EP3574038A1 - Flexible, feuerfeste thermoplastische zusammensetzungen mit hoher thermomechanischer festigkeit und verbesserter thermischer alterungsbeständigkeit - Google Patents

Flexible, feuerfeste thermoplastische zusammensetzungen mit hoher thermomechanischer festigkeit und verbesserter thermischer alterungsbeständigkeit

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Publication number
EP3574038A1
EP3574038A1 EP18707075.0A EP18707075A EP3574038A1 EP 3574038 A1 EP3574038 A1 EP 3574038A1 EP 18707075 A EP18707075 A EP 18707075A EP 3574038 A1 EP3574038 A1 EP 3574038A1
Authority
EP
European Patent Office
Prior art keywords
polyolefin
composition according
segment
composition
polyamide
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.)
Withdrawn
Application number
EP18707075.0A
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English (en)
French (fr)
Inventor
Jean-Jacques Flat
Mathieu SABARD
Dominique Jousset
David Meslet
Regis Cipriani
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.)
Arkema France SA
Original Assignee
Arkema France SA
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Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP3574038A1 publication Critical patent/EP3574038A1/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Withdrawn legal-status Critical Current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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/5205—Salts of P-acids with N-bases
    • 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
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/028—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyamide sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/46—Bases; Cases
    • H01R13/52—Dustproof, splashproof, drip-proof, waterproof, or flameproof cases
    • H01R13/527—Flameproof cases

Definitions

  • the present invention relates to thermomechanically resistant flexible thermoplastic flame retardant compositions based on polyolefins and polyamides containing at least one flame retardant and a color additive.
  • the present invention also relates to the use of such a composition and to a process for preparing this composition.
  • Thermoplastic polymers such as polyethylenes, polyamides or their mixtures are good electrical insulators and are easy to implement. They are used in particular to produce housings and electrical connectors and also cable coverings. Electrical installations can cause short circuits and ignite, they can also be put in contact with a flame and thus ignite and spread the fire along the cable trays.
  • halogenated additives is increasingly limited for questions of ecotoxicology and toxicology (toxicity and corrosivity of vapors emitted during fires).
  • thermal stability is meant the preservation of the mechanical properties (and more particularly the elongation at break) after various thermal aging (for example 1 week at 120 ° C. in hot air).
  • compositions based on functionalized polyolefms grafted with polyamides, flame-retarded without halogen which make it possible to produce a material that is efficient in terms of resistance to the propagation of the flame (according to the UL94 test), also having mechanical and thermomechanical properties of good level as well as a good thermal stability and a satisfactory rheology (no excessive viscosifcation, high MFI (Melt Flow Index)), without producing exudation on the materials obtained.
  • thermoplastic compositions so that, for example, the cables can be distinguished according to their section or number of conductors.
  • compositions described above have a drawback in that the materials darken over time.
  • the different colorations of cables are no longer differentiable.
  • the present invention thus relates to a composition, comprising:
  • a copolymer comprising at least one segment of a polyolefin and at least one segment of a polyamide
  • a color additive if appropriate, and optionally a molecular sieve.
  • the present invention relates to a composition, comprising:
  • a copolymer comprising at least one segment of a polyolefin and on average at least one segment of a polyamide attached to said polyolefin by the residues of at least one unsaturated monomer (X), piperazine pyrophosphate,
  • said composition is a flame retarded composition, preferably a flexible thermoplastic flame retardant composition.
  • flexible thermoplastic means a composition having a flexural modulus of less than or equal to 600 MPa at room temperature and an elastic modulus value, measured by dynamic mechanical analysis (DMA), of at least 0.5 MPa at 150 ° C.
  • DMA dynamic mechanical analysis consists in dynamically pulling (1Hz) the material to be analyzed over a temperature range of -100 ° C up to 250 ° C at a heating rate of 2 ° C / min, and to record the values of the elastic and loss modules as well as their ratio corresponding to the tangent of the angle of loss.
  • composition according to the present invention has a high thermal stability.
  • composition is considered to have satisfactory thermal stability when it retains on the order of 70% of its initial mechanical properties of elongation at break and breaking stress after aging under thermooxidation conditions.
  • the rheology of the composition is considered satisfactory when it is compatible with the usual transformation processes of the materials from the compositions according to the invention (extrusion, injection, etc.).
  • said composition does not comprise a halogenated compound.
  • the composition according to the present invention comprises from 50 to 70%, preferably 55 to 65%, and particularly preferably about 60% by weight of said copolymer relative to the total weight of the composition.
  • the composition according to the present invention comprises from 5 to 50%, preferably from 10 to 40%, particularly preferably from 10 to 30% by weight of said piperazine phosphate relative to the total weight of the composition.
  • the composition comprises 5 to 20%, and more particularly 10 to 15% by weight of said piperazine phosphate relative to the total weight of the composition.
  • composition according to the invention may comprise a coloring additive or not.
  • the composition according to the present invention can be colored or not colored.
  • the composition according to the present invention preferably comprises from 0.1 to 5%, preferably from 0.5 to 2% and particularly preferably from 1% by weight of coloring additive to the total weight of the composition.
  • the composition according to the present invention comprises from 0.1 to 5%, preferably from 0.5 to 3% and particularly preferably from approximately 2% by weight of molecular sieve relative to the total weight of the composition.
  • the present invention relates to a composition, comprising:
  • said copolymer comprises on average at least 1.3 moles of residues of the unsaturated monomer (X) attached to the at least one polyolefin segment per mole of polyolefin segment and preferably on average less than 20 moles of monomer residues.
  • unsaturated (X) bonds to the at least one polyolefin segment per mole of polyolefin segment.
  • said copolymer comprises on average between 3 and 5 moles of residues of the unsaturated monomer (X) attached to the at least one polyolefin segment per mole of polyolefin segment.
  • the copolymers of the present invention are characterized by a nano-structured organization with polyamide lamellae of thickness between 5 and 100 nanometers, preferably between 10 and 50 nanometers.
  • the polyolefin / polyamide weight ratio in the copolymer as defined above is between 90:10 and 50:50, preferably between 80:20 and 70:30.
  • Said unsaturated monomer X can be, for example, an unsaturated epoxide, a (meth) acrylic acid or an unsaturated carboxylic acid anhydride.
  • the unsaturated carboxylic acid anhydride may be chosen, for example, from the group consisting of: maleic, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic anhydride, 4-methylenecyclohex-4-ene-1 , 2-dicarboxylic, bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic acid and x-methylbicyclo (2,2,1) hept-5-ene-2,2-dicarboxylic acid.
  • said unsaturated carboxylic acid anhydride is maleic anhydride.
  • Polyolefin or “polyolefin segment” is understood to mean a polymer comprising a comonomer chosen from the group consisting of:
  • alpha-olefins advantageously those having from 3 to 30 carbon atoms.
  • said alpha olefin may be chosen from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene and 4-methyl-1.
  • pentene 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, dococene, 1 the - tetracocene, 1-hexacocene, 1-octacocene and 1-triacontene, preferably propylene or ethylene, particularly preferably ethylene;
  • esters of unsaturated carboxylic acids such as, for example, alkyl acrylates or alkyl methacrylates, preferably said alkyls containing from 1 to 24 carbon atoms, examples of alkyl acrylate or methacrylate are especially the methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate;
  • vinyl esters of saturated carboxylic acids such as, for example, acetate or vinyl propionate
  • dienes such as, for example, butadiene, isoprene or 1,4-hexadiene;
  • said polyolefin segment may be chosen from the group consisting of:
  • LDPE low density polyethylenes
  • HDPE high density polyethylenes
  • LLDPE linear low density polyethylenes
  • VLDPE very low density polyethylene
  • metallocene polyethylene metallocene polyethylene
  • ethylene / alpha-olefin polymers such as ethylene-propylene, ethylene-butylene, ethylene-propylene-diene monomer, ethylene-octene, only poy mixed with a PE;
  • SEBS Styrene / ethylene-butene / styrene block polymers
  • SBS styrene / butadiene / styrene
  • SIS styrene / isoprene / styrene
  • SEPS styrene / ethylene-propylene / styrene
  • ethylene-maleic anhydride and ethylene-alkyl (meth) acrylate-maleic anhydride polymers consist of an ethylene-alkyl (meth) acrylate polymer.
  • the proportion of alpha-olefin is less than 60% by weight, preferably between 2 and 40% by weight of said copolymer, and particularly preferably from 15 to 35% by weight of said copolymer.
  • said polyethylene segment is a mixture of several polymers, preferably it comprises at least 50%> and preferably 75% (moles) of ethylene relative to said mixture.
  • the proportion of alpha-olefin is less than 60% by weight, preferably between 2 and 40% by weight of said polyolefin / polyamide copolymer, and particularly preferably from 15 to 35% by weight of said copolymer.
  • said ethylene-maleic anhydride and ethylene-alkyl (meth) acrylate-maleic anhydride polymers comprise from 0.2 to 10% by weight of maleic anhydride relative to the total weight of said polymer.
  • said ethylene-alkyl (meth) acrylate-maleic anhydride polymer segments comprise from 0 to 50%, preferably 2 to 40% and more preferably 5 to 30% by weight of alkyl (meth) acrylate.
  • said at least one polyolefin segment has a viscosity index ("Melt Flow Index" (MFI)) of between 3 and 1000 g / 10 min, preferably between 20 and 400 g / 10 min (190 ° C., 2.16 kg). ASTM D 1238).
  • MFI Viscosity index
  • said at least one polyolefin segment has a density of between 0.86 and 0.98 g / cm 3 , more preferably between 0.90 and 0.94 g / cm 3 .
  • the melt temperature of the polyolefin polymers as described above is less than 180 ° C, preferably less than 160 ° C, particularly preferably between 80 and 120 ° C.
  • polyamide or "polyamide segment” means a polymer having amide functions.
  • said polyamide or polyamide segment is a condensation product:
  • amino acids such as aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids;
  • lactams such as caprolactam, oenantholactam and laurylactam
  • diamine salts or mixtures such as hexamethylenediamine, dodecamethylenediamine, metaxylylenediamine, bis-p-aminocyclohexylmethane and trimethylhexamethylenediamine with diacids such as isophthalic, terephthalic, adipic, azelaic and suberic acids, sebacic and dodecanedicarboxylic:
  • said polyamide segment is chosen from the group consisting of: PA 6, PA 11, PA 12, PA 6/11 (patterned polyamide 6 and units 11), PA 6/12 (polyamide with patterns 6 and 12), and PA 6 / 6-6 (polyamide based on caprolactam, hexamethylenediamine and adipic acid).
  • the degree of polymerization can vary widely.
  • said polyamide segment has an amino functional end.
  • Said amino-ended polyamide segment can be obtained using a chain limiter of formula:
  • R 1 is selected from the group consisting of hydrogen and a linear or branched alkyl group having up to 20 carbon atoms,
  • R-2 is selected from the group consisting of:
  • Said chain limiter can be for example laurylamine or oleylamine.
  • said polyamide has a molar mass Mn of between 500 and 10,000 g / mol, preferably between 1000 and 5000 g / mol and more preferably between 2000 and 3000 g / mol.
  • piperazine pyrophosphate is used as flame retardant.
  • flame retardant agent means compounds that make it possible to improve the fire resistance of plastic materials.
  • Piperazine pyrophosphate can be encapsulated in a melamine-based resin.
  • the only flame retardant of the composition according to the present invention is based on piperazine pyrophosphate.
  • flame-retardant agent based on piperazine pyrophosphate means a flame-retardant agent comprising at least 50, preferably 60, 70, 80, 90, and even more preferably 95% by weight of piperazine pyrophosphate relative to the weight fireproofing agent.
  • the term "color additive” means chemical or natural dyes, coloring pigments and brighteners. The color additive may for example be chosen from those listed in the document Dyes and Pigments, by Daniel WYART from the Techniques de l'In distributedur.
  • the coloring additive is used as a masterbatch.
  • the composition according to the present invention further comprises a molecular sieve, preferably selected from the group consisting of a hydrotalcite and a zeolite.
  • a molecular sieve preferably selected from the group consisting of a hydrotalcite and a zeolite.
  • said zeolite is selected from the group consisting of: type 3A, 4A, 5A, 10X and 13X zeolites.
  • composition according to the invention may further comprise at least one additive selected from the group consisting of: an antioxidant, a UV stabilizer, a thermal stabilizer, a fluidifying agent such as silica or ethylene-bis-amide, an implementing agent such as calcium stearate or magnesium stearate and mineral fillers.
  • at least one additive selected from the group consisting of: an antioxidant, a UV stabilizer, a thermal stabilizer, a fluidifying agent such as silica or ethylene-bis-amide, an implementing agent such as calcium stearate or magnesium stearate and mineral fillers.
  • the composition according to the invention comprises from 0 to 20% by weight of additive relative to the total weight of the composition.
  • the antioxidant makes it possible to protect the plastic material against thermal aggression due to the process of implementation or during the life of the plastic part.
  • said antioxidant may be selected from the group consisting of sterically hindered phenol compounds, phosphite groups, and mixtures thereof.
  • the composition according to the present invention comprises from 0 to 10%, preferably from 0.1 to 5% by weight of said antioxidant relative to the total weight of the composition.
  • the UV stabilizer prevents yellowing of the composition which may be due to UV radiation (Ultra Violet).
  • said UV stabilizer may be selected from the group consisting of: UV absorbers such as benzotriazole and benzophenone, and hindered amines (HALS).
  • the composition according to the present invention comprises from 0 to 10%, preferably from 0.1 to 5% and still more preferably from 0.2 to 2% by weight of said UV stabilizer relative to the total weight of the composition.
  • the composition according to the present invention further comprises at least one polyolefin, maleate or not. The presence of polyolefins makes it possible in particular to limit the water uptake of the composition at elevated temperature, especially at around 85 ° C.
  • said polyolefin is selected from the group consisting of homopolymers and copolymers of polypropylene, polyethylenes such as HDPE, LDPE, elastomeric polyolefins, especially based on monomers having 2 to 8, and in particular 2 to 4 carbon atoms, ethylene propylene (EPR) rubbers and olefinic block copolymers such as polyethylene block polypropylenes.
  • polyethylenes such as HDPE, LDPE
  • elastomeric polyolefins especially based on monomers having 2 to 8, and in particular 2 to 4 carbon atoms
  • EPR ethylene propylene
  • olefinic block copolymers such as polyethylene block polypropylenes.
  • the application relates to the use of a composition according to the invention for the manufacture of coating of metal cables, electrical parts such as electrical connectors or electrotechnical housings, thermal protection coatings or sleeves. , injection molded parts for electronic equipment such as computers and telephones, single or multi-layer tubes, corrugated tubes, preferably for the manufacture of wire rope lining.
  • the present invention relates to a method for preparing the composition as defined above, comprising the steps of:
  • the mixing step is carried out in an extruder, a co-kneader, an internal mixer or any other usual device for mixing thermoplastic polymers.
  • the mixture is made in an extruder, preferably a bi-screw corotative extruder.
  • steps a) and b) can be performed simultaneously, preferably in an extruder.
  • the grafting of said unsaturated monomer on said at least one polyolefin segment is carried out according to the methods usually known to those skilled in the art, for example at a temperature of between 200 and 350 ° C., under vacuum or under an inert atmosphere with stirring of the reaction mixture.
  • said grafting may be carried out by a melt-reactive extrusion process or by a solution-in-solvent process.
  • the copolymer can be obtained by reacting at least one amino-terminated polyamide segment with the residues of said unsaturated monomer X attached to said at least one polyolefin segment.
  • the addition of said at least one polyamide segment to said at least one X-containing polyolefin segment is achieved by reacting an amine function of said polyamide segment with X.
  • X has an anhydride or acid function, thereby creating amide or imide bonds.
  • this addition step is carried out in the molten state.
  • this addition step is carried out in an extruder.
  • this addition step is carried out between 230 and 300 ° C.
  • This addition step is preferably carried out between 5 seconds and 5 minutes, and preferably between 20 seconds and 1 minute, and corresponds to the residence time of the mixture of said at least one polyolefin segment containing X with said at least one segment. of polyamide.
  • the yield of this addition can be evaluated by selective extraction of said at least one segment of free polyamides, that is to say those which have not reacted to form the copolymer according to the invention.
  • the preparation of polyamide segments according to the present invention as well as their addition to a polyolefin containing X is described in US Patents 3976720, US 3963799, US 5342886 and FR 2291225.
  • the present invention relates to electronic, electrical or thermal protection components comprising the composition as defined above.
  • These components can be chosen in particular in the group consisting of metal cable covers, electrical parts such as electrical connectors, electro-technical housings, electronic components of computers or telephones and thermal protection coatings and sleeves.
  • Bondine HX8290, Lotader 5500 and 4210 are terpolymers of ethylene, alkyl acrylate and maleic anhydride marketed by the Applicant.
  • EVA 2403 is a copolymer of ethylene and vinyl acetate with an MFI
  • the PA6 (polyamide 6) prepolymer is a PA6 having a number average molecular weight of 2500 g / mol and terminated with a single primary amine function.
  • Siliporite NK10AP is a type 4A zeolite produced by CECA.
  • Irganox 1010 is a primary antioxidant produced by BASF.
  • Alkanox 240 is a secondary antioxidant produced by Chemtura Great Lakes.
  • Budit 3178 is a flame retardant based ammonium polyphosphate produced by the company Budenheim.
  • ADK STAB FP2500S is a flame retardant based on piperazine pyrophosphate marketed by the company ADK.
  • PE48 / 5 / 4025F is a blue masterbatch produced by the company Colloids.
  • Compositions 5 and 6 are counterexamples.
  • Protocol used to measure elongation at break, aging and fire properties (UL94 and LOI)
  • the granules from the preparation step are then shaped according to the following methods:
  • Test according to UL 94 Test specimens injected with dimensions 127 mm x 12.7 mm and having a thickness of 1.6 mm
  • the thermal aging conditions are as follows: The cut-off IFC specimens are placed in an air circulation oven, which is temperature-controlled for a certain period of time. Composition 1 2 3 4 5 6 7 8 9 10 11
  • Alkanox 240 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.475 0.5 0.5 0.5
  • the flame propagation test is carried out according to the UL94 standard on injected test pieces.
  • the tested material is classified V0 if:
  • the Oxygen Limit Index (LOI) test is carried out according to the ASTM D2863 standard on injected test pieces.
  • the materials according to the invention have satisfactory performance for the intended applications (initial elongation at break, retention of these elongations at break after aging of 240 hours at 175 ° C, fireproofing according to flame propagation test UL94 and Limit Index of oxygen).
  • the examples based on ammonium polyphosphate unlike against the examples based on ammonium polyphosphate, only the examples based on piperazine pyrophosphate have the property of remaining distinguishable in color after a thermal-oxidation aging of 240 hours at 175 ° C.
  • the resistance to fire on cable was measured on two samples obtained by coating a cable diameter of 1.7 and 1.9 mm respectively with a layer with a thickness of 0.3 mm of composition 3 and 11.
  • the tests were carried out on a test bench equipped with a propane gas burner and equipped with a 45 ° support at a temperature of 23 ° C without displacement of air.
  • Five samples of composition-based cable 3 and 11 with a length of 600 mm each were positioned on the support so as to be inclined at 45 ° to the horizontal, and then exposed for a period of 30 seconds to the burner flame forming a right angle with the sample and aimed at the lower end of the cable (length of the flame: 100 mm, with a blue dart of 50 mm temperature of 990 ° C). After removal of the flame, the combustion time and the length of insulator remained intact.
  • the upper end of the cable tested remained intact for at least 50mm in length.

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  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)
EP18707075.0A 2017-01-27 2018-01-26 Flexible, feuerfeste thermoplastische zusammensetzungen mit hoher thermomechanischer festigkeit und verbesserter thermischer alterungsbeständigkeit Withdrawn EP3574038A1 (de)

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FR1750697A FR3062390B1 (fr) 2017-01-27 2017-01-27 Compositions thermoplastiques souples a haute tenue thermomecanique et ignifugees a vieillissement thermique ameliore
PCT/FR2018/050179 WO2018138446A1 (fr) 2017-01-27 2018-01-26 Compositions thermoplastiques souples à haute tenue thermomécanique et ignifugées à vieillissement thermique amélioré

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EP3574038A1 true EP3574038A1 (de) 2019-12-04

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US (1) US20190367714A1 (de)
EP (1) EP3574038A1 (de)
JP (1) JP2020514487A (de)
KR (1) KR20190104071A (de)
CN (1) CN110214158A (de)
FR (1) FR3062390B1 (de)
WO (1) WO2018138446A1 (de)

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WO2021201085A1 (ja) * 2020-03-31 2021-10-07 株式会社Adeka 難燃剤組成物、難燃性合成樹脂組成物および成形体
FR3110860A1 (fr) 2020-06-02 2021-12-03 Arkema France Zéolithes à compatibilité améliorée
FR3124760A1 (fr) * 2021-07-02 2023-01-06 Nexans câble comprenant une gaine compacte retardante au feu

Family Cites Families (13)

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US3976720A (en) 1974-11-13 1976-08-24 E. I. Du Pont De Nemours And Company Polyamide/polyolefin plastic graft copolymers
US3963799A (en) 1974-11-13 1976-06-15 E. I. Du Pont De Nemours And Company Graft copolymer in polyamide polyethylene blends
JPS51125466A (en) 1974-11-13 1976-11-01 Du Pont Process for preparing graftcopolymer
US5342886A (en) 1988-03-24 1994-08-30 Atochem α-monoolefinic graft copolymers
AU3438400A (en) * 1999-03-31 2000-10-16 Atofina Polyamide and polypropylene mixtures and injected parts produced with said mixtures
JP4672505B2 (ja) * 2005-04-13 2011-04-20 信越化学工業株式会社 難燃性接着剤組成物、ならびにそれを用いた接着シート、カバーレイフィルムおよびフレキシブル銅張積層板
FR2897355B1 (fr) * 2006-02-16 2012-07-20 Arkema Copolymeres comportant des blocs polyamide et des blocs polyether, ayant des proprietes optiques et thermiques ameliorees
FR2901799B1 (fr) * 2006-06-02 2008-08-01 Arkema France Compositions thermoplastiques souples a haute tenue thermomecanique et ignifugees sans halogene
JP5570684B2 (ja) * 2007-02-28 2014-08-13 日本エイアンドエル株式会社 低発煙性樹脂組成物
JP5344742B2 (ja) * 2008-08-01 2013-11-20 株式会社Ａｄｅｋａ 難燃性熱可塑性樹脂組成物
CN102482239A (zh) * 2009-08-20 2012-05-30 堺化学工业株式会社 (聚)焦磷酸哌嗪粉粒体及其制造方法
FR2966464B1 (fr) * 2010-10-26 2012-11-02 Arkema France Compositions thermoplastiques a haute tenue thermomecanique et ignifugees, en particulier pour les cables electriques
CN105694443B (zh) * 2016-03-18 2018-02-23 上海化工研究院有限公司 一种无卤阻燃玻纤增强尼龙6材料及其制备方法

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FR3062390A1 (fr) 2018-08-03
FR3062390B1 (fr) 2020-11-06
CN110214158A (zh) 2019-09-06
JP2020514487A (ja) 2020-05-21
US20190367714A1 (en) 2019-12-05
KR20190104071A (ko) 2019-09-05
WO2018138446A1 (fr) 2018-08-02

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