WO2018071790A1 - Phosphorus based co-monomer for polyamides - Google Patents

Phosphorus based co-monomer for polyamides Download PDF

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Publication number
WO2018071790A1
WO2018071790A1 PCT/US2017/056549 US2017056549W WO2018071790A1 WO 2018071790 A1 WO2018071790 A1 WO 2018071790A1 US 2017056549 W US2017056549 W US 2017056549W WO 2018071790 A1 WO2018071790 A1 WO 2018071790A1
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Prior art keywords
polyamide
group
formula
anyone
saturated
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English (en)
French (fr)
Inventor
Gururajan Padmanaban
Kaustav CHAKRABORTY
Mayuri SHAIWALE
Imani JONES
Keshav S. Gautam
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Rhodia Operations SAS
Solvay Specialty Polymers USA LLC
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Rhodia Operations SAS
Solvay Specialty Polymers USA LLC
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Priority to BR112019007093-1A priority Critical patent/BR112019007093B1/pt
Priority to US16/342,135 priority patent/US11015022B2/en
Priority to KR1020197009971A priority patent/KR102433061B1/ko
Priority to CA3039054A priority patent/CA3039054A1/en
Priority to EP17861014.3A priority patent/EP3526264A4/en
Priority to JP2019519406A priority patent/JP7101666B2/ja
Priority to CN201780063295.9A priority patent/CN109843943B/zh
Publication of WO2018071790A1 publication Critical patent/WO2018071790A1/en
Priority to IL265580A priority patent/IL265580B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04Phosphorus linked to oxygen or to oxygen and carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives

Definitions

  • the subject matter described herein in general relates to a polyamide, an article made from the polyamide, and process for the same.
  • CN 103122501 describes the drawbacks of using halogen-based flame retardants.
  • Halogen-based flame retardants cause polymer colour variation, it reduces light performance and most importantly it produces toxic gases during combustion process thereby causing atmospheric pollution.
  • Phosphorus compounds are widely used to reduce the flammability of thermoplastic polymers.
  • US 4032517 teaches copolyamides having 0.5 to 7.5% by weight of phosphorus as an integral part of their polymer chain.
  • the used phosphorus-based reactive co-monomers are more expensive and hence unfit to be used commercially.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of formula I:
  • Ar is independently selected from the group consisting of aryl, arylene, heteroaryl and carbocyclic group
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, and alkylaromatics.
  • aryl refers to an aromatic carbocyclic group of 6 to 18 carbon atoms having a single ring (e.g. phenyl) or multiple rings (e.g. biphenyl), or multiple condensed (fused) rings (e.g. naphthyl or anthranyl).
  • Aryl groups may also be fused or bridged with alicyclic or heterocyclic rings that are not aromatic so as to form a polycycle, such as tetralin.
  • An "arylene” group is a divalent analog of an aryl group.
  • aliphatics refers to substituted or unsubstituted saturated alkyl chain having from 1 to 18 carbon atoms, substituted or unsubstituted alkenyl chain having from 1 to 18 carbon atoms, substituted or unsubstituted alkynyl chain having from 1 to 18 carbon atoms.
  • alkyl groups include saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclic alkyl groups (or "cycloalkyl” or “alicyclic” or “carbocyclic” groups), such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, branched-chain alkyl groups, such as isopropyl, tert-butyl, sec-butyl, and isobutyl, and alkyl- substituted alkyl groups, such as alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups.
  • aliphatic group includes organic moieties characterized by straight or branched-chains, typically having between 1 and 18 carbon atoms. In complex structures, the chains may be branched, bridged, or cross-linked. Aliphatic groups include alkyl groups, alkenyl groups, and alkynyl groups.
  • alkenyl or “alkenyl group” refers to an aliphatic hydrocarbon radical which can be straight or branched, containing at least one carbon-carbon double bond.
  • alkenyl groups include, but are not limited to, ethenyl, propenyl, n-butenyl, i-butenyl, 3-methylbut-2-enyl, n-pentenyl, heptenyl, octenyl, decenyl, and the like.
  • alkynyl refers to straight or branched chain hydrocarbon groups having at least one triple carbon to carbon bond, such as ethynyl.
  • arylaliphatics refers to an aryl group covalently linked to an aliphatics, where aryl and aliphatics are defined herein.
  • cycloaliphatics refers to carbocyclic groups of from 3 to 20 carbon atoms having a single cyclic ring or multiple condensed rings which may be partially unsaturated, where aryl and aliphatics are defined herein.
  • heterocyclic group includes closed ring structures analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, for example, nitrogen, sulfur, or oxygen. Heterocyclic groups may be saturated or unsaturated.
  • heteroaryl refers to an aromatic cyclic group having 3 to 10 carbon atoms and having heteroatoms selected from oxygen, nitrogen and sulfur within at least one ring (if there is more than one ring).
  • n and m are each integers, indicates that the group may contain from n carbon atoms to m carbon atoms per group.
  • Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • a temperature range of about 120°C to about 150°C should be interpreted to include not only the explicitly recited limits of about 120°C to about 150°C, but also to include sub-ranges, such as 125°C to 145°C, 130°C to 150°C, and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 122.2°C, 140.6°C, and 141.3°C, for example.
  • majority of the flame retardants used are additives. Therefore, these may leach out of the polymer over time and pollute the environment.
  • Use of the reactive co-monomers that are covalently incorporated within the polymer backbone can overcome the problem associated with leaching.
  • the present disclosure provides a monomer which is relatively inexpensive and may be synthesized from widely available inexpensive starting materials. The monomer brings in impressive flame retardant property even when used in lower amount as compared to the quantity of additives required for the same purpose.
  • the present disclosure relates to the use of an organophosphorus compound co-monomer which is chemically incorporated in the polymer backbone in turn improving the flame retardancy of the polymers.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is independently selected from the group consisting of an aryl, arylene, heteroaryl and carbocyclic group
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics.
  • Ar may notably be an aryl group or an arylene group depending on its position in the repeating unit backbone of formula (I).
  • Ar when Ar is a radical derived from an aromatic hydrocarbon, it may be a phenyl group or a phenylene group.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is independently selected from the group consisting of an aryl, arylene, heteroaryl and carbocyclic group
  • R is selected from the group consisting of hydrogenated aliphatics, cycloaliphatics, aromatics, and alicyclics.
  • R may be preferably selected from the group consisting of hydrogenated aliphatics, cycloaliphatics, aromatics, and alicyclics.
  • R may notably be selected from the group consisting of meta- xylelenyl moiety, and para- xylelenyl moiety.
  • Ar is preferably an aryl, arylene or heteroaryl or carbocyclic group having from C 4 to C 18 carbon atoms.
  • Ar is preferably a phenyl group or a phenylene group.
  • Repeating unit of Formula I may be for instance:
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is independently selected from the group consisting of an aryl, arylene, heteroaryl and carbocyclic group
  • R is selected from the group consisting of meta- xylelenyl moiety, and para- xylelenyl moiety.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is carbocyclic group having from C4 to CI 8 carbon atoms
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is phenyl group or phenylene group
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is an aryl or arylene
  • R is selected from the group consisting of hydrogenated aliphatics, cycloaliphatics, aromatics, and alicyclics.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is carbocyclic group having from C4 to CI 8 carbon atoms
  • R is selected from the group consisting of hydrogenated aliphatics, cycloaliphatics, aromatics, and alicyclics.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is phenyl group or phenylene group
  • R is selected from the group consisting of hydrogenated aliphatics, cycloaliphatics, aromatics, and alicyclics.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is an aryl or arylene
  • R is selected from the group consisting of meta- xylelenyl moiety, and para- xylelenyl moiety.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is carbocyclic group having from C4 to CI 8 carbon atoms
  • R is selected from the group consisting of meta- xylelenyl moiety, and para- xylelenyl moiety.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is phenyl group or phenylene group
  • R is selected from the group consisting of meta- xylelenyl moiety, and para- xylelenyl moiety.
  • the polyamide of the present invention may be a homopolyamide or a copolyamide.
  • the polyamide of the present invention may notably be a homopolyamide and then only made of repeating units of Formula I.
  • the polyamide of the present invention mays also be a copolyamide then further comprising other repeating units different from the unit of formula (I), said repeating units originating from co-monomers such as dicarboxylic acids, diamines, amino acids and/ or lactams.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is independently selected from the group consisting of an aryl, arylene, heteroaryl and carbocyclic group
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics
  • the polyamide is a copolyamide further comprising other repeating units different from the unit of formula (I), said repeating units originating from co-monomers such as dicarboxylic acids, diamines, amino acids and/ or lactams.
  • the present invention may notably relates to a copolyamide comprising at least one repeating unit of Formula I:
  • Ar is independently selected from the group consisting of an aryl, arylene, heteroaryl and carbocyclic group
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics
  • the polyamide is a copolyamide further comprising other repeating units different from the unit of formula (I), said repeating units originating from dicarboxylic acids.
  • the polyamide according to the present invention may comprise from 0.1 to 100 mole% of repeating unit of Formula I, based on the total amount of residues of monomers units, preferably from 0.2 to 50 mol%, more preferably from 0.5 to 25 mol%.
  • the polyamide according to the present invention comprises between 0.1 and 100 mole% of bis(p-methoxycarbonyl phenyl) phosphate in diacid part, more preferably between 1 and 20 mol% of bis(p-methoxycarbonyl phenyl) phosphate in diacid part, such as between 2 and 10 mol% of bis(p- methoxycarbonyl phenyl) phosphate in diacid part.
  • a mol% is based upon 100mole% of residues of monomers units of the polyamide.
  • the dicarboxylic acid is preferably chosen in the group constituted by aliphatic diacids, aromatic diacids, acyclic aliphatic diacids and mixtures thereof.
  • the diamine may be chosen in the group constituted by aliphatic diamines, aromatic diamines, cycloaliphatic diamines, acyclic aliphatic diamines and mixtures thereof.
  • Copolyamides of the invention may comprise then repeat units of polyamide 6, polyamide 7, polyamide 6.6, polyamide 10, polyamide 1 1, polyamide 12, polyamide 6.9, polyamide 510, polyamide 610, polyamide 612, polyamide 614, polyamide 1010, polyamide 1012, polyamide 1014, polyamide 1018, polyamide 1212, polyamide 46, polyamide 618, polyamide 636, polyamide 6T, polyamide 61, polyamide 9T, polyamide MXD6, polyamide PXD6, and copolymers based on these (co)polyamides.
  • Polymer of the invention may preferably comprise repeat units of polyamide 6, polyamide 66, polyamide 1 1, polyamide 12, polyamide 66/6 and copolymers based on these (co)polyamides.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics, wherein the repeating unit of formula (I) comprises between 0.1 and 100 mole% of bis(p- methoxycarbonyl phenyl) phosphate in diacid part.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is independently selected from the group consisting of an aryl, arylene, heteroaryl and carbocyclic group
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics, wherein the repeating unit of formula (I) comprises between 1 and 20 mol% of bis(p-methoxycarbonyl phenyl) phosphate in diacid part.
  • the present disclosure relates to a polyamide comprising at least one repeating unit of Formula I:
  • Ar is independently selected from the group consisting of an aryl, arylene, heteroaryl and carbocyclic group
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics, wherein the repeating unit of formula (I) comprises between 2 and 10 mol% of bis(p-methoxycarbonyl phenyl) phosphate in diacid part.
  • the present disclosure relates to a process of preparing the polyamide comprising at least one repeating unit of Formula I:
  • Ar is independently selected from the group consisting of an aryl, arylene, heteroaryl and carbocyclic group
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics; said process comprises a polycondensation reaction between:
  • Said process may also comprise addition of other monomers in the polycondensation reaction medium.
  • Said monomers are preferably chosen in the group consisting of: dicarboxylic acids, diamines, amino acids and/or lactams.
  • the process may comprise addition from 0.1 to 60 mole% of the dicarboxylic acid of Formula (II), based on the total amount of residues of monomers units, preferably from 0.2 to 40 mol%, more preferably from 0.5 to 25 mol%.
  • the polymer of the invention can, for example, be: -a polyamide synthesized from a dicarboxylic acid of Formula (II) in which Ar is phenyl or phenylene and a diamine of Formula (III) in which R is a xylene.
  • the present disclosure relates to a polyamide composition
  • a polyamide composition comprising: a polyamide comprising: at least one repeating unit of Formula I:
  • Ar is independently selected from the group consisting of an aryl, arylene, heteroaryl and carbocyclic group
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics; and at least one reinforcing filler and/ or at least one other additive.
  • the present disclosure relates to a process for preparing the polyamide composition by blending a polyamide comprising: at least one repeating unit of Formula I:
  • Ar is independently selected from the group consisting of an aryl, arylene, heteroaryl and carbocyclic group
  • R represents a covalent bond or a divalent hydrocarbon-based group selected from the group consisting of saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics, alicyclics, and alkylaromatics; and at least one reinforcing filler and/ or at least one other additive.
  • the process for preparing a polyamide according to the invention also comprises a polycondensation reaction between:
  • X100C-Ar-0-P( 0)(-Ar)-0-Ar-COOX2 (II) wherein XI and X2 are independently selected from hydrogen, alkyl group or halogen group; Ar as previously defined;
  • the polyamide composition may also comprise at least one other polyamide, notably one or two other polyamides.
  • semicrystalline or amorphous (co)polyamides ie. polyamides or copolyamides, such as aliphatic polyamides, semiaromatic polyamides and, more generally, linear polyamides obtained by polycondensation between a saturated aliphatic or aromatic diacid and a saturated aliphatic or aromatic primary diamine, polyamides obtained by condensation of a lactam or an amino acid, or linear polyamide
  • these copolyamides may be, for example, polyhexamethylene adipamide, polyphthalamides obtained from terephthalic and/or isophthalic acid, and copolyamides obtained from adipic acid, hexamethylenediamine and caprolactam.
  • the polyamide is selected from the group consisting of the polyamides obtained by polycondensation of:
  • At least one amino acid to itself the amino acid preferably being an omega aminoacid generated by opening of a lactam ring, or copolyamides obtained by the polycondensation of combinations of said diacid, diamine and/or aminoacid.
  • At least one of the diacid, diamine and/or aminoacid monomer used in the polycondensation may comprise from 2 to 40 carbon atoms.
  • MPMD methyl-pentamethylenediamine
  • composition of the invention may also comprise copolyamides derived especially from the above polyamides, or blends of these polyamides or copolyamides.
  • the preferred polyamides are polyhexamethylene adipamide, polycaprolactam, or copolymers and blends of polyhexamethylene adipamide and polycaprolactam.
  • Composition of the invention may be for instance:
  • the invention also concerns a polyamide composition
  • a polyamide composition comprising at least the polyamide of the invention and at least one reinforcing filler and/ or at least one other additive. Reinforcing filler and/ or additives may be added by blending with the polyamide.
  • Polyamide composition is then usually extruded in the form of rods, for example in a twin-screw extrusion device, said rods then being chopped into granules.
  • composition according to the invention may also comprise additives normally used for the manufacture of polymer compositions, especially intended to be molded.
  • additives normally used for the manufacture of polymer compositions especially intended to be molded.
  • Lubricants may be stearic acid or stearate salts such as calcium stearate.
  • Antidriping agents may be poly(tetrafluoroethylene), notably PTFE SN3306 for example.
  • the composition of the invention preferably comprises reinforcing fibers such as glass fibers or carbon fibers.
  • the composition can comprise from 5 to 50 % by weight of reinforcing fibers, based on the total weight of the flame retardant polymer composition.
  • Composition of the invention may also comprise at least one flame retardant additive.
  • flame retardant additives may be used according to the invention. They can provide several mechanisms of function such as endothermic degradation, thermal shielding, dilution of gas phase, dilution of combustible portion, and radical quenching.
  • Flame retardant additives for polymer compositions are notably described in Plastics Additives, Gachter/Miiller, Hansen, 1996, page 709 and passim.
  • Useful Flame retardant additives are notably cited in the following patents: US6344158, US6365071, US6211402 and US6255371.
  • Flame retardant additives used in the composition of the instant invention are preferably chosen in the group comprising :
  • Phosphorous containing flame retardant additives such as: - phosphine oxide such as for example triphenylphosphine oxide, tri-(3- hydroxypropyl) phosphine oxide and tri-(3-hydroxy-2-methylpropyl) phosphine oxide.
  • phosphinic acids and their salts such as for example phosphinic acid of zinc, magnesium, calcium, aluminium or manganese, notably aluminium salt of diethylphosphinic acid, aluminium salt of dimethylphosphinic acid, or zinc salt of dimethylphosphinic acid.
  • - cyclic phosphonates such as diphosphate cyclic esters that is for example Antiblaze 1045.
  • organic phosphates such as triphenylphosphate.
  • - inorganic phosphates such as ammonium polyphosphates and sodium polyphosphates.
  • Nitrogen containing flame retardant additives such as : triazines, cyanuric acid and/or isocyanuric acid, melamine or its derivatives such as cyanurate, oxalate, phtalate, borate, sulfate, phosphate, polyphosphate and/or pyrophosphate, condensed products of melamine such as melem, melam, melon, tris(hydroxyethyl) isocyanurate, benzoguanamine, guanidine, allanto ' ine and glycoluril.
  • triazines such as : triazines, cyanuric acid and/or isocyanuric acid, melamine or its derivatives such as cyanurate, oxalate, phtalate, borate, sulfate, phosphate, polyphosphate and/or pyrophosphate, condensed products of melamine such as melem, melam, melon, tris(hydroxyethyl
  • Halogen containing flame retardant additives such as:
  • PBDPO polybromodiphenyl oxides
  • BrPS brominated polystyrene
  • PrPS poly(pentabromobenzylacrylate)
  • brominated indane tetradecabromodiphenoxybenzene
  • Saytex 120 tetradecabromodiphenoxybenzene
  • PDBS-80 from Chemtura, Saytex HP 3010 from Albemarle or FR- 803P from Dea Sea Bromine Group, FR-1210 from Dea Sea Bromine Group, octabromodiphenylether (OBPE), FR-245 from Dead Sea Bromine Group, FR- 1025 from Dead Sea Bromine Group and F-2300 or F2400 from Dead Sea Bromine Group.
  • OBPE octabromodiphenylether
  • FR-245 from Dead Sea Bromine Group
  • FR- 1025 from Dead Sea Bromine Group
  • F-2300 or F2400 Dead Sea Bromine Group.
  • Chlorine containing flame retardant additives such as Dechlorane plus® from OxyChem (CAS 13560-89-9).
  • Inorganic flame retardant additives such as antimony trioxide, aluminium hydroxide, magnesium hydroxide, cerium oxide, boron containing compounds such as calcium borate.
  • Charring agents and charring catalysts may also be used if necessary.
  • composition according to the invention may comprise a flame retardant additive in an amount of 0.1 to 30 weight percent, preferably from 1 to 20 weight percent, based on the total weight of the composition.
  • compositions according to the invention may be used as raw material in the field of plastics processing, for example for the preparation of articles formed by injection- molding, by injection/blow- molding, by extrusion or by extrusion/blow-molding.
  • the modified polyamide is extruded in the form of rods, for example in a twin-screw extrusion device, said rods then being chopped into granules.
  • the molded components are then prepared by melting the granules produced above and feeding the molten composition into injection- molding devices.
  • the present disclosure also relates to the use of the polyamide of the present invention, for making articles, notably by moulding, injection- moulding, injection/blow- moulding, extrusion/blow- moulding, extrusion or spinning.
  • the present disclosure relates also to the use of the polyamide composition of the invention, for making articles notably by moulding, injection- moulding, injection/blow- moulding, extrusion/blow- moulding, extrusion or spinning.
  • the present disclosure also relates to an article obtained from the polyamide of the invention, wherein the article is notably selected from the group consisting of from yarns, fibres, automotive parts and wire & cable parts.
  • the present disclosure also relates to an article obtained from the polyamide composition of the invention , wherein the article is notably selected from the group consisting of yarns, fibres, automotive parts and wire & cable parts.
  • Methyl paraben (2.2 mmol) and THF (5.0 vol.) were charged in a 4-necked RBF (fitted with nitrogen inlet, reflux condenser, dropping funnel and overhead stirrer) at RT under N2, and stirred until a homogeneous solution is created.
  • Triethyl amine (5.0 mmol) was charged to the solution at RT with continuous stirring.
  • Phenylphosphonic dichloride (1.0 mmol) was added dropwise to the reaction mixture at RT under N2, and the resulting mixture was stirred at RT for 30 mins. Thereafter, the reaction mixture was refluxed for 2.0 hrs. White precipitate was observed in the reaction mixture. The reaction mixture was cooled to RT, and, filtered to obtain white residue.
  • the torque value reaches 30 N-m or beyond, the system is de-assembled and the polymer is quenched in ice-water mixture.
  • the molecular weight (Mn and Mw) and polydispersity index (PDI) of the polymer are determined by GPC as provided below in Table 1. Thermal stability of the polymer is determined by DSC and TGA experiments.
  • Table 1 depicts the GPC data (PMMA calibration) for PA MXD6 and its modified versions:
  • wt% of P C is expressed in relation to total amount of monomers used
  • TGA data of 2wt% P C incorporated MXD6 is provided in Figure and the TGA data of 5wt% P3C incorporated MXD6 is provided in Figure 2.
  • Example 4 Flame retardancy test of blends of P3C-incorporated MXD6 with PA610
  • Blends of PA610 with P3C-incorporated (2wt%) MXD6 in different ratios were evaluated for their flame retarding properties. All the blends contained 45% glass (FF-E glass, black colour).
  • the composition of the blends has been summarised in the following table 3 :
  • Total Burn time (s) -using MXD6 5% P3C 111 Total burn time is measured based on UL94 vertical burn test standards. Apply a flame to a flex bar and measure how long it takes for the flame to extinguish. The longer the burn time, the lower the flame rating. The total burn time is the sum of individual burning of 5 bars.
  • the present disclosure thus provides an economical and improved polyamides with flame-retardant property including a much less quantity of additives actually required for this purpose.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyamides (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/US2017/056549 2016-10-14 2017-10-13 Phosphorus based co-monomer for polyamides Ceased WO2018071790A1 (en)

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BR112019007093-1A BR112019007093B1 (pt) 2016-10-14 2017-10-13 Poliamida, seu uso e seu processo de preparação, composição de poliamida, e artigo
US16/342,135 US11015022B2 (en) 2016-10-14 2017-10-13 Phosphorus based co-monomer for polyamides
KR1020197009971A KR102433061B1 (ko) 2016-10-14 2017-10-13 폴리아미드용 인계 공단량체
CA3039054A CA3039054A1 (en) 2016-10-14 2017-10-13 Phosphorus based co-monomer for polyamides
EP17861014.3A EP3526264A4 (en) 2016-10-14 2017-10-13 PHOSPHORUS-BASED COMONOMER FOR POLYAMIDES
JP2019519406A JP7101666B2 (ja) 2016-10-14 2017-10-13 ポリアミド用リン含有コモノマー
CN201780063295.9A CN109843943B (zh) 2016-10-14 2017-10-13 用于聚酰胺的基于磷的共聚单体
IL265580A IL265580B (en) 2016-10-14 2019-03-24 Phosphorus-based co-monomer for polyamides

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023025741A1 (de) 2021-08-27 2023-03-02 Ems-Chemie Ag Flammgeschützte, teilaromatische polyamide

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230357539A1 (en) * 2022-05-06 2023-11-09 Celanese International Corporation Fiber Reinforced Thermoplastic Polymer Composition With Flame Retardant Properties
WO2024091994A1 (en) * 2022-10-26 2024-05-02 Celanese International Corporation Fiber reinforced thermoplastic polymer composition containing flame retardant package

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2646420A (en) * 1949-07-22 1953-07-21 Du Pont Synthetic linear condensation polymers containing phosphorus
US4032517A (en) * 1975-07-22 1977-06-28 Monsanto Company Phosphorus-containing copolyamides and fibers thereof

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1196195B (de) * 1963-02-14 1965-07-08 Gelsenberg Benzin Ag Verfahren zur Herstellung von Phosphonsaeureestern
GB1187981A (en) * 1965-06-23 1970-04-15 Ici Ltd Polyamides
DE2400317A1 (de) 1974-01-04 1975-07-24 Huels Chemische Werke Ag Verfahren zur herstellung von pillarmen faserprodukten aus polyestern
DE19614424A1 (de) 1996-04-12 1997-10-16 Hoechst Ag Synergistische Flammschutzmittel-Kombination für Polymere
DE19629432A1 (de) 1996-07-22 1998-01-29 Hoechst Ag Aluminiumsalze von Phosphinsäuren
US5750603A (en) 1997-05-23 1998-05-12 Solutia Inc. Polymer-bound non-halogen fire resistant compositions
DE19903709A1 (de) 1999-01-30 2000-08-10 Clariant Gmbh Flammschutzmittel-Kombination für thermoplastische Polymere II
DE19933901A1 (de) 1999-07-22 2001-02-01 Clariant Gmbh Flammschutzmittel-Kombination
CN102348761A (zh) * 2009-03-13 2012-02-08 巴斯夫欧洲公司 聚酯和聚酰胺的稳定共混物
CN103122501A (zh) 2011-11-18 2013-05-29 东丽纤维研究所(中国)有限公司 一种磷系阻燃阳离子可染聚酯纤维的生产方法
TWI457353B (zh) * 2012-05-08 2014-10-21 Ind Tech Res Inst 高分子、高分子混摻物、與阻燃材料
CN104211954B (zh) * 2013-05-30 2016-10-05 辽宁银珠化纺集团有限公司 一种无卤阻燃尼龙66聚合物的制备方法
SI3022274T1 (sl) * 2013-07-16 2019-10-30 Deutsche Inst Fuer Textil Und Faserforschung Denkendorf Postopek za proizvodnjo ognjevarnih kopoliamidov, tako pridobljene poliamidne preje in uporaba le-teh
CN105175717B (zh) * 2015-08-12 2019-02-05 中国人民解放军总后勤部军需装备研究所 一种阻燃聚酰胺及其制备方法与应用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2646420A (en) * 1949-07-22 1953-07-21 Du Pont Synthetic linear condensation polymers containing phosphorus
US4032517A (en) * 1975-07-22 1977-06-28 Monsanto Company Phosphorus-containing copolyamides and fibers thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JENG ET AL.: "Flame retardant epoxy polymers based on all phosphorus-containing components", EUROPEAN POLYMER JOURNAL, vol. 38, 12 February 2002 (2002-02-12), pages 683 - 693, XP004340237 *
See also references of EP3526264A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023025741A1 (de) 2021-08-27 2023-03-02 Ems-Chemie Ag Flammgeschützte, teilaromatische polyamide

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US11015022B2 (en) 2021-05-25
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CA3039054A1 (en) 2018-04-19
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