Classifications

• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
• • C—CHEMISTRY; METALLURGY
  • 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
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
  • Y10T428/1314—Contains fabric, fiber particle, or filament made of glass, ceramic, or sintered, fused, fired, or calcined metal oxide, or metal carbide or other inorganic compound [e.g., fiber glass, mineral fiber, sand, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/1372—Randomly noninterengaged or randomly contacting fibers, filaments, particles, or flakes

Definitions

• the present invention relates to a composition comprising at least one particular polyamide, at least one reinforcement and at least one particular flame retardant, a method of preparing said composition and uses of said composition.
• Raw materials derived from biomass usually called bio-sourced or bio-resourced, can be renewed and generally have a reduced impact on the environment, because already being functionalized, they require fewer processing steps.
• a renewable raw material is a natural animal or plant resource whose stock can be replenished over a short period of time on a human scale, it is necessary that this stock can be renewed as quickly as it is consumed.
• this stock can be renewed as quickly as it is consumed.
• being constituted of non-fossil carbon during their incineration or degradation, the CO 2 resulting from these materials is not a contributor in the accumulation of CO 2 in the atmosphere.
• Biomass is understood to mean the raw material of plant or animal origin naturally produced. This type of raw material is characterized by the fact that the plant for its growth has consumed atmospheric CO 2 while producing oxygen. The animals for their growth consumed this vegetable raw material and thus assimilated carbon derived from atmospheric CO 2 .
• these biomass raw materials require fewer refining and processing stages, which are very expensive in terms of energy.
• the production of CO 2 is reduced, so that these raw materials contribute less to global warming.
• the plant consumed atmospheric CO 2 at a rate of 44 g CO 2 per mole of carbon (or 12 g of carbon) for its growth.
• the use of a raw material from biomass begins by decreasing the amount of atmospheric CO 2 .
• Vegetable materials including algae and microalgae in the marine environment, have the advantage of being able to be grown in large quantities, depending on demand, over most of the globe.
• the present invention therefore firstly relates to a composition comprising; the weight percentages being given with respect to the total weight of the composition:
• At least one metal salt optionally contained in a polymer, selected from a metal salt of phosphinic acid, a metal salt of diphosphinic acid and mixtures thereof. It has been found that a composition comprising such characteristics makes it possible to obtain a stable melt viscosity during its conversion, while exhibiting very interesting flame retardant properties, that is to say a VO classification according to the UL94 test (according to the NFT 51072 standard) for a thickness of 0.8 mm, a satisfactory rigidity and a very satisfactory impact resistance, leading to a shock greater than 8 kJ / m 2 .
• the invention also relates to a process for preparing such a composition.
• raw materials from biomass contain 14 C in the same proportions as atmospheric CO 2 . All carbon samples from living organisms
• 14 C / 12 C of living tissue is identical to that of the atmosphere.
• 14 C exists in two main forms: in mineral form, and in organic form, that is to say of carbon integrated in organic molecules such as cellulose.
• the 14 C / 12 C ratio is kept constant by metabolism because carbon is continuously exchanged with the environment.
• the proportion of 14 C is constant in the atmosphere, it is the same in the body, as long as it is alive, since it absorbs this 14 C as it absorbs 12 C.
• the average ratio of 14 C / 12 C is equal to 1, 2x10 "12.
• Carbon 14 is derived from the bombardment of atmospheric nitrogen (14), and spontaneously oxidizes with the oxygen of the air to give CO 2 .
• the CO2 content of 14 increased as a result of atmospheric nuclear explosions, and has been decreasing after stopping the tests.
• 12 C is stable, that is to say that the number of atoms of 12 C in a given sample is constant over time.
• - no is the number of 14 C at the origin (at the death of the creature, animal or plant)
• - n is the number of 14 C atoms remaining at the end of time t
• - a is the disintegration constant (or radioactive constant); it is connected to the half-life.
• the half-life of 14 C is 5730 years. In 50 000 years, the 14 C content is less than 0.2% of the initial content and therefore becomes difficult to detect. Petroleum products, natural gas or coal therefore do not contain 14 C.
• T1 / 2) of 14 C the 14 C content is substantially constant since the extraction of raw materials from the biomass, until the manufacture of the polymer according to the invention and even until the end of its use.
• the polyamide present in the composition according to the invention comprises at least 50% of organic carbons (that is to say of carbon incorporated in organic molecules) derived from raw materials from biomass according to the ASTM D6866 standard. relative total amount of carbons of the polymer, preferably greater than 60%, and preferably greater than 80%.
• This content may be certified by determination of the 14 C content according to one of the methods described in ASTM D6866-06 (Standard Test Methods for
• This standard ASTM D6866-06 includes three methods of measuring organic carbon from raw materials derived from biomass, called in English "biobased carbon". These methods compare the measured data on the analyzed sample with the data of a 100% bio-sourced or biomass-derived sample to give a relative percentage of carbon from the biomass in the sample.
• the proportions indicated for the polymers of the invention are preferably measured according to the mass spectrometry method or the liquid scintillation spectrometry method described in this standard.
• Ci, Cj, Ck the respective number of carbon atoms of the monomers i, j and k in the polyamide
• Ck ' number of organic carbon atoms derived from biomass in monomer (s) k, nature (from biomass or fossil), ie the origin of each of monomers i, j and k, being determined according to one of the measurement methods of the standard
• the (co) monomers of the polyamide are monomers i, j and k within the meaning of equation (I).
• the polyamide contains a content% Corg.bio greater than or equal to 50%, advantageously greater than or equal to 70%, preferably greater than or equal to 80%.
• polyamide according to the invention can also be validly labeled
• the (co) monomer (s) may be derived from raw materials derived from biomass, such as vegetable oils or natural polysaccharides, such as starch or cellulose, the starch being extractable, for example corn or potato.
• biomass such as vegetable oils or natural polysaccharides, such as starch or cellulose, the starch being extractable, for example corn or potato.
• This or these (co) monomers, or starting materials may in particular come from various conversion processes, including conventional chemical processes, but also enzymatic transformation processes or by bio-fermentation.
• the diacid C12 (dodecanedioic acid) can be obtained by bio-fermentation of dodecanoic acid, also called lauric acid, lauric acid can be extracted from the rich oil formed of kernal palm and coconut , for example.
• the C14 diacid (tetradecanedioic acid) can be obtained by bio-fermentation of myristic acid, myristic acid being extractable from the rich oil of kernal palm and coconut, for example.
• the C16 diacid (hexadecanedioic acid) can be obtained by biofermentation of palmitic acid, the latter being found in palm oil mainly, for example. It is possible to refer to documents FR 2 912 753 and
• the polyamides used in the composition according to the invention are semi-crystalline or amorphous and comprise at least two identical or distinct repeating units, these units being able to be formed from a diacid carboxylic acid and a diamine, an aminocarboxylic acid, a lactam or mixtures thereof.
• the polyamide according to the invention may be a homopolyamide and comprise at least two identical repeating units obtained from an aminocarboxylic acid, obtained from a lactam, or corresponding to the formula (diamine Ca). (diacid in
• the polyamide according to the invention may also be a copolyamide and comprise at least two distinct repeating units, these units being obtainable from an aminocarboxylic acid, obtained from a lactam or corresponding to the formula (diamine in Ca). . (diacid in Cb), with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b being each between 4 and 36, as defined below.
• the polyamide according to the invention may comprise at least one aminocarboxylic acid chosen from 9-aminononanoic acid, 10-aminodecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid, and derivatives thereof, especially N-heptyl-1-aminoundecanoic acid.
• the polyamide according to the invention may comprise at least one lactam chosen from pyrrolidinone, piperidinone, caprolactam, enantholactam, caprylolactam, pelargolactam, decanolactam, undecanolactam and laurolactam.
• the polyamide according to the invention may comprise at least one unit corresponding to the formula (diamine Ca).
• (Cb diacid) the (diamine Ca) unit is of the formula H 2 N- (Cl-12) a-Nl-12, when the diamine is aliphatic and linear.
• Such aliphatic and linear diamines have the advantage of being able to comprise up to 100% of organic carbon derived from biomass and determined according to the ASTM D6866 standard.
• the diamine is cycloaliphatic, it is preferably chosen from those comprising two rings. They respond in particular to the following general formula:
• R 1, R 2 , R ⁇ and R 4 represent identical or different groups chosen from a hydrogen atom or alkyl groups of 1 to 6 carbon atoms and X represents either a single bond or a divalent group consisting of:
• a linear or branched aliphatic chain comprising from 1 to 10 carbon atoms, optionally substituted with cycloaliphatic or aromatic groups of 6 to 8 carbon atoms,
• the cycloaliphatic diamine of the polyamide according to the invention is chosen from bis (3,5-dialkyl-4-aminocyclohexyl) methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane, bis (3, 5-dialkyl-4-aminocyclohexyl) propane, bis (3,5-dialkyl-4-aminocyclohexyl) butane, bis (3-methyl-4-aminocyclohexyl) methane (denoted BMACM, MACM or B), p-bis (aminocyclohexyl) methane (PACM) and isopropylidenedi (cyclohexylamine) (PACP).
• bis (3,5-dialkyl-4-aminocyclohexyl) methane bis (3,5-dialkyl-4-aminocyclohexyl) ethane
• the diamine is alkylaromatic, it is chosen from 1,3-xylylenediamine, 1,4-xylylenediamine and their mixture.
• the monomer (Cb diacid) is aromatic, it is selected from terephthalic acid, denoted T and isophthalic acid, denoted I and naphthalenic diacid.
• the fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids with a long hydrocarbon chain (such as linoleic acid and oleic acid), as described in particular in the document EP 0 471 566.
• the diacid when it is cycloaliphatic, it may comprise the following carbon skeletons: norbornylmethane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl) propane.
• amino acids, diamines, diacids are effectively linear. there is nothing to prevent them from being wholly or partly branched, such as 2-methyl-1,5-diaminopentane, or partially unsaturated.
• the C18 dicarboxylic acid may be octadecanedioic acid, which is saturated, or octadecenedioic acid, which has an unsaturation.
• the homopolyamide may be chosen from a PA homopolyamide
• B.12 also noted BMACM.12 obtained by polycondensation of bis- (3-methyl-4-aminocyclohexyl) -methane and dodecanedioic acid, PA 10.12 obtained by polycondensation of decanediamine and dodecanedioic acid, PA 10.10 obtained by polycondensation of decanediamine and decanedioic acid, PA
• the copolyamide may be chosen from the following copolyamides: PA1 1 / 6.T, PA11 / 10.T, PA11 / B.10, PA11 / 6, PA11 / 6.10, PA11 / 6.12, PA1 1 / 6.6, PA1 1 / 10.12, PA11 / BI / BT
• the polyamide may be chosen from PA11, PA1 1 / 10.T and PA1 1 / B.10.
• the nomenclature used to define polyamides is described in ISO 1874-1: 1992 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", particularly on page 3 (Tables 1 and 2) and is well known to those skilled in the art.
• the composition according to the invention comprises between 25 and 52% by weight, advantageously between 30 and 52% by weight, preferably between 35 and 52% by weight and even more preferably between 40 and 52% by weight, relative to the weight. total of the composition, at least one semicrystalline or amorphous polyamide.
• composition according to the invention may also comprise one or more homopolyamides, semi-crystalline or amorphous copolyamides or a mixture thereof.
• a homo or a copolyamide ends with either an amino function and an acid function, when it is obtained by polycondensation of aminocarboxylic acids, by polycondensation of lactams or by polycondensation of diacids and diamines. However, in the latter case, it is also possible to obtain two acid functions or two amino functions.
• the chain terminating agents also called chain limiters (abbreviated as "LDC"
• LDC chain limiters
• the chain terminating agents are compounds capable of reacting with the amine terminal functions of the polyamides, thus modifying the reactivity of the amine end of the macromolecule, and thereby controlling the polycondensation of the polyamide and also the stability of the melt viscosity of the composition during its processing.
• the termination reaction may for example be illustrated as follows: Polyamide-NH 2 + R-CO 2 H ⁇ Polyamide-NH-CO-R + H 2 O
• the chain terminating agents suitable for reacting with the amino terminal functions of the polyamide present in the composition according to the invention are mono- or diacids, preferably comprising from 8 to 30 carbon atoms.
• the diacids can be chosen from adipic acid, decanedioic acid and dodecanedioic acid.
• the monoacids may be chosen from capric acid, acetic acid, benzoic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid and pivalic acid. and isobutyric acid.
• chain terminating agent when the chain terminating agent is a monoacid, the chain terminator is an alkyl group and when the terminating agent is chain is a diacid, chain termination is an acid function.
• the at least one homopolyamide or copolyamide contained in the composition according to the invention has an amine chain content of less than 0.04 meq / g, preferably less than 0.025 meq / g, preferably less than 0.015 meq / g.
• a polyamide having a content of zero amino chain ends This means that all the amine chain ends have reacted with a chain limiter and that the polyamide no longer has a free amine function at its ends.
• the end-of-chain content of the amine functions is measured in a conventional manner and known to those skilled in the art by potentiometry: the concentration at the end of amine chains is measured after dissolution of the polyamide in metacresol, by assaying with the aid of perchloric acid.
• the inherent viscosity of the polyamide of the composition according to the invention is between 0.5 and 3.0 dl / g, preferably between 0.9 and 1.4 dl / g.
• Inherent viscosity is evaluated according to ISO 307.
• the composition according to the invention also comprises between 24 and 40% by weight, and preferably between 24 and 30% by weight, relative to the total weight of the composition, of at least one reinforcement.
• the reinforcement may be chosen from glass beads, glass fibers, carbon fibers, polymeric fibers, natural fibers and mixtures thereof.
• these fibers may have a length of between 0.1 and 25 mm, advantageously between 0.1 and 10 mm.
• the reinforcement used is formed of glass fibers, the length of the fiber of which is advantageously between 0.10 and 25 mm and preferably between 0.1 and 5 mm.
• the reinforcement used is formed of carbon fibers
• the latter advantageously have a length of between 2.0 and 8.5 mm. If these carbon fibers are cylindrical, their diameter may advantageously be between
• a coupling agent may be included to improve the adhesion of the fibers to the polyamide, such as silanes or titanates, which are known to those skilled in the art.
• the composition according to the invention further comprises, as flame-retardant agent, at least one metal salt chosen from a metal salt of phosphinic acid, a metal salt of diphosphinic acid, and their mixture.
• the metal salt of phosphinic acid or the metal salt of diphosphinic acid may also be contained in a polymer.
• the content of such a flameproofing agent is between 24 and 35% by weight, and preferably between 24 and 30% by weight relative to the total weight of the composition.
• the metal salt of the phosphinic acid according to the invention is of formula (I) below and the metal salt of diphosphinic acid has the following formula (II):
• R 3 represents an alkylene group C 1 -C 1 0 linear or branched, arylene, C 6 -C 0, C 6 -C alkarylene 0, or arylalkylene, C 6 -C 0,
• M is an ion Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated amino base,
• n denotes an integer of 1 to 4,
• n denotes an integer of 1 to 4,
• x denotes an integer of 1 to 4,
• n and m being chosen so that the salt is neutral, that is to say that it does not carry an electrical charge.
• M represents an ion chosen from calcium, magnesium, aluminum and zinc.
• R 1 and R 2 independently of one another, denote a methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl group.
• R 3 is methylene, ethylene, n-propylene, iso-propylene, n-butylene, t-butylene, n-pentylene, n-octylene, n-dodecylene; phenylene, naphthylene; methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene; phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.
• the metal salt of mono- and diphosphinic acid may be chosen from the salts of the following compounds: dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, isobutylmethylphosphinic acid, octylmethylphosphinic acid , methyl-n-propylphosphinic acid, methane-1,2-di (methylphosphinic acid), ethane-1,2-di (methylphosphinic acid), hexane-1,6-di (methylphosphinic acid) ), benzene-1,4-di (methylphosphinic acid), methylphenylphosphinic acid, and diphenylphosphinic acid.
• the salt is chosen from aluminum methylethylphosphinate and aluminum diethylphosphinate.
• composition according to the invention may also comprise usual additives for polyamides, such as dyes, light stabilizers (UV) and / or heat stabilizers, plasticizers, impact modifiers, surfactants, pigments , optical brighteners, antioxidants, natural waxes, functional or non-functional polyolefins, cross-linked or otherwise, release agents or fillers.
• additives for polyamides such as dyes, light stabilizers (UV) and / or heat stabilizers, plasticizers, impact modifiers, surfactants, pigments , optical brighteners, antioxidants, natural waxes, functional or non-functional polyolefins, cross-linked or otherwise, release agents or fillers.
• the envisaged fillers include conventional inorganic fillers, such as those chosen from the group, given as a non-limiting example, comprising talc, kaolin, magnesia, slags, silica, carbon black, carbon nanotubes, expanded graphite or not, titanium oxide.
• the additives of the composition according to the present invention may be present in an amount of less than or equal to 20%, and preferably less than 10% by weight relative to the weight of the composition.
• the invention also relates to a method for preparing a composition as defined above.
• the composition may be prepared by any method which makes it possible to obtain a homogeneous mixture containing the composition according to the invention, and optionally other additives, such as extrusion in the molten state, compacting or roller blender.
• the composition according to the invention is prepared by melt blending all the ingredients in a so-called live process.
• the composition can be obtained in the form of granules by compounding on a tool known to those skilled in the art such as: twin screw extruder, comalaxer, internal mixer.
• composition according to the invention obtained by the process of preparation described above can then be transformed for a subsequent use or transformation known to those skilled in the art using tools such as: injection molding machine, extruder, etc.
• the invention thus also relates to an article obtained by injection, extrusion, coextrusion, multi-injection from at least one composition as defined above.
• the process for preparing the composition according to the invention may also use a twin-screw extruder feeding, without intermediate granulation, an injection molding machine or an extruder according to an implementation device known to those skilled in the art.
• the composition according to the invention can be used to form a structure.
• This structure can be monolayer when it is formed only of the composition according to the invention.
• This structure can also be a multilayer structure, when it comprises at least two layers and that at least one of the various layers forming the structure is formed of the composition according to the invention.
• the structure, whether monolayer or multilayer may especially be in the form of fibers (for example to form a woven or a nonwoven), a film, a sheet, a tube, a body hollow or injected part.
• films and sheets can be used in fields as varied as electronics or decoration.
• the composition according to the invention can advantageously be envisaged for the production of all or part of items of electrical and electronic equipment goods, such as encapsulated solenoids, pumps, telephones, computers, monitors, remote controls, cameras, circuit breakers, sheaths. electric cables, optical fibers, switches, multimedia systems. It can also be used for the realization of all or part of automotive equipment such as tubes, tube connectors, pumps, parts injected under the bonnet, injected parts type bumper, dashboard, door trim.
• the elements of automotive equipment when they have the shape of tubes and / or connectors, can in particular be used in air intake devices, cooling (for example by air, coolant, ..
• compositions A1, B1 and C1 comprising:
• compositions A1, B1 and C1 are produced by compounding the polyamides A, B and C, respectively, on a corotating twin-screw extruder type Werner 40 at 260 ° C., the glass fibers and the flame retardant being added in lateral gavage. .
• the end-of-chain content of the amine functions is measured in a conventional manner and known to those skilled in the art by potentiometry: the concentration at the end Amino chain is measured after dissolution of the polyamide in metacresol by assay using perchloric acid (0.02N solution).
• the inherent viscosity (denoted ⁇ ) is measured according to the ISO 307 standard.
• a homopolyamide PA1 1 has a viscosity of between 1.0 and 1.4 dl / g, and its amine concentration is between 0.05 and 0.065 meq / g. 2. Measurement of the melt viscosity
• the melt viscosity is measured in capillary rheometry at 260 ° C., at a shear rate of 100 s -1.
• composition B1 comprising the comparative polyamide B (505 Pa ⁇ s).
• the difference in melt viscosity between the composition and the particular polyamide used for the composition is less important when the content of amine chain ends in the polyamide is lower.
• the initial viscosity of the composition is measured at an imposed shear rate (1 rad / s) and at an imposed temperature (260 ° C.).
• the viscosity of the composition is then measured as a function of time (30 minutes). Measurements are made using an ARES device.
• a percentage is calculated in order to highlight the evolution of the melt viscosity of the compositions tested.
• the flow length is measured for the compositions tested.
• a percentage of evolution is calculated relative to the comparative composition A1.
• composition C1 according to the invention is much more fluid, that is to say much easier to implement than the comparative compositions A1 and B1.
• the temperature required to fill the cavity is of the order of 260- 280 0 C for the comparative compositions A1 and B1. These compositions also generate fumes related to their implementation at high temperature, causing the formation of appearance defects on the part.
• the composition C1 according to the invention makes it possible to avoid the formation of these fumes thanks to a lower processing temperature that can be implemented thanks to its better fluidity.
• the bars of the composition C1 according to the invention were evaluated according to the ISO 179. They are tested in pendulum shock Charpy ISO 179-1 eU with a pendulum of 7.5 Joules. The energy absorbed by the bars is measured in kJ / m 2 .
• the VO ranking is the best ranking according to this test. It corresponds to a material that is not easily flammable, does not produce burning drops during the test.
• the material is more easily flammable, but does not produce inflamed drops during the test.
• the classification V2 tolerates, him, longer times of extinction and the presence of inflamed drops during the combustion.
• compositions C2, C3 and C4 were prepared according to the protocol described in paragraph 1 above. These compositions comprise the products listed below, the respective proportions by weight of polyamide, reinforcement (glass fibers) and flame retardant being mentioned in Table 7 below: polyamide C (homopolyamide PA11 obtained by polycondensation of acid aminoundecanoic acid derived from biomass in the presence of 0.5% lauric acid as chain limiter) comprising an end-of-chain NH 2 content of 0.023 meq / g,
• the UL94 flame propagation test described in paragraph 5 above was carried out in specimens of thickness 3.2 mm, 1, 6 mm or 0.8 mm made from each of the compositions C2 (according to the invention ), C3 and C4 (comparative).
• the burning time of the specimen (referred to as the sum of the 10 times in Table 8) is measured.
• This sum of times evaluated consists of the sum of the 5 times obtained at the first extinction of the specimen after ignition plus the sum of the 5 times obtained at the second extinction of the specimen after ignition. This experience is explained in more detail in the NFT 51072. To obtain the VO classification, it is necessary to obtain a sum of times less than 50 s.
• composition C2 makes it possible to reach the VO classification which corresponds to a material that is not easily flammable and does not produce ignited drops during the test.
• the respective weight proportions of the main compounds used in the composition according to the invention namely the reinforcement (s), agent (s) flame retardant (s) and polyamide (s), therefore play an important role to simultaneously obtain a composition that is easier to implement, thanks to a lower melting viscosity of the composition (see paragraphs 2 and 4.1) and also more stable over time (see paragraph 3) and which makes it possible to obtain a material having good impact resistance and rigidity (see paragraph 5) as well as excellent flame retardant properties (see paragraphs 5 and 6).

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