wt%, or about 7.5-30 wt%.
  • the nitrogen containing compounds used herein may include, without limitation, those described, for example in U.S. Patent Nos. 6,365,071 ; and 7,255,814.
  • the nitrogen containing compounds used herein are selected from melamine, benzoguanamine, tris(hydroxyethyl)isocyanurate, allantoine, glycouril, dicyandiamide, guanidine, carbodiimide, and derivatives thereof.
  • the nitrogen containing compounds used herein may be selected from melamine derivatives, which include, without limitation, (i) melamine cyanurate, (ii) condensation products of melamine, (iii) reaction products of phosphoric acid with melamine, and (iv) reaction products of phosphoric acid with condensation products of melamine.
  • Suitable condensation products may include, without limitation, melem, melam, melon, as well as higher derivatives and mixtures thereof.
  • Condensation products of melamine can be produced by any suitable methods (e.g., those described in PCT Patent Publication No. WO9616948).
  • Reaction products of phosphoric acid with melamine or reaction products of phosphoric acid with condensation products of melamine are herein understood compounds, which result from the reaction of melamine with a phosphoric acid or the reaction of a condensation product of melamine (e.g., melem, melam, or melon) with a phosphoric acid.
  • Examples include, without limitation, dimelaminephosphate, dimelamine pyrophosphate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate, and melem polyphosphate, as are described, e.g., in PCT Patent Publication No. WO9839306.
  • the at least one nitrogen containing compound used herein is selected from melamine phosphate and melamine cyanurate.
  • the at least one nitrogen containing compound used herein is melamine cyanurate.
  • the at least one nitrogen containing compound may be present at a level of about 0.1 -20 wt%, or about 1 -15 wt%, or about 2-15 wt%.
  • aromatic phosphate used herein may be represented by the following general formula (III):
  • n indicates an integer of 0 or more, and the compound may be a mixture with different integers of n.
  • k and m each indicates an integer of 0-2, and (k+m) is an integer of 0-2.
  • k and m each is an integer of 0 or 1 ; more preferably, k and m are both 1 .
  • Ar 1 , Ar 2 , Ar 3 , and Ar 4 in formula (III) are the same or different, and each represents a phenyl group, or a phenyl group substituted by an organic residue containing no halogen.
  • X in formula (III) represents any of the following:
  • R 2 to R 9 are the same or different, and each represents a hydrogen atom, or an alkyl group having from 1 to 5 carbon atoms.
  • the alkyl group having from 1 to 5 carbon atoms are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, etc.
  • preferred are a hydrogen atom, a methyl group, and an ethyl group; and more preferred is a hydrogen atom.
  • Y represents a direct bond, O, S, SO2, C(CH 3 )2, CH 2 , or CHPh, with Ph representing a phenyl group.
  • Exemplary aromatic phosphates used herein include, without limitation, triaryl phosphates (e.g., triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate) and trialkylaryl phosphates (e.g., octyldiphenyl phosphate).
  • triaryl phosphates e.g., triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate
  • trialkylaryl phosphates e.g., octyldiphenyl phosphate
  • the aromatic phosphates used herein are selected from triphenyl phosphate; tri(4- methylphenyl)phosphate; tri(2,6-dimethylphenyl)phosphate; tri(2,4,6- trimethylphenyl)phosphate; tri(2,4-ditertiary butylphenyl)phosphate; tri(2,6-ditertiary butylphenyl)phosphate; resorcinol bis(diphenyl phosphate) (RDP); bisphenol A bis(diphenyl phosphate) (BDP); resorcinol bis(dixylenyl phosphate) (XDP) hydroquinol bis(diphenyl phosphate); resorcinol bis-(di-2,6-dimethylphenyl phosphate); 4,4'-biphenyl bis-(di-2,6- dimethylphenyl phosphate); and the like.
  • aromatic phosphates used herein may also be obtained commercially from Daihachi Chemical Industry Co., Ltd. (Japan) under the trade name PX-200 (resorcinol bis- (di-2,6-dimethylphenyl phosphate), CAS Number: 139189-30-3) or PX-202 (4,4'-biphenyl bis-(di-2,6-dimethylphenyl phosphate), CAS Number: 147263-99-8) .
  • PX-200 resorcinol bis- (di-2,6-dimethylphenyl phosphate), CAS Number: 139189-30-3)
  • PX-202 4,4'-biphenyl bis-(di-2,6-dimethylphenyl phosphate), CAS Number: 147263-99-8) .
  • the at least one aromatic phosphate may be present at a level of about 0.1 -10 wt%, or about 0.1 -7.5 wt%, or about 0.1 -5 wt%.
  • the phenoxy resins used herein are high molecular weight thermoplastic
  • the phenoxy resins used herein have the following basic formula (IV)
  • n is an integer from 30-100 or from 50-90.
  • the phenoxy resins used herein may also be obtained commercially from Tohto Kasei Co., Ltd. (Japan) under the trade name PhenotohtoTM YP-50, PhenotohtoTM YP-50S, PhenotohtoTM YP-55, PhenotohtoTM YP-70, or FX280; or from Japan Epoxy Resins Co., Ltd. (Japan) under the trade name JER1256, JER4250, or JER4275; or from InChem
  • PKHB PKHB
  • PKHC PKHH
  • PKHJ PKFE
  • PKHP-200 PKHP-80
  • PKHB-100 PKHB-300.
  • the at least one phenoxy resin may be present at a level of about 0.1 -10 wt%, or about 0.1 -7.5 wt%, or about 0.1 -5 wt%.
  • the flame-retardant copolyetherester composition disclosed herein may further comprise other additives, such as colorants, antioxidants, UV stabilizers, UV absorbers, heat stabilizers, lubricants, tougheners, impact modifiers, reinforcing agents, viscosity modifiers, nucleating agents, plasticizers, mold release agents, scratch and mar modifiers, impact modifiers, emulsifiers, pigments, optical brighteners, antistatic agents, fillers, and combinations of two or more thereof.
  • Suitable fillers may be selected from calcium
  • carbonates silicates, talcum, carbon black, and combinations of two or more thereof.
  • such additional additive(s) may be present at a level of about 0.01 -20 wt% or about 0.01 -10 wt%, or about 0.2-5 wt%, or about 0.5-2 wt%.
  • copolyetherester compositions disclosed herein are melt-mixed blends, wherein all of the polymeric components are well-dispersed within each other and all of the non- polymeric ingredients are homogeneously dispersed in and bound by the polymer matrix, such that the blend forms a unified whole. Any melt-mixing method may be used to combine the polymeric components and non-polymeric ingredients of the composition disclosed herein.
  • thermoplastic polyurethane elastomers the addition of solid phosphates (such as XDP or resorcinol bis-(di-2,6-dimethylphenyl phosphate)) instead of liquid phosphates (such as BDP or RDP) may solve the blooming issue.
  • solid phosphates such as XDP or resorcinol bis-(di-2,6-dimethylphenyl phosphate)
  • liquid phosphates such as BDP or RDP
  • articles comprising one or more component parts formed of the flame-retardant copolyetherester compositions disclosed herein, wherein the articles include, without limitation, motorized vehicles, electrical/electronic devices, furniture, footwear, roof structure, outdoor apparels, water management system, etc.
  • the articles are selected from motorized vehicles.
  • the flame-retardant copolyetherester compositions disclosed herein may be used to form component parts such as airduct, constant velocity joint (CVJ) boot, etc.
  • the articles are selected from electrical/electronic devices.
  • the flame-retardant copolyetherester composition disclosed herein may be used to form insulating layers or jacket for wire and cable.
  • the articles may be selected from wires and cables, which comprise insulating layers and/or jackets formed of the flame-retardant copolyetherester compositions disclosed herein.
  • the article may be an insulated wire or cable, which comprises two or three electrically conductive cores, two or three insulating layers each surrounding one of the electrically conductive cores, and optionally a insulating jacket surrounding the electrically conductive cores and the insulating layers, wherein the insulating layers and/or the insulating jacket are formed of the flame-retardant copolyetherester composition disclosed herein.
  • Copolyetherester- 1 copolyetherester elastomer obtained from DuPont under the trade name Hytrel® 3078;
  • Copolvetherester-2 copolyetherester elastomer obtained from DuPont under the trade name Hytrel® G4074;
  • ⁇ AO-2 trisarylphosphite processing stabilizer obtained from BASF under the trade name IrgafosTM 168;
  • FR a flame retardant masterbatch comprising 60 wt% of aluminum hypophosphite (obtained from Italmatch under the trade name PhosliteTM IP-A) and 40 wt% of copolyetherester (obtained from DuPont under the trade name Hytrel® 3078);
  • ⁇ MC melamine cyanurate obtained from Hangzhou JLS Flame Retardants Chemical Co., Ltd. (China) under the trade name JLS-MC15;
  • Aromatic Phosphate resorcinol bis-(di-2,6-dimethylphenyl phosphate obtained from Daihachi Chemical Industry Co., Ltd. (Japan) under the trade name PX-200;
  • Phenoxy phenoxy resin obtained from InChem Corporation (U.S.A.) under the
  • a copolyetherester composition resin was prepared as follows: appropriate amounts of copolyetherester, flame retardants, and other additives were dried, pre-mixed, and melt blended in a ZSK26 twin-screw extruder (purchased from Coperion Werner & Pfleiderer GmbH & Co., Germany) with the extruder temperature set at 190-210°C, the extrusion speed at 300 rpm, and the throughput at 20 kg/hr.
  • insulated conducting wires were prepared using the resin obtained above, wherein each of the insulated conducting wires had a circular cross section and a diameter of about 2 mm, and wherein each of the insulated conducting wires had an insulating jacket made of the copolyetherester composition and encircling conductive core that was made of 91 stranded copper wires.
  • VW-1 the flammability
  • tensile-strength the tensile-strength
  • ultimate-elongation of the insulated conducting wires as such prepared were measured and results are tabulated in Table 1 below.
  • 100x100x2 mm molding plaques were prepared by injection molding with the temperature of the molding machine set at 190-210°C and the
  • the molding plaques in each example were conditioned in a climate controlled chamber that was set at 65°C and 95% relative humidity (RH) for 3 days.

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Abstract

La présente invention concerne une composition de copolyétherester ignifuge qui comprend: (a) au moins un copolyétherester; (b) environ 5 à 35 % en poids d'au moins un agent retardateur de flamme sans halogène; (c) environ 0,1 à 20 % en poids d'au moins un composé contenant de l'azote; (d) environ 0,1 à 10 % en poids d'un phosphate aromatique et (e) environ 0,1 à 10 % en poids d'au moins une résine phénoxy. L'invention concerne également des articles comprenant des parties constitutives formées à partir de la composition de copolyétherester retardant la flamme.
EP12795297.6A 2012-11-24 2012-11-24 Composition de copolyétherester ignifuge et articles comprenant ladite composition Withdrawn EP2788365A1 (fr)

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EP3359596A1 (fr) 2015-10-09 2018-08-15 Sasol (USA) Corporation Composition d'ester de phosphate et utilisation
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