EP1546244A2 - Flammfeste verzweigtes polyamid enthaltende zusammensetzung - Google Patents

Flammfeste verzweigtes polyamid enthaltende zusammensetzung

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Publication number
EP1546244A2
EP1546244A2 EP03784227A EP03784227A EP1546244A2 EP 1546244 A2 EP1546244 A2 EP 1546244A2 EP 03784227 A EP03784227 A EP 03784227A EP 03784227 A EP03784227 A EP 03784227A EP 1546244 A2 EP1546244 A2 EP 1546244A2
Authority
EP
European Patent Office
Prior art keywords
acid
radical
composition according
polyamide
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03784227A
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English (en)
French (fr)
Inventor
James Mitchell
Daniele Galli
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Engineering Plastics SAS
Rhodia Engineering Plastics SpA
Original Assignee
Rhodia Engineering Plastics SAS
Rhodia Engineering Plastics SpA
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Application filed by Rhodia Engineering Plastics SAS, Rhodia Engineering Plastics SpA filed Critical Rhodia Engineering Plastics SAS
Publication of EP1546244A2 publication Critical patent/EP1546244A2/de
Withdrawn legal-status Critical Current

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5357—Esters of phosphonic acids cyclic
    • 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
    • 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
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • 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
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic 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
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
    • 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

Definitions

  • the present invention relates to a flame retardant composition
  • a flame retardant composition comprising at least one branched polyamide and a flame retardant system.
  • Such a composition makes it possible to obtain articles having a low propagation of flames when they enter into combustion as well as satisfactory mechanical properties.
  • This composition is particularly useful for the production of molded articles used in the field of electrical or electronic connectors.
  • the polyamide resin-based compositions are used for the production of articles by various shaping methods. These articles are used in many technical fields.
  • the fireproofing of compositions based on linear polyamide resin has been studied for a very long time.
  • the main flame retardants used are red phosphorus, halogenated compounds such as polybromodiphenyls, polybromodiphenoxides, brominated polystyrenes, nitrogenous organic compounds belonging to the class of triazines such as melamine or its derivatives such as melamine cyanurate and more recently melamine phosphates, polyphosphates and pyrophosphates, organophosphorous acids and their salts, in particular in combination with thermoplastic polymers, such as linear polyamides (DE-A-2 252 258, DE-A-2 447 727 and US 6,255,371).
  • Polyamide-based compositions with increasing flame retardancy properties are constantly being sought.
  • flame retardants generally used in large quantities, lead to problems in shaping the parts.
  • certain flame retardants containing halogens or red phosphorus can generate toxic gases or vapors during the combustion of the composition.
  • polyamide In addition, flame retardants are known to be unstable at elevated temperatures. Thus, part of the flame retardants degrades during the polyamide manufacturing process, thus reducing their flame retardant efficiency.
  • the present invention relates to a composition, in particular intended for the manufacture of articles, comprising at least branched polyamides and a flame retardant system based on flame retardants.
  • branched polyamides and the flame retardants act in synergy and make it possible to obtain articles having a low flame spread, good mechanical properties and good thermal stability compared to the compositions of the invention.
  • prior art comprising linear polyamides.
  • the present invention relates to a flame retardant composition
  • a flame retardant composition comprising at least: a) a branched polyamide comprising a core having at least three polymerization initiating functions, and b) a flame retardant system, with the exception of a combination of acid salt phosphinic acid and a reaction product between phosphoric acid and melamine or a melamine derivative.
  • branched polyamide is understood to mean a nonlinear polyamide comprising macromolecular chains generally linked to multifunctional compounds or monomers.
  • a branched polyamide comprises at least one core having at least three polymerization initiating functions, identical or different, capable of forming an amide bond. These are generally acid functions or derivatives of acids and amino functions or derivatives of amines.
  • Branched polyamides are described in numerous patents and publications and are well known to those skilled in the art.
  • the branched polyamides can be, for example, polyamides with structure H, star (star), tree (tree), hyperbranchée.
  • the preferred branched polyamides are those having a higher melt flow, compared to the linear polyamide of the same molecular weight.
  • the polymers or polymer compositions comprising star or H structures are for example described in the documents FR743077, FR2779730, US5959069, EP0632703, EP0682057, US6160080 and EP0832149.
  • the polymers or polymer compositions comprising tree structures, or tree are for example described in documents FR2766197 and WO9903909.
  • the polymers or polymer compositions comprising hyperbranched polyamides are for example described in the document WO0068298.
  • the star polyamides can be obtained by using a multifunctional compound having at least three reactive functions, all of the reactive functions possibly being identical or different.
  • This multifunctional compound can be used as a comonomer in the presence of other monomers in a polymerization process.
  • Star structures have a core and a number of polyamide branches, usually at least three.
  • the branches are linked to the heart by a covalent bond of the polyamide type.
  • the heart is an organic or organometallic chemical compound, preferably a hydrocarbon compound optionally comprising heteroatoms and to which the branches are linked.
  • the branches are polyamide chains.
  • the polyamide chains constituting the branches are preferably of the type of those obtained by polymerization of lactams or amino acids, for example of the polyamide 6 type.
  • the preferred star polyamide according to the invention is a polyamide comprising at least macromolecular chains of formula (I): R, - [- AX - (- YR 2 -Z-) n -R 3 ] m (I) and optionally macromolecular chains of formula (II):
  • - Y is the radical: R 5 when X and Z represent the radical: r °! ;
  • I i - Y is the radical: ° when X and Z represent the radical: 5 ;
  • - A is a covalent bond or an aliphatic hydrocarbon radical which may comprise heteroatoms and comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms;
  • - Ri is a hydrocarbon radical comprising at least 2 carbon atoms, linear or cyclic, aromatic or aliphatic, preferably from 2 to 6 carbon atoms, and which can comprise heteroatoms;
  • - R 2 is a branched or unbranched aliphatic or aromatic hydrocarbon radical comprising from 2 to 20 carbon atoms, preferably from 6 to 12 carbon atoms;
  • R 3 and Rt independently of one another represent hydrogen, an —OH radical, and / or a hydrocarbon radical comprising at least one group:
  • R 5 represents hydrogen or a hydrocarbon radical comprising in particular from 1 to 6 carbon atoms
  • - m represents an integer between 3 and 8 (limits included), preferably between 3 and 4;
  • - N represents an integer between 50 and 200 (limits included), preferably between 100 and 200, particularly between 150 and 200; and
  • - p represents an integer between 50 and 200 (limits included), preferably between 100 and 200, particularly between 150 and 200.
  • the composition according to the invention comprises from 30 to 99% by weight of star polyamide, preferably from 30 to 77%, relative to the total weight of the composition.
  • the radical Ri can be a radical chosen from the cycloaliphatic, arylaliphatic, and linear aliphatic group.
  • the mass ratio between the weight of polymer chains of formula (I) and the total weight of polymer chains of formulas (I) and (II) is between 0.10 and 1.
  • the radical Ri can to be an aromatic radical.
  • the mass ratio between the weight of polymer chains of formula (I) and the total weight of polymer chains of formulas (I) and (II) is less than 1, preferably less than 0.9.
  • Ri may represent a radical chosen from the cyclohexanontetrayl radical, the 1,1,1-triyl propane radical, the radical
  • N-CH 2 -H 2 CN ⁇ 1, 2,3-triyl propane and the radical: ⁇ .
  • radicals Rj suitable for the invention mention may be made, by way of example, of trivalent phenyl and cyclohexanyl radicals, substituted or not, tetravalent radicals of diaminopolymethylene with a number of methylene groups advantageously between 2 and 12 such that the radical originating from EDTA (ethylene diamino tetracetic acid), the octovalent radicals of cyclohexanonyl or cyclohexadinonyl, and radicals originating from compounds derived from the reaction of polyols such as glycol, pentaerythritol, sorbitol or mannitol with acrylonitrile.
  • EDTA ethylene diamino tetracetic acid
  • octovalent radicals of cyclohexanonyl or cyclohexadinonyl radicals originating from compounds derived from the reaction of polyols such as glycol, pentaerythritol,
  • the R2 radicals are residues of amino acids or lactams.
  • R can be a pentamethylene radical.
  • the polyamide has a structure type polycaproamide or PA 6.
  • Other radicals R2 can be used such as the undecamethylene radicals which lead to a polyamide with structure type PA 12. It is also possible to obtain polyamides having R2 radicals comprising 8 or
  • the radical A preferably, is a methylenic or polymethylenic radical such as the ethyl, propyl or butyl radicals, or a polyoxyalkylene radical such as the polyoxyethylene radical.
  • R and R 4 may represent a hydrogen atom and / or a radical -OH. It is understood that R 3 can represent a radical -OH, when Z
  • R 4 may represent a radical -OH, when Y
  • R 3 can represent a hydrogen atom
  • R 3 and ⁇ may also represent a hydrocarbon radical, preferably having from 1 to 10 carbon atoms, comprising at least one group:
  • R 3 and R 4 represent a hydrocarbon radical comprising at least one group:
  • the polymer chains of formula (I) define a star polyamide comprising polyamide branches of type PA 6 in one of the preferred embodiments of the invention, and a central core constituted by a cycloaliphatic core.
  • These polymer chains of formula (I) are, in one of the preferred modes of the invention, in admixture with linear polyamide chains of formula (II).
  • the length or molecular weight of the linear chains of formula (II) or of the branches of the star polyamide can be high.
  • the linear polymer like the chain of each branch of the star polymer has an Mn advantageously greater than 5,000.
  • the star polyamide according to the invention is obtained at least from the monomers of formula: and / or a lactam of formula:
  • the reactive function of the polyfunctional compound of formula (N) represented by the symbol X-H is a function capable of forming an amide function, that is to say for example an acid or amino function.
  • the compounds of the preferred formulas (N) are the following:
  • the polycondensation initiator can be water, a mineral or carboxylic acid and / or a primary amine. This compound is advantageously added to obtain a weight concentration of between 0.5 and 5% by weight relative to the total mixture.
  • the polyfunctional compound of formula (N) can be chosen from the group comprising the compound 2,2,6,6-tetra- ( ⁇ -carboxyethyl) cyclohexanone, the diaminopropane compound - ⁇ , ⁇ , ⁇ ' , Ét tetraacetic acid, the triamines marketed under the name JEFF AMINES T®, and obtained by reaction of propylene oxide on trimethylol propane or glycerol and amination of the hydroxide ends.
  • P represents a 1,1,1-triyl propane or 1,2,3-triyl propane radical
  • - D represents a polyoxyethylene radical
  • polyfunctional compound of formula (V) can be used, preferably 0.3 to 1 mol%, relative to the total number of moles of the polyamide obtained.
  • the polycondensation can be carried out according to the conventional operating conditions for polycondensation of amino acids or lactams of formula (III) or (IN), when this is carried out in the absence of the multifunctional compound of formula (N).
  • the polycondensation process can briefly include: heating with stirring and under pressure of the mixture of monomers: compounds of formula (III) and / or (IN) and of the compound of formula (N) with the initiator (generally of the water), maintaining the mixture at this temperature for a determined period, then decompressing and maintaining under a current of inert gas (for example nitrogen) for a determined period at a temperature above the melting point of the mixture for _ thus continue the polycondensation by elimination of the water formed.
  • inert gas for example nitrogen
  • the duration of the maintenance under inert gas, or in other words of finishing the polycondensation makes it possible to determine and control the concentration of polymer chains of formula (I) in the polyamide mixture. So the more time to maintenance will be long the higher the concentration of polymer chains of formula (I).
  • concentration of polymer chains of formula (I) or star polyamide is a function of the amount of multifunctional compound of formula (N) added to the mixture.
  • Diacid or diamine monomers may be added at a concentration by weight of less than 20% relative to the total mixture.
  • the polymer At the outlet of polycondensation, the polymer is advantageously cooled with water, and extruded in the form of a rod. These rods are cut to produce granules.
  • the granules can be washed with water and then dried under vacuum.
  • the preferred tree branched polyamide according to the invention is a polyamide capable of being obtained at least by reaction of the monomers corresponding to the following formulas:
  • n is an integer greater than or equal to 2, preferably between 2 and 10 (limits included);
  • - R 6 and R may be the same or different and represent a covalent bond or an aliphatic, arylaliphatic, aromatic or alkylaromatic hydrocarbon radical;
  • R 8 is chosen from a linear or branched aliphatic radical, a substituted or unsubstituted cycloaliphatic radical, a substituted or unsubstituted aromatic radical which may optionally comprise one or more aromatic rings and / or heteroatoms, and a polymeric chain which may comprise one or more heteroatoms ;
  • B represents an amino functional group or amine salt when A represents an acid, ester, halogen acid or amide functional group; or a functional group acid, ester, halogen of acid or amide when A represents an amino functional group or amine salt;
  • Ai represents a functional group selected from the group comprising: acid, ester and acid chloride
  • - Bi represents a functional group chosen from the group comprising: the amine and the amine salt
  • R 9 , Rio and Ru can be the same or different and represent an alkyl, arylalkyl, alkylaryl, cycloaliphatic or aromatic, branched or linear, substituted or unsubstituted and / or saturated or unsaturated radical.
  • R 8 is an aromatic radical
  • R 6 and R 7 represent a covalent bond
  • B is an acid functional group
  • A is an amino functional group
  • n is equal to 2.
  • the compound of formula (VI) is preferably chosen from 5-amino-isophatalic acid and / or 6-amino-undecandioic acid.
  • the difunctional monomers of formulas NII to IX are the monomers used for the manufacture of linear thermoplastic polyamide.
  • ⁇ -aminoalkanoic compounds comprising a hydrocarbon chain having from 4 to 12 carbon atoms, or the lactams derived from these amino acid such as r ⁇ -caprolactam, the saturated aliphatic dicarboxylic acids having from 6 to 12 carbon atoms such that, for example adipic acid, azelaic acid, sebacic acid, dodecanoic acid, the linear or branched saturated preferably primary aliphatic diamines having from 6 to 12 carbon atoms such as, for example, hexamethylene diamine, trimethylhexamethylene diamine , tetramethylene diamine, m-xylene diamine.
  • the preferred bifunctional monomers of the invention are ⁇ -caprolactam, or hexamethylene diamine and adipic acid or a mixture of these.
  • the molar ratio between the multifunctional monomers of formula VI and the sum of the bifunctional monomers of formulas VII to IX, and possibly other monomers of the tree polyamide, is between 0.01% and 5%, preferably between 0.05% and 1%.
  • the tree polyamide of the invention can be obtained in different ways. In a first embodiment of this manufacturing process, a mixture of monomers is produced with determined proportions of each component. Said mixture is polymerized under conditions and according to a procedure equivalent to those used for the manufacture of linear polyamide corresponding to the bifunctional monomers used. Thus, when ⁇ -caprolactam is used, water is added to the mixture of monomers to initiate the hydrolytic opening of the caprolactam.
  • a linear polyamide prepolymer is produced by polycondensation of the bifunctional monomers to obtain a prepolymer of molecular weight in number M n of the order of approximately 2000 to 3000.
  • the polyfunctional monomer is added to the linear prepolymer and the polymerization is continued either in a molten medium or in the solid phase.
  • This embodiment makes it possible in particular to obtain hyperbranched copolyamides using polyfunctional monomers having thermal stability at relatively low temperatures, for example less than 200 ° C., since the post-condensation temperature in solid phase is carried out at temperatures lower than those of melt polymerization.
  • the addition of the polyfunctional monomer can be carried out in an extruder or in a reactor, the solid phase postcondensation being implemented according to the conventional and usual conditions used for that of linear polyamides.
  • the polyfunctional monomer is added with a catalyst thus making it possible to carry out the reaction directly in the extruder.
  • Suitable catalysts are the catalysts conventionally used for amidation or polycondensation reactions of amide functions such as phosphorous compounds for example.
  • the preferred hyperbranched polyamide according to the invention is a hyperbranched copolyamide of the type of those obtained by reaction between at least: a monomer of formula (X) below: ARB f (X) and a monomer of formula (XI) below:
  • the X / XI molar ratio is defined as follows: 0.05 ⁇ X / XI; more preferably 0.125 ⁇ X / XI ⁇ 2.
  • (XI) is aliphatic, cycloaliphatic or arylaliphatic.
  • the hydrocarbon-based entities R, R ′ of the monomers (X) and (XI) respectively, can each comprise:
  • carboxylic function means any COOH acid, ester, acid halide or anhydride function.
  • amine function is meant in the sense of the invention, any function of amine type or amine salt.
  • the hyperbranched polymer can consist of a mixture of several different monomers (X) and of several monomers
  • the hyperbranched copolyamide may also comprise, as constituent elements, mono or multi-functional monomers (XII) of the "heart" (or “nucleus”) type. and / or monofunctional monomers (XIII) of the "chain limiter" type.
  • the “core” type monomers optionally included in the copolyamide - hyperbranched according to the invention can be those of formula (XII) below:
  • R 1 is a substituted or unsubstituted hydrocarbon radical, of the genus silicone, linear or branched alkyl, aromatic, alkylaryl, arylalkyl or cycloaliphatic which can comprise unsaturations and / or heteroatoms;
  • B is a reactive function of the same nature as B or B '; and - n> 1, preferably 1 ⁇ n ⁇ 100.
  • the monomers of the “chain limiter” type optionally included in the hyperbranched copolyamide according to the invention can be those of formula (XIII):
  • R 2 -A "(XIII) in which: - R 2 is a substituted or unsubstituted hydrocarbon radical, of the silicone, linear or branched alkyl, aromatic, arylalkyl, alkylaryl or cycloaliphatic radical which may comprise one or more unsaturations and / or one or more heteroatoms; and
  • at least part of the bifunctional monomers (XI) are in the form of a prepolymer.
  • the radicals R and R can advantageously comprise functionalities which confer particular properties on the hyperbranched polymer. These functionalities do not react with the functions A, B, A ', B' during the polymerization of the hyperbranched polyamide.
  • f corresponds to 2 so that the monomer (X) is trifunctional: ARB 2 , A is an amino function, B is a carboxylic function and R is an aromatic radical.
  • the monomer (X) is for example chosen from the group comprising: 5-amino-isophthalic acid, 6-amino-undecandioic acid, 3-aminopimelic acid, aspartic acid, acid 3, 5-diaminobenzoic acid, 3,4-diaminobenzoic acid, lysine, and / or mixtures thereof.
  • the bifunctional monomer of formula (XI) is chosen - from the group comprising: ⁇ -caprolactam and / or the corresponding amino acid: aminocaproic acid; para or metaaminobenzoic acid; amino-11-undecanoic acid; lauryllactam and / or the corresponding amino acid: amino-12-dodecanoic acid, and / or mixtures thereof.
  • the bifunctional monomers of formula (XI) may be the monomers used for the manufacture of linear thermoplastic polyamides.
  • ⁇ -aminoalkanoic compounds comprising a hydrocarbon chain having from 4 to 12 carbon atoms, or lactams derived from these amino acids such as ⁇ -caprolactam.
  • the preferred bifunctional monomer (XI) of the invention is ⁇ -caprolactam.
  • the monomers (XII) can be chosen from the group comprising: saturated aliphatic dicarboxylic acids having from 6 to 36 carbon atoms such as, for example, adipic acid, azelaic acid, l sebacic acid, dodecanoic acid; biprimary, preferably saturated linear or branched aliphatic diamines having from 6 to 36 carbon atoms such as, for example, hexamethylenediamine, trimethylhexamethylene diamine, tetramethylenediamine, n-xylenediamine; polymeric compounds such as amino polyalkylene oxides sold under the trademark JEFF AMINE ®; or alternatively silicone chain amine, eg polydimethylsiloxane mono or diamine; aromatic or aliphatic monoamines; aromatic or aliphatic monoacids; aromatic or aliphatic triamines or triacids; and
  • the preferred monomers (XII), "core” are: hexamethylene diamine and adipic acid, JEFF AMINE ® T403 or 1,3,5-benzene tricarboxylic acid.
  • the molar ratio of the monomers (XIII) to the bifunctional monomers (X) may be less than or equal to 10, preferably less than or equal to 5, and more preferably still between 0 and 2 (limits included).
  • the molar ratio of the monomers (XII) relative to the multifunctional monomers (X) may be less than or equal to 1, preferably less than or equal to 0.5, and more preferably still between 0 and 0.3 (limits included).
  • hyperbranched copolyamides can be obtained by a process consisting essentially in carrying out a polycondensation between monomers (X) and monomers (XI) which react with one another and optionally with monomers (XII) and / or (XIII); and this under appropriate temperature and pressure conditions.
  • This "polymerization takes place in the melt phase, in the solvent phase or in the solid phase, preferably in the melt or solvent phase; the monomer (XI) advantageously playing the role of solvent.
  • the process for the synthesis of hyperbranched polyamides according to the invention can use at least one polycondensation catalyst. polycondensation is carried out, for example, under conditions and according to a procedure equivalent to those used for the manufacture of the linear polyamide corresponding to the monomers (XI).
  • the functionalities which can be supported by the hyperbranched polyamides according to the invention are, for example, fluorinated radicals, hydrocarbon radicals, fatty chains, silicone radicals, radicals with anti-UV, antioxidant, surfactant, softening properties, anti-fouling, stabilizing, hydrophobic and / or hydrophilic, or radicals with encapsulation and / or vectorization properties of active principles, for example of agrochemical nature or of dyes and / or pigments.
  • the hydrophilic functionalization may be provided by polyoxyalkylene radicals coming from amino polyoxyalkylene type JEFF AMINE ®.
  • hydrophobic functionalization can be provided by hydrocarbon radicals originating from a mono-acid or mono-amine aliphatic compound, such as n-hexadecylamine, n-octadecylamine and n-dodecylamine. These functions are advantageously carried by the monomers (XII) or (XIII).
  • composition of the present invention can also comprise, in addition to a branched polyamide as defined above, a thermoplastic matrix composed of linear polymer.
  • concentration of the branched polyamide relative to the total mass of the composition can be between 0.001 and 70%, preferably between 0.001 and 50% and, more preferably between 0.001 and 30%.
  • the thermoplastic matrix is composed of linear polyamides.
  • All the polyamide types can be used for carrying out the invention, for example polyamides of the type of those obtained by polycondensation of a diamine with a dicarboxylic acid, such as polyamide 66, or polyamides of the type of those which are obtained by polycondensation of amino acids or lactams, such as polyamide 6.
  • Particularly preferred is polyamide 6, polyamide 11, polyamide 12, copolyamides 6 / 6.6, and 6 / 6.36, mixtures and copolymers based on these polyamides or copolyamides.
  • the flame retardant system according to the present invention can comprise any type of flame retardant, that is to say compounds which make it possible to reduce the propagation of the flame and / or which have flame retardant properties, well known to man. of career.
  • flame retardants are usually used in flame retardant compositions and are notably described, for example, in patents US6344158, US6365071, US6211402 and US6255371, cited here for reference.
  • the fireproofing system comprises at least one fireproofing agent chosen from the group comprising: - magnesium derivatives such as for example magnesium hydroxide; aluminum derivatives such as for example aluminum hydroxide and aluminum phosphate; phosphorus derivatives such as for example red phosphorus; nitrogenous organic compounds such as for example triazines, cyanuric and / or isocyanuric acid, melamine or its derivatives such as melamine cyanurate, Poxalate, phthalate, borate, sulfate, phosphate, polyphosphate and / or pyrophosphate melamine, condensed melamine products, such as melem, melam and melon, tris (hydroxyethyl) isocyanurate, benzoguanamine, guanidine, allantoin, and glycoluril; - Bromine derivatives such as for example PBDPO (polybromodiphenyl oxide), BrPS (polystyrene bro e and polybromostyrene), poly
  • inorganic phosphates such as ammonium phosphates and polyphosphates; their salts and / or their mixtures.
  • the flame retardants mentioned above can be used alone or in combination.
  • the salts of the organophosphorous compounds can be, for example, aluminum, calcium, zinc, alkaline earth and / or magnesium salts.
  • flame retardants are used having a variation in weight greater than or equal to 1%, preferably greater than or equal to 5% at temperatures greater than or equal to 270 ° C. This change in weight can be measured by thermogravimetric analysis (TGA).
  • Synergistic agents can also be added to the flame retardant system, which will increase the flame retardant properties of the flame retardants.
  • the fireproofing system can comprise at least one synergistic agent chosen from the group comprising: - zeolites, such as for example phillipsites, chabazites and natrolites; ceramic powders; nanocomposites, such as for example momorillonite and alpha Zr-P; hydrotalcites such as for example magnesium carbonates and other alkaline earth carbonates, for example MgCO 3 , 5Mg (OH) 2 and 2Al (OH) 3 ; - zinc derivatives such as for example zinc oxide, zinc stannate, zinc hydroxystannate, zinc phosphate, zinc borate and zinc sulfide; flame retardants by intumescence, such as, for example, silico- and / or phospho-tungstic acid, polyhedral alcohols such as pentaeritritol, glycerin and polyvinyl alcohol,
  • the fireproofing system is chosen from the group comprising: - a system based on melamine cyanurate; a combination of poly dibromo styrene and antimony trioxide; and / or a system based on a cyclic diphosphate ester, such as for example the antiblaze 1045 (sold by Rhodia Consumer Specialties, see CAS no. 42595-45-9), optionally comprising glass fibers.
  • composition according to the invention can also comprise reinforcing fillers well known to those skilled in the art and chosen from the group comprising glass fibers, carbon fibers, mineral fibers, powders and / or ceramic fibers, heat-resistant organic fibers such as polyphthalamide fibers and mineral fillers such as wollastonite, kaolin, talc, clay, silica and mica, and mineral nanofillers such as montmorillonite and ⁇ -Zr phosphate; or their mixtures. Glass fibers are particularly preferred according to the invention.
  • the glass fibers preferably used are glass fibers for polyamide, having, for example, an average diameter of between 5 and 20 ⁇ m, preferably between 10 and 14 ⁇ m, such as for example glass fibers CS123D-10C (Owens Corning Fiberglass), CS1103 (Owens Corning Fiberglass) and CS983 (Vetrotex) and CS99B (Vetrotex). It is advantageous to use ground glass fibers and / or non-enzymatic fibers at the surface.
  • Reinforcement fillers can represent from 0 to 80%, preferably from 5 to 55%, even more preferably from 10 to 40% by weight relative to the total weight of the composition.
  • the composition according to the invention may also comprise one or more additives usually used by a person skilled in the art in the polyamide-based compositions used for the manufacture of molded articles.
  • additives include thermal stabilizers, molding agents such as calcium stearate, stearamides and erucamides, UN stabilizers, antioxidants, lubricants, abrasion reducers. , pigments, dyes, plasticizers, laser labeling promoters or impact modifiers.
  • the antioxidants and heat stabilizers are, for example, alkali halides, copper halides, sterically hindered phenolic compounds, organic phosphates and aromatic amines.
  • UN stabilizers are generally benzotriazoles, benzophenones or HALS in combination with antioxidants.
  • the present invention also relates to a process for manufacturing a flame retardant composition according to the invention in which at least one branched polyamide and a flame retardant system as described above are mixed, for example by melt extrusion.
  • the mixing can be carried out in the molten state, for example in a single or twin screw extruder, or by mixing without going into the molten state, even example in a mechanical mixer.
  • the compounds can be introduced simultaneously or successively. All the means known to those skilled in the art concerning the introduction of the various compounds of a thermoplastic composition can be used.
  • An extrusion device is generally used in which the material is heated, subjected to a shearing force, and conveyed. Such devices are perfectly known to those skilled in the art.
  • the composition according to the invention, when it is prepared using an extrusion device can be packaged in the form of granules or used directly for shaping an article.
  • the present invention also relates to a process for manufacturing an article by shaping a composition according to the invention by a process chosen from the group comprising an extrusion process, such as the extrusion of sheets and films, molding, such as compression molding, injection molding, such as injection molding, and spinning.
  • an extrusion process such as the extrusion of sheets and films
  • molding such as compression molding, injection molding, such as injection molding, and spinning.
  • the present invention is particularly suitable for the manufacture of articles used in the automotive field, electrical or electronic connections such as elements of circuit breakers, switches, connectors or the like.
  • PA 6 having a melt index of 140 ml / g (ISO 307, formic acid), and Mn 17600 g / mol (by GPC), sold by Rhodia, France;
  • PA B PA 6 star obtained by copolymerization of caprolactam of formula (IV) with 0.5 mol% of 2,2,6,6-tetra- ( ⁇ -carboxyethyl) cyclohexanone (polyfunctional compound of formula (V)) by relative to the total number of moles of the polyamide.
  • Polyamide has a melt flow index (MFI) of 40 g / 10 minutes (according to standard ASTM D1238, at a temperature of 275 ° C. under a load of 325 g), and an Mn of 18,000 g / mol (by GPC);
  • Zinc borate Firebrake® ZB (US Borax);
  • PDBS 80 poly di-bromo styrene, containing 59% bromine (Caldic) - Sb O: antimony trioxide;
  • Irganox 1098 (Ciba-Geigy);
  • Antiblaze 1045 CAS No. 42595-45-9 (Rhodia Consumer Specialties)
  • the compositions are prepared by mixing the components in the proportions indicated in the examples, on a Werner & Pfleiderer ZSK 30 twin-screw extruder, having a screw speed of 250 rpm and an output of 15 Kg / h. Temperatures of around 240 ° C are used for PA6.
  • Glass fibers and mineral compounds are added to the mixture at the throat of the extruder.
  • the granules are dried and molded on an Arburg 320 M500-210 injection molding machine at a temperature of 240 ° C (PA6 and PA connected) and then molded at 80 ° C.
  • the properties are determined on test pieces according to the following methods:
  • the flame resistance is measured according to the UL-94 test ("Underwriters Laboratories"). This test is carried out with test specimens of 1.6 mm and 0.8 mm thickness, after conditioning for 48 hours at 50% RH (relative humidity). The result is coded as follows:
  • V-2 the average combustion time is less than 25 seconds, the maximum combustion time - less than 30 seconds (self-extinguishing); drop of polyamide igniting cotton
  • Vl average combustion time is less than 25 seconds, the maximum combustion time is less than 30 seconds (self-extinguishing); no inflammation of cotton by gout
  • V-0 average combustion time is less than 5 seconds, the maximum combustion time is less than 10 seconds (self-extinguishing); no cotton inflammation
  • the compound burn times during the UL-94 test are measured in seconds.
  • the resistance to glowing wire (GWT) is measured according to standard IEC 695-2-1 on test pieces with a thickness of 3.0 mm, 1.5 mm and 1.0 mm. Results at different temperatures are classified as follows:
  • the mechanical properties are determined according to the following methods:

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Connector Housings Or Holding Contact Members (AREA)
EP03784227A 2002-08-13 2003-08-08 Flammfeste verzweigtes polyamid enthaltende zusammensetzung Withdrawn EP1546244A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0210274 2002-08-13
FR0210274A FR2843593B1 (fr) 2002-08-13 2002-08-13 Composition polyamide branche ignifugee
PCT/FR2003/002494 WO2004014993A2 (fr) 2002-08-13 2003-08-08 Composition a base de polyamide branche ignifugee

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CN103146153A (zh) * 2011-12-07 2013-06-12 杜邦公司 阻燃的共聚醚酯组合物及包含其的制品
DE102011121504A1 (de) * 2011-12-16 2013-06-20 Clariant International Ltd. Gemische von Diphosphinsäuren und Alkylphosphonsäuren, ein Verfahren zu deren Herstellung und ihre Verwendung
DE102011121503A1 (de) * 2011-12-16 2013-06-20 Clariant International Ltd. Gemische von Dioshinsäuren und Dialkylphosphinsäuren, ein Verfahren zu deren Herstellung und ihre Verwendung
CN109844001B (zh) 2016-10-13 2022-03-11 巴斯夫欧洲公司 阻燃性聚酰胺
CN108178923B (zh) * 2018-02-01 2020-12-08 南方科技大学 一种改性的尼龙纤维母粒及使用其制备的改性尼龙纤维
CN118516077B (zh) * 2024-06-05 2025-02-11 东莞市腾威电子材料技术有限公司 一种阻燃型聚氨酯胶粘剂及其制备方法和应用

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FR2695395B1 (fr) * 1992-05-22 1994-10-28 Atochem Elf Sa Compositions thermoplastiques ignifuges à base de polyamide.
ATE325152T1 (de) * 1995-12-29 2006-06-15 Rhodia Eng Plastics Srl Polyamid und verfahren zu dessen herstellung
FR2774689B1 (fr) * 1998-02-11 2001-05-04 Nyltech Italia Composition polyamide ignifugee

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AU2003276324A8 (en) 2004-02-25
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WO2004014993A3 (fr) 2004-04-08
FR2843593A1 (fr) 2004-02-20
AU2003276324A1 (en) 2004-02-25

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