WO2018071790A1 - Phosphorus based co-monomer for polyamides - Google Patents
Phosphorus based co-monomer for polyamides Download PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyamide
- group
- formula
- anyone
- saturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides 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
-
- 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
- C08G79/00—Macromolecular 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
- C08G79/02—Macromolecular 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
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- 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
- C08K3/013—Fillers, 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.
Landscapes
- 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)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN201621035136 | 2016-10-14 | ||
| IN201621035136 | 2016-10-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2018071790A1 true WO2018071790A1 (en) | 2018-04-19 |
Family
ID=61905978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2017/056549 Ceased WO2018071790A1 (en) | 2016-10-14 | 2017-10-13 | Phosphorus based co-monomer for polyamides |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US11015022B2 (enExample) |
| EP (1) | EP3526264A4 (enExample) |
| JP (1) | JP7101666B2 (enExample) |
| KR (1) | KR102433061B1 (enExample) |
| CN (1) | CN109843943B (enExample) |
| BR (1) | BR112019007093B1 (enExample) |
| CA (1) | CA3039054A1 (enExample) |
| IL (1) | IL265580B (enExample) |
| WO (1) | WO2018071790A1 (enExample) |
Cited By (1)
| 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)
| 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)
| 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)
| 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 |
-
2017
- 2017-10-13 CA CA3039054A patent/CA3039054A1/en active Pending
- 2017-10-13 KR KR1020197009971A patent/KR102433061B1/ko active Active
- 2017-10-13 EP EP17861014.3A patent/EP3526264A4/en not_active Withdrawn
- 2017-10-13 CN CN201780063295.9A patent/CN109843943B/zh active Active
- 2017-10-13 BR BR112019007093-1A patent/BR112019007093B1/pt active IP Right Grant
- 2017-10-13 WO PCT/US2017/056549 patent/WO2018071790A1/en not_active Ceased
- 2017-10-13 JP JP2019519406A patent/JP7101666B2/ja active Active
- 2017-10-13 US US16/342,135 patent/US11015022B2/en active Active
-
2019
- 2019-03-24 IL IL265580A patent/IL265580B/en unknown
Patent Citations (2)
| 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)
| 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023025741A1 (de) | 2021-08-27 | 2023-03-02 | Ems-Chemie Ag | Flammgeschützte, teilaromatische polyamide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7101666B2 (ja) | 2022-07-15 |
| EP3526264A1 (en) | 2019-08-21 |
| BR112019007093A2 (pt) | 2019-07-02 |
| KR102433061B1 (ko) | 2022-08-17 |
| KR20190069413A (ko) | 2019-06-19 |
| CN109843943A (zh) | 2019-06-04 |
| US11015022B2 (en) | 2021-05-25 |
| BR112019007093B1 (pt) | 2023-04-25 |
| JP2019530786A (ja) | 2019-10-24 |
| IL265580A (en) | 2019-05-30 |
| US20190256656A1 (en) | 2019-08-22 |
| IL265580B (en) | 2022-06-01 |
| EP3526264A4 (en) | 2020-05-06 |
| CA3039054A1 (en) | 2018-04-19 |
| CN109843943B (zh) | 2021-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8487024B2 (en) | Polyamide, polyamide composition, and method for producing polyamide | |
| KR102460868B1 (ko) | 난연성 및 우수한 장기 내열노화성을 가진 폴리아미드 성형 화합물 | |
| US7294661B2 (en) | Flame resistant aromatic polyamide resin composition and articles therefrom | |
| BR112013009232A2 (pt) | composição de poliamida retardadora e artigo | |
| JP2015522094A (ja) | ハロゲンフリー難燃性ポリアミド組成物 | |
| TW201510076A (zh) | 阻燃熱塑性模塑組成物 | |
| US11015022B2 (en) | Phosphorus based co-monomer for polyamides | |
| US20230043028A1 (en) | Reactive phosporous contaning flame retardant and intrinsically flame retardant polymer obtainable by polycondensation with it | |
| JP2018193547A (ja) | 熱可塑性樹脂組成物およびそれを成形してなる成形体 | |
| JP2007507596A (ja) | フェノール樹脂を含む耐燃焼性ポリアミド樹脂組成物、およびそれから作製された物品 | |
| WO2019081226A1 (en) | FLAME RETARDANT POLYMER, PROCESS FOR PREPARING THE SAME, AND THERMOPLASTIC POLYMER COMPOSITION COMPRISING THE SAME | |
| US20210214490A1 (en) | Flame-retardant polymer; method for preparing it and thermoplastic polymer composition comprising it | |
| US20100001430A1 (en) | Flame resistant semiaromatic polyamide resin composition including zinc stannate, and articles therefrom | |
| JP7732462B2 (ja) | 難燃性ポリアミド樹脂組成物及びそれからなる成形品 | |
| US10385166B2 (en) | Polyamide resin, polyamide resin composition containing same, preparation method therefor, and molded product including same | |
| KR101611002B1 (ko) | 난연성 폴리아미드계 수지 조성물 및 이를 포함하는 성형품 | |
| JP2018177874A (ja) | ポリアミド樹脂組成物およびそれを成形してなる成形体 | |
| TWI891962B (zh) | 阻燃性聚醯胺樹脂組成物及由其構成之成形品 | |
| JP2013056969A (ja) | ポリアミド樹脂組成物およびそれを成形してなる成形体 | |
| JP2001081316A5 (enExample) | ||
| JPH0496970A (ja) | 難燃性ポリアミド組成物 | |
| JPH0417984B2 (enExample) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17861014 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 3039054 Country of ref document: CA |
|
| ENP | Entry into the national phase |
Ref document number: 20197009971 Country of ref document: KR Kind code of ref document: A |
|
| ENP | Entry into the national phase |
Ref document number: 2019519406 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112019007093 Country of ref document: BR |
|
| ENP | Entry into the national phase |
Ref document number: 2017861014 Country of ref document: EP Effective date: 20190514 |
|
| ENP | Entry into the national phase |
Ref document number: 112019007093 Country of ref document: BR Kind code of ref document: A2 Effective date: 20190408 |
|
| WWW | Wipo information: withdrawn in national office |
Ref document number: 2017861014 Country of ref document: EP |