US20230340255A1 - Copolyetherester - Google Patents

Copolyetherester Download PDF

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US20230340255A1
US20230340255A1 US17/996,483 US202117996483A US2023340255A1 US 20230340255 A1 US20230340255 A1 US 20230340255A1 US 202117996483 A US202117996483 A US 202117996483A US 2023340255 A1 US2023340255 A1 US 2023340255A1
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aluminium
acid
copolyetherester
mixtures
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Eleni Karayianni
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DuPont Polymers Inc
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DuPont Polymers Inc
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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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/20—Tetrahydrofuran
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing 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
    • C08K5/16—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
    • C08K5/34922—Melamine; Derivatives thereof
    • 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
    • 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
    • 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
    • H01B3/421—Polyesters
    • 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
    • H01B3/421—Polyesters
    • H01B3/422—Linear saturated polyesters derived from dicarboxylic acids and dihydroxy 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/327—Aluminium phosphate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/329—Phosphorus containing acids
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

Definitions

  • the present invention relates to the field of copolyetheresters, particularly flame-retardant copolyetheresters.
  • Copolyetheresters are a group of elastomeric polyesters having hard segments comprising polyester blocks and soft segments comprising long-chain polyether diols. They are widely used in applications in which resilience and elasticity are required.
  • a typical copolyetherester is made by reacting one or more diacid moieties with a short-chain diol and a long-chain polyether diol.
  • Copolyetheresters show excellent elasticity, maintenance of mechanical properties at low temperature and good fatigue performance.
  • Dialkyl phosphinate salts are well-known, non-halogenated flame retardant molecules.
  • U.S. Pat. No. 7,420,007 [Clariant Kunststoff (Deutschland) GmbH] describes the use of dialkylphosphinic salts of the formula (I):
  • R 1 , R 2 are identical or different and are C 1 -C 6 -alkyl linear or branched;
  • M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or is a protonated nitrogen base; and m is from 1 to 4; as flame-retardants in many different polymers, including polyetheresters.
  • US2013/0190432 describes the use of aluminium diethyl phosphinate together with the aluminium salt of phosphorous acid as a flame-retardant stabilizer combination in nylon-6,6, nylon-6T/6,6, nylon-4,6, and PBT.
  • the invention provides a flame-retardant polymer composition comprising:
  • the invention provides a flame-retardant copolyetherester composition
  • a flame-retardant copolyetherester composition comprising:
  • the invention provides a shaped article made from a flame-retardant copolyetherester composition comprising:
  • the invention provides a cable comprising a light or electrical conducting core and at least one sheath made from a flame-retardant copolyetherester composition comprising:
  • the invention provides a method for making a composition of the invention, comprising the step of:
  • Copolyetheresters suitable for the compositions of the invention are polymers made by reacting a C 2 -C 6 diol with an aromatic diacid moiety and a poly(alkyleneoxide)diol.
  • the poly(alkyleneoxide)diol is preferably selected from poly(ethyleneoxide)diol, poly(propyleneoxide)diol, poly(tetramethyleneoxide)diol (“PTMEG”), and mixtures of two or more of these.
  • the poly(propyleneoxide)diol, poly(tetramethylene-oxide)diol may be straight-chain or branched. If they are branched at a carbon containing the terminal hydroxyl, they are preferably end-capped with ethylene glycol or poly(ethyleneoxide)diol.
  • Particularly preferred are poly(propyleneoxide)diol and poly(tetramethyleneoxide)diol (“PTMEG”), and mixtures of these, with PTMEG being more particularly preferred.
  • the C 2 -C 6 diol is preferably selected from ethylene glycol, propylene glycol, butylene glycol, and mixtures of two or more of these, with butylene glycol being more preferred.
  • the aromatic diacid is preferably selected from terephthalate, iso-phthalate, and mixtures of these, with terephthalate being particularly preferred.
  • copolyetheresters are selected from:
  • copolyetherester made from butylene diol, terephthalate and PTMEG.
  • copolyetherester made from butylene diol, terephthalate, isophthalate and PTMEG.
  • copolyetheresters is affected by the chain-length (i.e. molecular weight) of the poly(alkyleneoxide)diol and by the relative amount of poly(alkyleneoxide)diol that is used to make the polymer.
  • the poly(alkyleneoxide)diol has a molecular weight of at or about 2000 g/mol.
  • the poly(alkyleneoxide)diol constitutes from 40 wt % to 80 wt % of the copolyetherester based on the total weight of the copolyetherester, more preferably 50 to 75 wt %, particularly preferably 72.5 wt %.
  • the copolyetherester comprises a poly(alkyleneoxide)diol having a molecular weight of at or about 2000 g/mol at 40 wt % to 80 wt % of the copolyetherester, based on the total weight of the copolyetherester, more preferably 50 to 75 wt %, particularly preferably 72.5 wt %.
  • a particularly preferred copolyetherester comprises at or about 72.5 weight percent of polytetramethylene oxide, preferably having an average molecular weight of about 2000 g/mol, as polyether block segments, the weight percentage being based on the total weight of the copolyetherester elastomer, the short chain ester units of the copolyetherester being polybutylene terephthalate segments.
  • compositions of the invention comprise aluminium diethyl phosphinate (“DEPAI”).
  • the total phosphinate concentration is 2 to 25 wt %, more preferably 10 to 20 wt %, particularly 15 wt %, based on the total weight of the copolyetherester composition.
  • the DEPAI has a D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ⁇ 10 microns.
  • compositions of the invention comprise at least one aluminium salt of phosphorous acid (“Al phosphite”).
  • Phosphorous acid is also referred to as phosphonic acid, HP( ⁇ O)(OH) 2 .
  • Phosphorous acid has tautomeric forms as shown below:
  • Salts of phosphorous acid are also referred to as phosphites.
  • Preferred aluminium phosphites are those having the CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [56287-23-1], [156024-71-4], [71449-76-8] and [15099-32-8].
  • Particularly preferred are aluminium phosphites of the type Al 2 (HPO 3 ) 3 *0.1-30 Al 2 O 3 *0-50H 2 O, more preferably of the type Al 2 (HPO 3 ) 3 *0.2-20 Al 2 O 3 *0-50H 2 O, most preferably of the type Al 2 (HPO 3 ) 3 *1-3 Al 2 O 3 *0-50H 2 O.
  • aluminium phosphite having the CAS number [56287-23-1].
  • the aluminium phosphite has a D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ⁇ 10 microns.
  • aluminium phosphite [56287-23-1] having a D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ⁇ 10 microns.
  • compositions of the invention may additionally comprise a zinc salt of phosphorous acid (Zn phosphite).
  • Phosphorous acid is also referred to as phosphonic acid, HP( ⁇ O)(OH) 2 .
  • Phosphorous acid has tautomeric forms as shown below:
  • Salts of phosphorous acid are also referred to as phosphites.
  • Zinc and aluminium phosphites comprise reaction products of phosphorous acid with compounds of the respective metal.
  • Zinc salts of phosphorous acid are also referred to herein as zinc phosphites. Particularly preferred is zinc phosphite having CAS number [14332-59-3], depicted below.
  • the zinc phosphite has a particle size of D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ⁇ 10 microns.
  • the zinc phosphite preferably has particle sizes from 0.1 to 100 ⁇ m and particularly preferably from 0.1 to 30 ⁇ m.
  • zinc phosphite [14332-59-3] having a D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ⁇ 10 microns.
  • the composition of the invention comprises zinc phosphite having CAS number [14332-59-3] and aluminium phosphite having the CAS number [56287-23-1].
  • the composition comprises aluminium phosphite having the CAS number [56287-23-1] and having a D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ⁇ 10 microns.
  • the total phosphite concentration is preferably greater than 0.5 wt %.
  • the total phosphite concentration is from 3 to 15 wt %, more preferably 5 to 8 wt %, based on the total weight of the copolyetherester composition.
  • Aluminium phosphite is preferably used at a concentration of from 3 to 10 wt %, more preferably 5 to 8 wt %.
  • the aluminium phosphite having CAS number [CAS 56287-23-1] is used at 3 to 10 wt %, more preferably 5 to 8 wt %.
  • copolyetherester compositions of the invention additionally comprise component (D) at least one melamine derivative, selected from melamine salts with organic or inorganic acids and mixtures of these. Particularly preferred are salts of melamine with boric acid, cyanuric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, and mixtures of two or more of these.
  • Component (D) is preferably present at 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, based on the total weight of the copolyetherester composition.
  • Particularly preferred as component (D) is melamine pyrophosphate, particularly at 2 to 15 wt %, more preferably at 5 to 12 wt %, particularly preferably 8 wt %, based on the total weight of the copolyetherester composition.
  • Component (D) preferably has a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone.
  • melamine pyrophosphate having a mean particle diameter of 15 microns, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone, particularly at 2-15 wt %, more preferably 4 to 12 wt %, based on the total weight of the copolyetherester composition.
  • compositions comprise the ingredients listed below, or consist of the ingredients listed below:
  • copolyetherester compositions described herein may additionally comprise (B′) 0.2 to 16% by weight of aluminum salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid and/or dihexylphosphinic acid, or mixtures of two or more of these.
  • Component (B′) when present, is preferably selected from aluminium salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, and mixtures of two or more of these.
  • copolyetherester compositions described herein may additionally comprise (E) 0 to 10% by weight of one or more inorganic synergists selected from zinc borate, zinc stannate, boehmite and hydrotalcite.
  • copolyetherester compositions described herein may additionally comprise (F) 0 to 3% by weight of an organic phosphonite and/or a mixture of an organic phosphonite and an organic phosphite.
  • copolyetherester compositions described herein may additionally comprise (G) 0 to 3% by weight of an ester and/or salt of long-chain aliphatic carboxylic acids (fatty acids) which typically have chain lengths of C 14 to C 40 .
  • fatty acids long-chain aliphatic carboxylic acids
  • Particularly preferred are stearic acid and its esters and/or salts, and esters and/or salts of montanic acid, in particular calcium salts.
  • flame-retardant mixture refers to all of the components of the copolyether composition, excluding only the copolyetherester.
  • the copolyetherester composition comprises a flame-retardant mixture comprising the following components:
  • the copolyetherester composition comprises a flame-retardant mixture comprising the following components:
  • the copolyetherester composition comprises a flame-retardant mixture comprising the following components:
  • the copolyetherester composition comprises a flame-retardant mixture comprising the following components:
  • the copolyetherester composition comprises a flame-retardant mixture comprising the following components:
  • copolyetherester compositions described herein may further comprise one or more optional additives that include, but are not limited to, one or more of the following components as well as combinations of two or more of these: metal deactivators, such as hydrazine and hydrazide; heat stabilizers; antioxidants; modifiers; colorants, lubricants, fillers and reinforcing agents, impact modifiers, flow enhancing additives, antistatic agents, crystallization promoting agents, conductive additives, viscosity modifiers, nucleating agents, plasticizers, mold release agents, scratch and mar modifiers, drip suppressants, adhesion modifiers and other processing aids known in the polymer compounding art.
  • metal deactivators such as hydrazine and hydrazide
  • heat stabilizers such as heat stabilizers; antioxidants; modifiers; colorants, lubricants, fillers and reinforcing agents, impact modifiers, flow enhancing additives, antistatic agents, crystallization promoting agents, conductive additives, viscosity
  • the additives are selected from the group consisting of stabilizers, processing agents, metal deactivators, antioxidants, UV stabilizers, heat stabilizers, dyes and/or pigments.
  • the total amount of these additives is preferably about 0.05 to about 10 weight percent, based on the total weight of the copolyetherester formulation.
  • compositions of the invention show excellent flammability performance. Flammability can be assessed by methods known to one skilled in the art. One method is Limiting Oxygen Index (“LOI”) according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7 ⁇ 0.1 mm.
  • LOI Limiting Oxygen Index
  • compositions of the invention show an LOI of 19 or greater, more preferably 21 or greater, more particularly preferably 23 or greater or 25 or greater when measured according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7 ⁇ 0.1 mm.
  • compositions of the invention show a ratio of LOI of the composition incorporating the DEPAI and metal phosphite(s) and component (D) to LOI of the composition without component (D) of about 0.75 or greater, more preferably 0.8 or greater, more particularly preferably 0.86 or greater when measured according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7 ⁇ 0.1 mm.
  • compositions showing good flammability performance produce excessive smoke on exposure to heat and/or flame.
  • the compositions of the invention achieve a superior combination of good flammability performance and reduced smoke production.
  • Smoke density testing can be performed according to ISO 5659 test standard inside a NBS smoke chamber.
  • Test specimens are prepared as plaques having an area of 75 mm ⁇ 75 mm and thickness of 2 mm.
  • the specimens are mounted horizontally within the chamber and exposed to a constant thermal irradiance on their upper surface of 25 kW/m 2 via a radiator cone and heat flux meter and in the presence of a pilot flame for a period of about 10 min.
  • the smoke evolved over time is collected in the chamber, and the attenuation of a light beam passing through the smoke is measured with a photometric system including a 6.5 V incandescent lamp, a photomultiplier tube, and a high accuracy photodetector.
  • D s is inversely proportional to light transmission and is given for a specific path length equal to the thickness of the molded specimen.
  • Smoke production is measured as max specific optical density, and the total smoke production during the first 4 min of the test, VOF4.
  • VOF4 is calculated as: D s1min +D s2min +D s3min +(D s4min /2), where D s1min , D s2min , D s3min , and D s4min are the values of the specific optical density recorded at the 1 st , 2 nd , 3 rd and 4 th minutes respectively.
  • the parameters VOF4 and D s,max, ret can be used to evaluate smoke performance.
  • compositions of the invention preferably show a VOF4 measured according to ISO 5659 test standard and using plaques having an area of 75 mm ⁇ 75 mm and thickness of 2 mm, of not greater than 800, more preferably not greater than 600, more particularly not greater than 500.
  • compositions of the invention preferably show a D s,max, ret measured according to ISO 5659 test standard and using plaques having an area of 75 mm ⁇ 75 mm and thickness of 2 mm, of not greater than 45, more preferably not greater than 35, more particularly not greater than 30.
  • compositions of the invention preferably show a ratio of D s,max, ret, ex of the composition including the DEPAI and metal phosphite(s) and component (D) to D s,max, ret, 0 of the composition without component (D) measured according to ISO 5659 test standard and using plaques having an area of 75 mm ⁇ 75 mm and thickness of 2 mm, of not greater than 0.8, more preferably not greater than 0.6, more particularly not greater than 0.5.
  • the compositions of the invention have an LOI of 21 or greater, more preferably 23 or greater, more particularly preferably 25 or greater when measured according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7 ⁇ 0.1 mm, and a D s,max, ret measured according to ISO 5659 test standard and using plaques having an area of 75 mm ⁇ 75 mm and thickness of 2 mm, of not greater than 45, more preferably not greater than 35, more particularly not greater than 30.
  • the compositions of the invention have a ratio of LOI of the composition incorporating the DEPAI and metal phosphite(s) and component (D) to LOI of the composition with DEPAI alone of about 0.75 or greater, more preferably 0.9 or greater, more particularly preferably 1.0 or greater when measured according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7 ⁇ 0.1 mm, and a ratio of D s,max, ret, ex of the composition including the DEPAI and metal phosphite(s) and component (D) to D s,max, ret, 0 of the composition DEPAI alone measured according to ISO 5659 test standard and using plaques having an area of 75 mm ⁇ 75 mm and thickness of 2 mm, of not greater than 0.7, more preferably not greater than 0.6, more particularly not greater than 0.5.
  • compositions of the invention are made by melt blending the ingredients until a homogeneous blend is obtained. Melt-blending can be carried out, for example, in a twin-screw extruder.
  • compositions of the invention are suited to any use in which flame retardancy and reduced smoke production are important.
  • the compositions of the invention are suitable for making moulded articles (injection moulding, blow-moulding), extruded articles, films, filaments and/or fibres.
  • the compositions of the invention are particularly suited to housings for electrical connectors, parts in contact with current in power distributors, circuit boards, casting compounds, current plugs, circuit breakers, lamp housings, LED lamp housings, capacitor housings, bobbins, fans, protective contacts, plugs, in/on circuit boards, housings for plugs, cables, flexible printed circuit boards, charging cables, and motor covers.
  • Some particularly preferred applications include wire and cable sheathing (including optical cables), automotive uses, trains and aeronautic uses.
  • a particularly preferred application is wire and cable, in which a light-conducting element or an electrically conductive element or both are surrounded by a sheath made from a composition of the invention.
  • the invention thus extends to wires and cables comprising an electrically conductive element as core, such as a metal wire (for example copper, silver, etc.) and a sheath made from a composition of the invention.
  • the invention also extends to optical cables, comprising a light-conducting element as core and a sheath made from a composition of the invention.
  • a preferred method for making cables or wires according to the invention is co-axial extrusion.
  • the conductive element is fed through a die while the sheath of composition is extruded around it.
  • the wire or cable may comprise other elements in the core, such as reinforcing structures or fibers. It may additionally comprise additional sheathing materials both interior to the sheath of the composition of the invention or exterior to the sheath of the composition of the invention.
  • the sheath of the composition of the invention may serve as the insulation, the jacket or both.
  • Copolyetherester a copolyetherester elastomer comprising about 72.5 weight percent of copolymerized polytetramethylene oxide having an average molecular weight of about 2000 g/mol as polyether block segments, the weight percentage being based on the total weight of the copolyetherester elastomer, the short chain ester units of the copolyetherester being polybutylene terephthalate segments.
  • the copolyetherester elastomer contained up to 6 weight percent of heat stabilizers, antioxidants and metal deactivators.
  • Flammability testing was performed according to Limiting Oxygen Index (“LOI”) Test method ISO 4589-1/-2.
  • Test specimen were prepared from the compositions of the tables by melt-extruding narrow flat strips in a standard extruder having barrel temperatures set at about 170° C. to about 190° C. and cutting test specimens, in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7 ⁇ 0.1 mm, from the thus-obtained flat strips.
  • Test specimens were conditioned for at least 72 hours at room temperature and 50% relative humidity before testing.
  • LOI is the minimum concentration of oxygen, expressed as a volume percentage, required to sustain the combustion of the sample indicated by a target burning time after ignition of less than 180 sec. High values of LOI are desirable and indicative of less easily ignited and less flammable material.
  • Smoke density testing was performed according to ISO 5659 test standard inside a NBS smoke chamber, supplied by Fire Testing Technologies.
  • Test specimens were prepared from the compositions of the tables by melt-extruding narrow flat strips in a standard extruder having barrel temperatures set at about 170° C. to about 190° C. and compression molding the strips to form plaques having an area of 75 mm ⁇ 75 mm and thickness of 2 mm.
  • the specimens were mounted horizontally within the chamber and exposed to a constant thermal irradiance on their upper surface of 25 kW/m 2 via a radiator cone and heat flux meter and in the presence of a pilot flame for a period of about 40 min.
  • the smoke evolved over time was collected in the chamber, and the attenuation of a light beam passing through the smoke was measured with a photometric system including a 6.5 V incandescent lamp, a photomultiplier tube, and a high accuracy photodetector.
  • the results were measured in terms of light transmission over time and reported in terms of specific optical density, D s .
  • D s is inversely proportional to light transmission and is given for a specific path length equal to the thickness of the molded specimen. Comparison between the material compositions is made via the measurement of max specific optical density, D s,max and the total smoke production during the first 4 min of the test, VOF4.
  • VOF4 is calculated as: D s1min +D s2min +D s3min +(D s4min /2), where D s1min , D s2min , D s3min , and D s4min are the values of the specific optical density recorder at the 1 st , 2 nd , 3 rd and 4 th minutes respectively. Any dripping from the plaque test specimen occurring during the test is recorded. The weight of the dripped material is subtracted from the weight of the 75 mm ⁇ 75 mm ⁇ 2 mm test plaque. This difference is reported in grams as the “mass retained” during experiment time. A normalised D s,max can be calculated by dividing D s,max over the mass retained during the experiment time, and is reported as D s, max, ret .
  • D s,max and VOF4 values were calculated automatically by the software of the NBS smoke chamber.
  • the software is consistent with the applicable ISO standard. Low values of D s,max,ret and VOF4 are desirable and indicative of material that will have a less adverse effect on visibility in the event of fire, and thus will present a lesser obstacle to the rapid escape of people from confined spaces. Without any smoke, light transmittance is 100% and D s is 0.
  • compositions designated with “CE” are comparative, and compositions designated with “E” are inventive.
  • Table 1 shows comparative copolyetherester compositions CE3 (DEPAI alone) and CE4 (DEPAI+Al phosphite) as well as a composition according to the invention (DEPAI+Al phosphite+melamine pyrophosphate).
  • the inventive compositions have good flame retardancy as evidenced by an LOI of 25.
  • LOI ex LOI 0 means the ratio of the LOI of the experimental material (i.e., containing DEPAI plus phosphite plus MDP), to the LOI of the control material (i.e., containing DEPAI alone).
  • D s, max, ret, ex /D s, max, ret, 0 means the ratio of the D s, max, ret of the experimental material (i.e., containing DEPAI plus phosphite plus MDP), to the D s, max, ret of the control material (i.e., containing DEPAI alone).

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Abstract

The invention provides a copolyetherester compositions that are resistant to burning and which show reduced smoke production when exposed to heat or flame.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application claims priority under 35 U.S.C. § 365 to U.S. Provisional Application Nos. 63/039,098; 63/039,133; and 63/039,171, each of which was filed on Jun. 15, 2020, and each of which is incorporated herein by reference in its entirety.
    • FIELD OF THE INVENTION
  • The present invention relates to the field of copolyetheresters, particularly flame-retardant copolyetheresters.
    • BACKGROUND OF THE INVENTION
  • Several patents, patent applications and publications are cited in this description in order to more fully describe the state of the art to which this invention pertains. The entire disclosure of each of these patents, patent applications and publications is incorporated by reference herein.
  • Copolyetheresters are a group of elastomeric polyesters having hard segments comprising polyester blocks and soft segments comprising long-chain polyether diols. They are widely used in applications in which resilience and elasticity are required.
  • A typical copolyetherester is made by reacting one or more diacid moieties with a short-chain diol and a long-chain polyether diol.
  • Copolyetheresters show excellent elasticity, maintenance of mechanical properties at low temperature and good fatigue performance.
  • There is an ongoing need for non-halogen-containing fire resistant (“NHFR”) copolyetheresters. Dialkyl phosphinate salts are well-known, non-halogenated flame retardant molecules. U.S. Pat. No. 7,420,007 [Clariant Produkte (Deutschland) GmbH] describes the use of dialkylphosphinic salts of the formula (I):
  • Figure US20230340255A1-20231026-C00001
  • where R1, R2 are identical or different and are C1-C6-alkyl linear or branched;
  • M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or is a protonated nitrogen base; and m is from 1 to 4; as flame-retardants in many different polymers, including polyetheresters. US2013/0190432 describes the use of aluminium diethyl phosphinate together with the aluminium salt of phosphorous acid as a flame-retardant stabilizer combination in nylon-6,6, nylon-6T/6,6, nylon-4,6, and PBT.
  • While the use of flame retardants in polymer resins can significantly reduce flammability, it can unfortunately result in high smoke production upon exposure to heat or flame. This is of concern since smoke can be a significant contributor to damage and mortality in fires.
  • There is a need for resin and flame-retardant combinations that show not only reduced flammability but also reduced smoke production on exposure to heat and/or flames.
    • SUMMARY OF THE INVENTION
  • In a first aspect, the invention provides a flame-retardant polymer composition comprising:
      • (A) at least one polymer selected from copolyetherester, polyamide elastomer, thermoplastic polyolefinic elastomers, styrenic elastomer, thermoplastic polyurethane, thermoplastic vulcanisate;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) at least one melamine derivative, selected from melamine salts with organic or inorganic acids and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
  • In a second aspect, the invention provides a flame-retardant copolyetherester composition comprising:
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) at least one melamine derivative, selected from melamine salts with organic or inorganic acids and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
  • In a third aspect, the invention provides a shaped article made from a flame-retardant copolyetherester composition comprising:
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) at least one melamine derivative, selected from melamine salts with organic or inorganic acids and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
  • In a fourth aspect, the invention provides a cable comprising a light or electrical conducting core and at least one sheath made from a flame-retardant copolyetherester composition comprising:
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) at least one melamine derivative, selected from melamine salts with organic or inorganic acids and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
  • In a fifth aspect, the invention provides a method for making a composition of the invention, comprising the step of:
      • melt-mixing the ingredients listed above, and optionally others, in an extruder.
    DETAILED DESCRIPTION OF THE INVENTION Definitions and Abbreviations
      • PBT poly(butylene terephthalate)
      • PTMEG polytetramethylene ether glycol
      • Copolyetherester or TPC thermoplastic elastomer arising from the reaction of at least one diol, at least one diacid and at least one poly(alkylenoxide)diol
      • DEPAI aluminum diethylphosphinate salt
      • MDP melamine pyrophosphate, also known as melamine diphosphate
      • Phosphite as used herein is synonymous with “salt of phosphorous acid” or “salt of phosphonic acid”
  • Copolyetheresters suitable for the compositions of the invention are polymers made by reacting a C2-C6 diol with an aromatic diacid moiety and a poly(alkyleneoxide)diol.
  • The poly(alkyleneoxide)diol is preferably selected from poly(ethyleneoxide)diol, poly(propyleneoxide)diol, poly(tetramethyleneoxide)diol (“PTMEG”), and mixtures of two or more of these. The poly(propyleneoxide)diol, poly(tetramethylene-oxide)diol may be straight-chain or branched. If they are branched at a carbon containing the terminal hydroxyl, they are preferably end-capped with ethylene glycol or poly(ethyleneoxide)diol. Particularly preferred are poly(propyleneoxide)diol and poly(tetramethyleneoxide)diol (“PTMEG”), and mixtures of these, with PTMEG being more particularly preferred.
  • The C2-C6 diol is preferably selected from ethylene glycol, propylene glycol, butylene glycol, and mixtures of two or more of these, with butylene glycol being more preferred.
  • The aromatic diacid is preferably selected from terephthalate, iso-phthalate, and mixtures of these, with terephthalate being particularly preferred.
  • Particularly preferred copolyetheresters are selected from:
      • 1. Copolyetheresters made from butylene diol, terephthalate and PTMEG;
      • 2. Copolyetheresters made from butylene diol, a mixture of terephthalate and isophthalate, and PTMEG;
      • 3. Copolyetheresters made from butylene diol, terephthalate and poly(propyleneoxide)diol;
      • 4. Copolyetheresters made from propylene diol, terephthalate and PTMEG; and
      • 5. Copolyetheresters made from propylene diol, terephthalate and poly(propyleneoxide)diol.
  • Particularly preferred is a copolyetherester made from butylene diol, terephthalate and PTMEG.
  • Particularly preferred is a copolyetherester made from butylene diol, terephthalate, isophthalate and PTMEG.
  • The softness of copolyetheresters is affected by the chain-length (i.e. molecular weight) of the poly(alkyleneoxide)diol and by the relative amount of poly(alkyleneoxide)diol that is used to make the polymer.
  • In a preferred embodiment, the poly(alkyleneoxide)diol has a molecular weight of at or about 2000 g/mol.
  • In another preferred embodiment, the poly(alkyleneoxide)diol constitutes from 40 wt % to 80 wt % of the copolyetherester based on the total weight of the copolyetherester, more preferably 50 to 75 wt %, particularly preferably 72.5 wt %.
  • In a particularly preferred embodiment, the copolyetherester comprises a poly(alkyleneoxide)diol having a molecular weight of at or about 2000 g/mol at 40 wt % to 80 wt % of the copolyetherester, based on the total weight of the copolyetherester, more preferably 50 to 75 wt %, particularly preferably 72.5 wt %.
  • A particularly preferred copolyetherester comprises at or about 72.5 weight percent of polytetramethylene oxide, preferably having an average molecular weight of about 2000 g/mol, as polyether block segments, the weight percentage being based on the total weight of the copolyetherester elastomer, the short chain ester units of the copolyetherester being polybutylene terephthalate segments.
  • In addition to at least one copolyetherester, the compositions of the invention comprise aluminium diethyl phosphinate (“DEPAI”).
  • The total phosphinate concentration is 2 to 25 wt %, more preferably 10 to 20 wt %, particularly 15 wt %, based on the total weight of the copolyetherester composition.
  • In a preferred embodiment, the DEPAI has a D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ≤10 microns.
  • The compositions of the invention comprise at least one aluminium salt of phosphorous acid (“Al phosphite”). Phosphorous acid is also referred to as phosphonic acid, HP(═O)(OH)2.
  • Phosphorous acid has tautomeric forms as shown below:
  • Figure US20230340255A1-20231026-C00002
  • Salts of phosphorous acid are also referred to as phosphites.
  • Preferred aluminium phosphites are those having the CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [56287-23-1], [156024-71-4], [71449-76-8] and [15099-32-8]. Particularly preferred are aluminium phosphites of the type Al2(HPO3)3*0.1-30 Al2O3*0-50H2O, more preferably of the type Al2(HPO3)3*0.2-20 Al2O3*0-50H2O, most preferably of the type Al2(HPO3)3*1-3 Al2O3*0-50H2O.
  • Particularly preferred are mixtures of aluminium phosphite and aluminium hydroxide having the composition of 5-95% by weight of Al2(HPO3)3*nH2O and 95-5% by weight of Al(OH)3, more preferably 10-90% by weight of Al2(HPO3)3*nH2O and 90-10% by weight of Al(OH)3, most preferably 35-65% by weight of Al2(HPO3)3*nH2O and 65-35% by weight of Al(OH)3 and in each case n=0 to 4.
  • Particularly preferred is the aluminium phosphite having the CAS number [56287-23-1].
  • In a preferred embodiment, the aluminium phosphite has a D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ≤10 microns.
  • Particularly preferred is aluminium phosphite [56287-23-1] having a D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ≤10 microns.
  • The compositions of the invention may additionally comprise a zinc salt of phosphorous acid (Zn phosphite). Phosphorous acid is also referred to as phosphonic acid, HP(═O)(OH)2.
  • Phosphorous acid has tautomeric forms as shown below:
  • Figure US20230340255A1-20231026-C00003
  • Salts of phosphorous acid are also referred to as phosphites.
  • Zinc and aluminium phosphites comprise reaction products of phosphorous acid with compounds of the respective metal.
  • Zinc salts of phosphorous acid are also referred to herein as zinc phosphites. Particularly preferred is zinc phosphite having CAS number [14332-59-3], depicted below.
  • Figure US20230340255A1-20231026-C00004
  • In a preferred embodiment, the zinc phosphite has a particle size of D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ≤10 microns. Alternatively, the zinc phosphite preferably has particle sizes from 0.1 to 100 μm and particularly preferably from 0.1 to 30 μm.
  • Particularly preferred is zinc phosphite [14332-59-3] having a D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ≤10 microns.
  • In a preferred embodiment, the composition of the invention comprises zinc phosphite having CAS number [14332-59-3] and aluminium phosphite having the CAS number [56287-23-1].
  • In a particularly preferred embodiment, the composition comprises aluminium phosphite having the CAS number [56287-23-1] and having a D95 (volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone) of ≤10 microns.
  • In compositions of the invention the total phosphite concentration is preferably greater than 0.5 wt %. Preferably the total phosphite concentration is from 3 to 15 wt %, more preferably 5 to 8 wt %, based on the total weight of the copolyetherester composition.
  • Aluminium phosphite is preferably used at a concentration of from 3 to 10 wt %, more preferably 5 to 8 wt %. Preferably the aluminium phosphite having CAS number [CAS 56287-23-1] is used at 3 to 10 wt %, more preferably 5 to 8 wt %.
  • The copolyetherester compositions of the invention additionally comprise component (D) at least one melamine derivative, selected from melamine salts with organic or inorganic acids and mixtures of these. Particularly preferred are salts of melamine with boric acid, cyanuric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, and mixtures of two or more of these.
  • Component (D) is preferably present at 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, based on the total weight of the copolyetherester composition. Particularly preferred as component (D) is melamine pyrophosphate, particularly at 2 to 15 wt %, more preferably at 5 to 12 wt %, particularly preferably 8 wt %, based on the total weight of the copolyetherester composition.
  • Component (D) preferably has a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone. Particularly preferred is melamine pyrophosphate having a mean particle diameter of 15 microns, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone, particularly at 2-15 wt %, more preferably 4 to 12 wt %, based on the total weight of the copolyetherester composition.
  • Some particularly preferred compositions comprise the ingredients listed below, or consist of the ingredients listed below:
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) at least one melamine derivative selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) at least one melamine derivative selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these, having a mean particle diameter of less than 20 microns, more preferably microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) melamine pyrophosphate;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) melamine pyrophosphate having a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, of at least one melamine derivative selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, at least one melamine derivative selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these, having a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, melamine pyrophosphate;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, melamine pyrophosphate having a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite selected from CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [56287-23-1], [156024-71-4], [71449-76-8], [15099-32-8] and mixtures of two or more of these; and
      • (D) at least one melamine derivative selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite selected from CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [56287-23-1], [156024-71-4], [71449-76-8], [15099-32-8] and mixtures of two or more of these; and
      • (D) at least one melamine derivative selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these, having a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite selected from CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [56287-23-1], [156024-71-4], [71449-76-8], [15099-32-8] and mixtures of two or more of these; and
      • (D) melamine pyrophosphate;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite selected from CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [56287-23-1], [156024-71-4], [71449-76-8], [15099-32-8] and mixtures of two or more of these; and
      • (D) melamine pyrophosphate having a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite selected from CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [56287-23-1], [156024-71-4], [71449-76-8], [15099-32-8] and mixtures of two or more of these; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite selected from CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [56287-23-1], [156024-71-4], [71449-76-8], [15099-32-8] and mixtures of two or more of these; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these, having a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite selected from CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [56287-23-1], [156024-71-4], [71449-76-8], [15099-32-8] and mixtures of two or more of these; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, melamine pyrophosphate;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite selected from CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [56287-23-1], [156024-71-4], [71449-76-8], [15099-32-8] and mixtures of two or more of these; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, melamine pyrophosphate having a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite of CAS number [56287-23-1]; and
      • (D) at least one melamine derivative selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite of CAS number [56287-23-1]; and
      • (D) at least one melamine derivative selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these, having a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite of CAS number [56287-23-1]; and
      • (D) melamine pyrophosphate;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite of CAS number [56287-23-1]; and
      • (D) melamine pyrophosphate having a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite of CAS number [56287-23-1]; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, of at least one melamine derivative selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite of CAS number [56287-23-1]; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, of at least one melamine derivative selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these, having a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite of CAS number [56287-23-1]; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, melamine pyrophosphate;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium phosphite of CAS number [56287-23-1]; and
      • (D) 1 to 15 wt %, more preferably 2 to 15 wt %, more particularly preferably 5 to 12 wt %, melamine pyrophosphate having a mean particle diameter of less than 20 microns, more preferably 15 microns or less, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester made from butylene diol, terephthalate and PTMEG;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) at least one melamine derivative, selected from melamine salts with organic or inorganic acids and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester made from butylene diol, terephthalate and PTMEG;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) aluminium salt of phosphorous acid [CAS 56287-23-1]; and
      • (D) at least one melamine derivative, selected from melamine salts with organic or inorganic acids and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester made from butylene diol, terephthalate and PTMEG;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these;
      • wherein the weight percentages are based on the total weight of the composition.
      • (A) at least one copolyetherester made from butylene diol, terephthalate and PTMEG;
      • (B) 2 to 25 wt % aluminium diethylphosphinate;
      • (C) at least one aluminium salt of phosphorous acid; and
      • (D) melamine pyrophosphate;
      • wherein the weight percentages are based on the total weight of the composition.
  • The copolyetherester compositions described herein may additionally comprise (B′) 0.2 to 16% by weight of aluminum salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid and/or dihexylphosphinic acid, or mixtures of two or more of these.
  • Component (B′), when present, is preferably selected from aluminium salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, and mixtures of two or more of these.
  • The copolyetherester compositions described herein may additionally comprise (E) 0 to 10% by weight of one or more inorganic synergists selected from zinc borate, zinc stannate, boehmite and hydrotalcite.
  • The copolyetherester compositions described herein may additionally comprise (F) 0 to 3% by weight of an organic phosphonite and/or a mixture of an organic phosphonite and an organic phosphite.
  • The copolyetherester compositions described herein may additionally comprise (G) 0 to 3% by weight of an ester and/or salt of long-chain aliphatic carboxylic acids (fatty acids) which typically have chain lengths of C14 to C40. Particularly preferred are stearic acid and its esters and/or salts, and esters and/or salts of montanic acid, in particular calcium salts.
  • The term “flame-retardant mixture” as used herein refers to all of the components of the copolyether composition, excluding only the copolyetherester.
  • In a particularly preferred embodiment, the copolyetherester composition comprises a flame-retardant mixture comprising the following components:
      • 20 to 97.8 wt % (B);
      • 0.2 to 16 wt % (B′);
      • 1 to 80 wt % (C);
      • 1 to 80 wt % (D);
      • wherein the sum of components equals 100 wt % based on the total weight of the flame-retardant mixture.
  • In a particularly preferred embodiment, the copolyetherester composition comprises a flame-retardant mixture comprising the following components:
      • 20 to 97.6 wt % (B);
      • 0.2 to 16 wt % (B′);
      • 1 to 50 wt % (C);
      • 1 to 30 wt % (D);
      • 0 to 10 wt % (E);
      • 0.1 to 2 wt % (F);
      • 0.1 to 2 wt % (G);
      • wherein the sum of components equals 100 wt % based on the total weight of the flame-retardant mixture.
  • In a particularly preferred embodiment, the copolyetherester composition comprises a flame-retardant mixture comprising the following components:
      • 20 to 97.6 wt % (B);
      • 0.2 to 16 wt % (B′);
      • 1 to 30 wt % (C);
      • 1 to 10 wt % (D);
      • 0 to 10 wt % (E);
      • 0.1 to 2 wt % (F);
      • 0.1 to 2 wt % (G);
      • wherein the sum of components equals 100 wt % based on the total weight of the flame-retardant mixture.
  • In a particularly preferred embodiment, the copolyetherester composition comprises a flame-retardant mixture comprising the following components:
      • 20 to 96.6 wt % (B);
      • 0.2 to 16 wt % (B′);
      • 1 to 50 wt % (C);
      • 1 to 10 wt % (D);
      • 0 to 10 wt % (E);
      • 0.1 to 2 wt % (F);
      • 0.1 to 2 wt % (G);
      • wherein the sum of components equals 100 wt % based on the total weight of the flame-retardant mixture.
  • In a particularly preferred embodiment, the copolyetherester composition comprises a flame-retardant mixture comprising the following components:
      • 20 to 96.6 wt % (B);
      • 0.2 to 16 wt % (B′);
      • 1 to 50 wt % (C);
      • 1 to 10 wt % (D);
      • 1 to 10 wt % (E);
      • 0.1 to 2 wt % (F);
      • 0.1 to 2 wt % (G);
      • wherein the sum of components equals 100 wt % based on the total weight of the flame-retardant mixture.
  • The copolyetherester compositions described herein may further comprise one or more optional additives that include, but are not limited to, one or more of the following components as well as combinations of two or more of these: metal deactivators, such as hydrazine and hydrazide; heat stabilizers; antioxidants; modifiers; colorants, lubricants, fillers and reinforcing agents, impact modifiers, flow enhancing additives, antistatic agents, crystallization promoting agents, conductive additives, viscosity modifiers, nucleating agents, plasticizers, mold release agents, scratch and mar modifiers, drip suppressants, adhesion modifiers and other processing aids known in the polymer compounding art. Preferably, the additives are selected from the group consisting of stabilizers, processing agents, metal deactivators, antioxidants, UV stabilizers, heat stabilizers, dyes and/or pigments. When used, the total amount of these additives is preferably about 0.05 to about 10 weight percent, based on the total weight of the copolyetherester formulation.
  • The compositions of the invention show excellent flammability performance. Flammability can be assessed by methods known to one skilled in the art. One method is Limiting Oxygen Index (“LOI”) according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7±0.1 mm.
  • Preferably the compositions of the invention show an LOI of 19 or greater, more preferably 21 or greater, more particularly preferably 23 or greater or 25 or greater when measured according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7±0.1 mm.
  • Preferably the compositions of the invention show a ratio of LOI of the composition incorporating the DEPAI and metal phosphite(s) and component (D) to LOI of the composition without component (D) of about 0.75 or greater, more preferably 0.8 or greater, more particularly preferably 0.86 or greater when measured according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7±0.1 mm.
  • Often compositions showing good flammability performance produce excessive smoke on exposure to heat and/or flame. The compositions of the invention achieve a superior combination of good flammability performance and reduced smoke production.
  • Smoke density testing can be performed according to ISO 5659 test standard inside a NBS smoke chamber. Test specimens are prepared as plaques having an area of 75 mm×75 mm and thickness of 2 mm. The specimens are mounted horizontally within the chamber and exposed to a constant thermal irradiance on their upper surface of 25 kW/m2 via a radiator cone and heat flux meter and in the presence of a pilot flame for a period of about 10 min. The smoke evolved over time is collected in the chamber, and the attenuation of a light beam passing through the smoke is measured with a photometric system including a 6.5 V incandescent lamp, a photomultiplier tube, and a high accuracy photodetector. The results are measured in terms of light transmission over time and reported in terms of specific optical density, Ds. Ds is inversely proportional to light transmission and is given for a specific path length equal to the thickness of the molded specimen. Smoke production is measured as max specific optical density, and the total smoke production during the first 4 min of the test, VOF4. VOF4 is calculated as: Ds1min+Ds2min+Ds3min+(Ds4min/2), where Ds1min, Ds2min, Ds3min, and Ds4min are the values of the specific optical density recorded at the 1st, 2nd, 3rd and 4th minutes respectively. Any dripping from the plaque test specimen occurring during the test is recorded. The weight of the dripped material is subtracted from the weight of the 75 mm×75 mm×2 mm test plaque. This difference is reported in grams as the “mass retained” during experiment time. A normalised Ds,max can be calculated by dividing Ds,max over the mass retained during the experiment time, and is reported as Ds, max, ret.
  • Low values of Ds,max, ret and VOF4 are desirable and indicative of material that will less distract visibility in the event of fire, thus allowing rapid escape of people from confined spaces. Without any smoke light transmittance is 100% and Ds is 0.
  • The parameters VOF4 and Ds,max, ret can be used to evaluate smoke performance.
  • The compositions of the invention preferably show a VOF4 measured according to ISO 5659 test standard and using plaques having an area of 75 mm×75 mm and thickness of 2 mm, of not greater than 800, more preferably not greater than 600, more particularly not greater than 500.
  • The compositions of the invention preferably show a Ds,max, ret measured according to ISO 5659 test standard and using plaques having an area of 75 mm×75 mm and thickness of 2 mm, of not greater than 45, more preferably not greater than 35, more particularly not greater than 30.
  • The compositions of the invention preferably show a ratio of Ds,max, ret, ex of the composition including the DEPAI and metal phosphite(s) and component (D) to Ds,max, ret, 0 of the composition without component (D) measured according to ISO 5659 test standard and using plaques having an area of 75 mm×75 mm and thickness of 2 mm, of not greater than 0.8, more preferably not greater than 0.6, more particularly not greater than 0.5.
  • In a more particularly preferred embodiment, the compositions of the invention have an LOI of 21 or greater, more preferably 23 or greater, more particularly preferably 25 or greater when measured according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7±0.1 mm, and a Ds,max, ret measured according to ISO 5659 test standard and using plaques having an area of 75 mm×75 mm and thickness of 2 mm, of not greater than 45, more preferably not greater than 35, more particularly not greater than 30.
  • In a more particularly preferred embodiment, the compositions of the invention have a ratio of LOI of the composition incorporating the DEPAI and metal phosphite(s) and component (D) to LOI of the composition with DEPAI alone of about 0.75 or greater, more preferably 0.9 or greater, more particularly preferably 1.0 or greater when measured according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7±0.1 mm, and a ratio of Ds,max, ret, ex of the composition including the DEPAI and metal phosphite(s) and component (D) to Ds,max, ret, 0 of the composition DEPAI alone measured according to ISO 5659 test standard and using plaques having an area of 75 mm×75 mm and thickness of 2 mm, of not greater than 0.7, more preferably not greater than 0.6, more particularly not greater than 0.5.
  • The compositions of the invention are made by melt blending the ingredients until a homogeneous blend is obtained. Melt-blending can be carried out, for example, in a twin-screw extruder.
  • The compositions of the invention are suited to any use in which flame retardancy and reduced smoke production are important. In particular, the compositions of the invention are suitable for making moulded articles (injection moulding, blow-moulding), extruded articles, films, filaments and/or fibres. The compositions of the invention are particularly suited to housings for electrical connectors, parts in contact with current in power distributors, circuit boards, casting compounds, current plugs, circuit breakers, lamp housings, LED lamp housings, capacitor housings, bobbins, fans, protective contacts, plugs, in/on circuit boards, housings for plugs, cables, flexible printed circuit boards, charging cables, and motor covers. Some particularly preferred applications include wire and cable sheathing (including optical cables), automotive uses, trains and aeronautic uses.
  • A particularly preferred application is wire and cable, in which a light-conducting element or an electrically conductive element or both are surrounded by a sheath made from a composition of the invention. The invention thus extends to wires and cables comprising an electrically conductive element as core, such as a metal wire (for example copper, silver, etc.) and a sheath made from a composition of the invention. The invention also extends to optical cables, comprising a light-conducting element as core and a sheath made from a composition of the invention.
  • A preferred method for making cables or wires according to the invention is co-axial extrusion. In this method, the conductive element is fed through a die while the sheath of composition is extruded around it. The wire or cable may comprise other elements in the core, such as reinforcing structures or fibers. It may additionally comprise additional sheathing materials both interior to the sheath of the composition of the invention or exterior to the sheath of the composition of the invention. The sheath of the composition of the invention may serve as the insulation, the jacket or both.
  • The invention is further illustrated by certain embodiments in the examples below which provide greater detail for the compositions, uses and processes described herein. These examples, which set forth a preferred mode presently contemplated for carrying out the invention, are intended to illustrate and not to limit the invention.
    • EXAMPLES
  • Materials
  • The following materials were used to prepare the flame-retardant polymer compositions described herein and the compositions of the comparative examples.
  • Copolyetherester (TPC): a copolyetherester elastomer comprising about 72.5 weight percent of copolymerized polytetramethylene oxide having an average molecular weight of about 2000 g/mol as polyether block segments, the weight percentage being based on the total weight of the copolyetherester elastomer, the short chain ester units of the copolyetherester being polybutylene terephthalate segments. The copolyetherester elastomer contained up to 6 weight percent of heat stabilizers, antioxidants and metal deactivators.
      • DEPAI: Aluminium diethylphosphinate.
      • Al Phosphite: Phosphorous acid, Aluminium salt [CAS 56287-23-1]
      • Melamine pyrophosphate (MDP): melamine pyrophosphate having a mean particle diameter of 15 microns, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone.
  • Test Methods
  • Flame Retardance
  • Flammability testing was performed according to Limiting Oxygen Index (“LOI”) Test method ISO 4589-1/-2. Test specimen were prepared from the compositions of the tables by melt-extruding narrow flat strips in a standard extruder having barrel temperatures set at about 170° C. to about 190° C. and cutting test specimens, in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7±0.1 mm, from the thus-obtained flat strips. Test specimens were conditioned for at least 72 hours at room temperature and 50% relative humidity before testing. According to this test, the specimen is clamped vertically at the centre of a glass chimney at room temperature in an atmosphere of a mixture of oxygen and nitrogen slowly fed into the glass column upwards, where the relative concentration of oxygen and nitrogen can be changed. The upper end of the test sample is ignited with a pilot flame and burns downward. The burning behaviour of the specimen is observed to compare the period for which burning continues. LOI is the minimum concentration of oxygen, expressed as a volume percentage, required to sustain the combustion of the sample indicated by a target burning time after ignition of less than 180 sec. High values of LOI are desirable and indicative of less easily ignited and less flammable material.
  • Smoke Density
  • Smoke density testing was performed according to ISO 5659 test standard inside a NBS smoke chamber, supplied by Fire Testing Technologies. Test specimens were prepared from the compositions of the tables by melt-extruding narrow flat strips in a standard extruder having barrel temperatures set at about 170° C. to about 190° C. and compression molding the strips to form plaques having an area of 75 mm×75 mm and thickness of 2 mm. The specimens were mounted horizontally within the chamber and exposed to a constant thermal irradiance on their upper surface of 25 kW/m2 via a radiator cone and heat flux meter and in the presence of a pilot flame for a period of about 40 min. The smoke evolved over time was collected in the chamber, and the attenuation of a light beam passing through the smoke was measured with a photometric system including a 6.5 V incandescent lamp, a photomultiplier tube, and a high accuracy photodetector. The results were measured in terms of light transmission over time and reported in terms of specific optical density, Ds. Ds is inversely proportional to light transmission and is given for a specific path length equal to the thickness of the molded specimen. Comparison between the material compositions is made via the measurement of max specific optical density, Ds,max and the total smoke production during the first 4 min of the test, VOF4. VOF4 is calculated as: Ds1min+Ds2min+Ds3min+(Ds4min/2), where Ds1min, Ds2min, Ds3min, and Ds4min are the values of the specific optical density recorder at the 1st, 2nd, 3rd and 4th minutes respectively. Any dripping from the plaque test specimen occurring during the test is recorded. The weight of the dripped material is subtracted from the weight of the 75 mm×75 mm×2 mm test plaque. This difference is reported in grams as the “mass retained” during experiment time. A normalised Ds,max can be calculated by dividing Ds,max over the mass retained during the experiment time, and is reported as Ds, max, ret.
  • Ds,max and VOF4 values were calculated automatically by the software of the NBS smoke chamber. The software is consistent with the applicable ISO standard. Low values of Ds,max,ret and VOF4 are desirable and indicative of material that will have a less adverse effect on visibility in the event of fire, and thus will present a lesser obstacle to the rapid escape of people from confined spaces. Without any smoke, light transmittance is 100% and Ds is 0.
  • Experimental Data
  • Compositions designated with “CE” are comparative, and compositions designated with “E” are inventive.
  • Table 1
  • Table 1 shows comparative copolyetherester compositions CE3 (DEPAI alone) and CE4 (DEPAI+Al phosphite) as well as a composition according to the invention (DEPAI+Al phosphite+melamine pyrophosphate).
  • The inventive compositions have good flame retardancy as evidenced by an LOI of 25.
  • In Table 1, LOIex LOI0 means the ratio of the LOI of the experimental material (i.e., containing DEPAI plus phosphite plus MDP), to the LOI of the control material (i.e., containing DEPAI alone).
  • In Table 1, Ds, max, ret, ex/Ds, max, ret, 0 means the ratio of the Ds, max, ret of the experimental material (i.e., containing DEPAI plus phosphite plus MDP), to the Ds, max, ret of the control material (i.e., containing DEPAI alone).
  • While certain of the preferred embodiments of this invention have been described and specifically exemplified above, it is not intended that the invention be limited to such embodiments. Various modifications may be made without departing from the scope and spirit of the invention, as set forth in the following claims.
  • TABLE 1
    DEPAI/AI
    phosphite/
    melamine CE3 CE4 E1
    pyrophosphate [%] [%] [%]
    TPC 85 77 69
    DEPAl 15 15 15
    Al phosphite — 8 8
    Melamine — — 8
    pyrophosphate
    Total (%) of all 100 100 100
    ingredients
    LOI 29 26 25
    LOIex/LOI0 — 0.90 0.86
    VOF4 992 769 462
    Ds, max, ret 50 34 20
    Ds, max, ret, ex/ — 0.68 0.4
    Ds, max, ret, 0

Claims (21)

1-43. (canceled)
44. A flame-retardant polymer composition comprising:
(A) at least one polymer selected from copolyetherester, polyamide elastomer, thermoplastic polyolefinic elastomers, styrenic elastomer, thermoplastic polyurethane, thermoplastic vulcanisate;
(B) 2 to 25 wt % aluminium diethylphosphinate;
(C) at least one aluminium salt of phosphorous acid; and
(D) at least one melamine derivative, selected from melamine salts with organic or inorganic acids and mixtures of two or more of these;
wherein the weight percentages are based on the total weight of the composition.
45. The composition of claim 44, wherein the at least one polymer comprises a copolyetherester.
46. The composition of claim 44, wherein the copolyetherester is made by reacting a C2-C6 diol with an aromatic diacid moiety and a poly(alkyleneoxide)diol.
47. The composition of claim 44, wherein the copolyetherester is made using one or more of the following:
a poly(alkyleneoxide)diol selected from poly(ethyleneoxide)diol, poly(propyleneoxide)diol, poly(tetramethyleneoxide)diol, and mixtures of two or more of these;
a C2-C6 diol selected from ethylene glycol, propylene glycol, butylene glycol, and mixtures of two or more of these; and
an aromatic diacid selected from terephthalate, iso-terephthalate, and mixtures of these.
48. The composition of claim 44, additionally comprising (B′) 0.2 to 16 wt % of aluminum salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid, dihexylphosphinic acid, or mixtures of two or more of these.
49. The composition of claim 44, wherein the at least one aluminium salt of phosphorous acid is selected from mixtures of aluminium phosphite and aluminium hydroxide having the composition of 5-95% by weight of Al2(HPO3)3*nH2O and 95-5% by weight of Al(OH)3 wherein n=0 to 4.
50. The composition of claim 44, wherein the at least one aluminium salt of phosphorous acid is selected from those having the CAS numbers [15099 32-8], [119103-85-4], [220689-59-8], [56287-23-1], [156024-71-4], [71449-76-8], [15099-32-8], and mixtures of two or more of these.
51. The composition of claim 44, comprising a zinc salt of phosphorous acid which is CAS number [14332-59-3].
52. The composition of claim 44, wherein (D) is selected from salts of melamine with boric acid, cyanuric acid, phosphoric acid and/or pyro/polyphosphoric acid, and mixtures of two or more of these.
53. The composition of claim 44, wherein (D) is melamine pyrophosphate.
54. The composition of claim 44, wherein (D) is present at 1 to 15 wt % based on the total weight of the composition.
55. The composition of claim 44, comprising:
(A) at least one copolyetherester;
(B) aluminium diethylphosphinate; and
(C) 3 wt % or more of an aluminium salt of phosphorous acid;
wherein the weight percentages are based on the total weight of the composition.
56. The composition of claim 44, wherein the aluminium diethylphosphinate, the aluminium salt of phosphorous acid, or a combination thereof has a D95, volume %, measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone, of 10 microns.
57. The composition of claim 44, wherein component (D) has a mean particle diameter of less than 20 microns, as measured using laser diffraction technology with a Malvern Mastersizer 2000 particle size analyser instrument, in acetone.
58. The composition of claim 44, having an LOI of 19 or greater when measured according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7±0.1 mm.
59. The composition of claim 44, having a ratio of LOI of the composition incorporating the aluminium diethylphosphinate, metal phosphite(s) and component (D) to LOI of the composition with aluminium diethylphosphinate alone of about 0.75 or greater when measured according to test method ISO 4589-1/-2, using test bars in the shape of rectangular bars of dimension 125 mm long by 13 mm wide and having an average thickness of about 1.7±0.1 mm.
60. The composition of claim 44, having a Ds,max, ret measured according to ISO 5659 test standard and using plaques having an area of 75 mm×75 mm and thickness of 2 mm, of not greater than 45.
61. The composition of claim 44, having a ratio of Ds,max, ret of the composition including the aluminium diethylphosphinate, metal phosphite(s) and component (D) to Ds,max, ret of the composition with aluminium diethylphosphinate alone measured according to ISO 5659 test standard and using plaques having an area of 75 mm×75 mm and thickness of 2 mm, of not greater than 0.9.
62. A shaped article made from the composition of claim 44.
63. A cable comprising a light or electrical conducting core and at least one sheath made from a composition of claim 44.
US17/996,483 2020-06-15 2021-06-15 Copolyetherester Pending US20230340255A1 (en)

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Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10359814A1 (en) 2003-12-19 2005-07-28 Clariant Gmbh Dialkylphosphinic salts
US7790790B2 (en) * 2006-11-14 2010-09-07 E. I. Du Pont De Nemours And Company Flame retardant thermoplastic elastomer compositions
US20100025643A1 (en) * 2008-07-31 2010-02-04 Clariant International Ltd. Flame-retardant mixture for thermoplastic polymers, and flame-retardant polymers
WO2012024280A1 (en) * 2010-08-17 2012-02-23 E. I. Du Pont De Nemours And Company Heat stable halogen-free flame retardant copolyester thermoplastic elastomer compositions
DE102010048025A1 (en) 2010-10-09 2012-04-12 Clariant International Ltd. Flame retardant stabilizer combination for thermoplastic polymers
US8781278B2 (en) * 2011-03-02 2014-07-15 E I Du Pont De Nemours And Company Low smoke halogen free flame retardant thermoplastic elastomer compositions containing zeolites
CN103146153A (en) * 2011-12-07 2013-06-12 杜邦公司 Flame-retardant copolyether ester composition and product comprising the flame-retardant copolyether ester composition
WO2014135376A1 (en) * 2013-03-06 2014-09-12 Dsm Ip Assets B.V. Flame retardant composition comprising a thermoplastic copolyetherester elastomer
DE102014001222A1 (en) * 2014-01-29 2015-07-30 Clariant lnternational Ltd Halogen-free solid flame retardant mixture and its use
JP2019515985A (en) * 2016-03-31 2019-06-13 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ Halogen-free flame retardant thermoplastic elastomer composition containing cyclodextrin
JP7406481B2 (en) * 2017-07-14 2023-12-27 デュポン ポリマーズ インコーポレイテッド Low smoke flame reduction cable
CN107936297A (en) * 2017-11-22 2018-04-20 江苏利思德新材料有限公司 Glass fiber enhanced nylon halogen-free flameproof compound system and its application in halogen-free flame-retardant glass fiber strengthens nylon material

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