Self-flame retardant polyamide and polyether block amide

Abstract

Self-flame retardant polyamide and polyether block amide The present invention relates to a polyamide comprising a repeating unit of formula (I): a polyether block amide (PEBA) resulting from the polycondensation of one or more polyamides as defined above with one or more polyether blocks, their uses for the preparation of an article and an article comprising them. Figure for abstract: None

Description

Title of the invention: Self-flame retardant polyamide and polyether block amide

[0001] The present invention relates to a self-flame retardant polyamide and polyether block amide. They comprise in their polymer chain a repeating unit which confers flame retardant properties. The invention relates to their preparation process and their uses as a flame retardant additive in thermoplastic polymer matrices or for the preparation of articles.

[0002] Polyamides, for example polyamide 11, known worldwide under its trademark Rilsan®, have exceptional performance in many applications such as transport, energy, consumer goods such as

[0003] sporting goods and consumer electronics, anti-corrosion protective coatings and objects obtained by 3D printing.

[0004] Polyamides in general, and PA11 in particular, certainly have a very high level of performance. However, they are not naturally fire resistant: they burn easily, giving off flaming drops that can spread fires. However, many applications in the electrical, electrotechnical, electronic fields, but also in transport (air, rail, electric vehicles, etc.) require flame retardant performance.

[0005] Many solutions have been developed by adding, by melt mixing, initially halogenated additives, now halogen-free, based on phosphorus, nitrogen or hydrated fillers. These additives are not integrated into the polymer chain of polyamides. For example, melamine cyanurate, melamine polyphosphate, red phosphorus and metal dialkylphosphinates are used as flame retardant additives. Some 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives are also used as additives in polymers. However, flame retardancy performance is often achieved at the expense of other material properties such as ductility, dielectric properties, thermo-oxidation resistance, dimensional stability, water uptake and rheology.

[0006] Some attempts to incorporate flame retardant repeating units have been reported, particularly with acid-derived units 3-[10-(9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide-10-y 1)]itaconic acid (DOPO-ITA). However, as detailed in the article Negrell et al. Polymer De-gradation and Stability 134 (2016) 10-18 (paragraph 3.3 and figure 12), this DOPO-ITA based on diacids with 4 carbon atoms plays a chain-limiting role in polyamidation and therefore cannot allow the synthesis of PAs with high molar masses.

[0007] Another diacid monomer has been reported in WO 17 / 021355, namely 3-(hydroxy(phenyl)phosphoryl)propanoic acid. This monomer having a carboxylic acid end and a phosphonic acid end also acts as a chain limiter and also does not allow the synthesis of high molecular weight polyamides.

[0008] An aim of the invention is to provide a polyamide having good flame retardant properties while retaining its other properties, in particular those listed above.

[0009] An object of the invention is also to provide a polyamide having good flame retardant properties and which can have a high molar mass.

[0010] For this purpose, the subject of the invention is a polyamide comprising a repeating unit of formula (I):

[0011] [Chem.l]

[0012] wherein R1 and R2 are independently selected from NH and C=O,

[0013] the polyamide having a polydispersity index IP less than or equal to 15.0.

[0014] The repeating unit of formula (I) comprises phosphorus atoms. It includes two 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) groups, which makes it advantageously rich in phosphorus. Advantageously, the alpha carbon of the DOPO groups does not carry hydrogen. In the present invention, the flame retardant is incorporated as a unit within the polymer chain of the polyamide. The flame retardant is thus integrated reactively and not additively. Advantageously, the polyamides according to the invention are classified V0 in the UL94-vertical burning test, in particular for tests with a 1.6 mm thick polyamide sample. The invention is also based on the discovery that such polyamides not only have good flame retardant properties, but also that they retain the intrinsic performances of the polyamide from which they are derived (polyamides free of repeating units of formula (I), but whose other repeating units are identical. For example, a copolyamide PA11 whose polymer chain includes repeating units of formula (I) has good flame retardant properties, but retains the properties of PAU. Finally, it is possible to prepare polyamides with high molar masses.

[0015] According to advantageous aspects of the invention, the polyamide comprises one or more of the following characteristics, taken in isolation or in all technically possible combinations:

[0016] - R1 and R2 represent NH or, alternatively, R1 and R2 represent C=O,

[0017] - the polyamide further comprises one or more aliphatic repeating units chosen from a unit obtained from at least one aliphatic amino acid, a unit obtained from at least one aliphatic lactam, a unit obtained from the polycondensation of at least one aliphatic diamine and at least one aliphatic dicarboxylic acid,

[0018] - the polyamide further comprises at least one repeating unit X1.Y1 obtained from from the polycondensation of at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl, and optionally an aliphatic repeating unit Al chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam,

[0019] - the polyamide is semi-crystalline or amorphous, preferably it is amorphous,

[0020] - the polyamide further comprises a repeating unit X2.Y2 obtained from the poly condensation of at least one alkylaromatic diamine X2 and a dicarboxylic acid Y2 chosen from linear or branched aliphatic dicarboxylic acids and cycloaliphatic dicarboxylic acids,

[0021] - the polyamide further comprises a repeating unit X3.Y3 obtained from from the polycondensation of at least one aliphatic, linear or branched or cycloaliphatic diamine X3 and an aromatic dicarboxylic acid Y3, the repeating unit X3.Y3 preferably being obtained from the polycondensation of at least one aliphatic, linear or branched or cycloaliphatic diamine X3 and terephthalic acid, isophthalic acid or a mixture thereof,

[0022] - the polyamide further comprises an aliphatic repeating unit A2 chosen from a motif obtained from at least one amino acid and a motif obtained from at least one lactam,

[0023] - the polyamide has a mass proportion of atomic phosphorus of at least 0.1% and / or at most 10.0%,

[0024] - the polyamide comprises fillers, reinforcing fibers, in particular glass fibers, additives, in particular chosen from flame retardants, antioxidants, plasticizers and mixtures thereof, or a mixture of these.

[0025] The invention also relates to a polyether block amide (PEBA) resulting from the polycondensation:

[0026] - of one or more polyamides as defined above and having ends of diamine or dicarboxylic acid chains,

[0027] - with one or more polyether blocks with chain ends capable of reacting with the ends of polyamide chains to form amide or ester functions.

[0028] According to advantageous aspects of the invention, the PEBA comprises one or more of the following characteristics, taken in isolation or in all technically possible combinations:

[0029] - PEBA results from one of the following polycondensations:

[0030] - PEBA results from polycondensation:

[0031] - of one or more polyamides as defined above and having ends of diamine chains,

[0032] - with one or more polyether blocks with dicarboxylic acid chain ends, which is(are) preferably a polyoxyalkylene with dicarboxylic acid chain ends, or

[0033] - PEBA results from polycondensation:

[0034] - of one or more polyamides as defined above and having ends of dicarboxylic acid chains,

[0035] - with one or more polyether blocks with diamine chain ends, which is (are) preferably a polyoxyalkylene with diamine chain ends, or

[0036] - PEBA results from polycondensation:

[0037] - of one or more polyamides as defined above and having ends of dicarboxylic acid chains,

[0038] - with one or more polyetherdiol blocks,

[0039] the polyether block amide then being a polyetheresteramide,

[0040] - the PEBA has a mass proportion of atomic phosphorus of at least 0.1% and / or of at most 10.0%,

[0041] - PEBA comprises fillers, reinforcing fibers, in particular glass fibers, additives, in particular chosen from flame retardants, antioxidants, plasticizers and mixtures thereof, or a mixture thereof.

[0042] The invention also relates to the use of the polyamide or PEBA defined above as a flame retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof.

[0043] Definitions

[0044] An amorphous polyamide, within the meaning of the application, designates an amorphous transparent polyamide having only one glass transition temperature (no glass transition temperature) melting temperature (Tf)), or a very low crystalline polyamide having a glass transition temperature and a melting point such that the enthalpy of crystallization during the cooling step at a rate of 20K / min in differential scanning calorimetry (DSC) measured according to ISO 11357-3:2013 is less than 30 J / g, in particular less than 20 J / g, preferably less than 15 J / g. The glass transition temperature (Tg) measured by DSC at a heating rate of 20K / min according to ISO 11357-1:2009 and ISO 11357-2:2013 for these polyamides is greater than 75°C, in particular greater than or equal to 100°C, in particular greater than or equal to 120°C, preferably greater than or equal to 140°C.

[0045] A semi-crystalline polyamide (PA), within the meaning of the application, designates a polyamide which has a melting temperature (Tf) in DSC according to the ISO 11357-3:2013 standard, and an enthalpy of crystallization during the cooling step at a rate of 20K / min in DSC measured according to the ISO 11357-3 of 2013 standard greater than 30 J / g, preferably greater than 40 J / g.

[0046] The nomenclature used to define polyamides is described in ISO 16396-1:2022 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation" and is well known to those skilled in the art.

[0047] The term "polyamide" used in the present description covers both homopolyamides and copolyamides.

[0048] In the PA XY notation, X represents the number of carbon atoms from the diamine residues, and Y represents the number of carbon atoms from the diacid residues, conventionally.

[0049] In the PA X notation, X represents the number of carbon atoms derived from the amino acid or lactam residues.

[0050] The notations PA X / Y, PA X / Y / Z, etc. refer to copolyamides in which X, Y, Z, etc. represent homopolyamide units.

[0051] The polydispersity index IP is equal to the ratio of the molar mass by weight to the molar mass by number (Mw / Mn).

[0052] The number-average molar masses Mn and weight-average molar masses Mw are measured by size exclusion chromatography (or gel permeation chromatography) according to ISO 16014-1:2019. Typically, the polyamide is solubilized in hexafluoroisoproponol stabilized with 0.05 M potassium trifluoroacetate for 24 h at room temperature (20°C) at a concentration of 1 g / L. The solution obtained is then filtered through a PTFE membrane with a porosity of 0.2 pm, then injected at a flow rate of 1 mL / min, into a liquid chromatography system equipped with a set of PFG columns from Polymer Standards Service consisting of a pre-column with dimensions of 50 x 8 mm, a 1000 Å column with dimensions of 300 x 8 mm and a particle size of 7 pm, and a 100 Å column, with dimensions of 300 x 8 mm and particle size of 7 pm. The molar masses are measured by the refractive index and are expressed in PMMA equivalents, used as a calibration standard, then converted to g / mol.

[0053] The number-average molar mass of the polyether blocks of PEBAs can be measured before copolymerization of the blocks by gel permeation chromatography (GPC) according to ISO 16014-1:2019, in tetrahydrofuran (THF).

[0054] Total acidity and total basicity are measured by potentiometry.

[0055] The acidity is measured according to the following method. A sample of polyamide is dissolved in benzyl alcohol. Then, this sample is dosed potentiometrically with a 0.02N tetrabutylammonium hydroxide solution.

[0056] The basicity is measured according to the following method. A sample of polyamide is dissolved in metacresol. Then, this sample is dosed potentiometrically with a 0.02N perchloric acid solution.

[0057] The inherent viscosity is measured at a polyamide concentration of 0.5% by weight in solution in metacresol on the total weight of the solution, at 20°C, using a viscometer equipped with a Micro-Ubbelohde viscometer tube.

[0058] The inherent viscosity is measured at a polyamide concentration of 0.5% by weight in solution in metacresol on the total weight of the solution, at 20°C, using a viscometer equipped with a Micro-Ubbelohde viscometer tube.

[0059] The crystallinity rate is calculated according to the following formula:

[0060] [Math.l] x = x in which

[0061] x denotes the crystallinity rate,

[0062] AHf * denotes the enthalpy of fusion of the polyamide

[0063] AHf denotes the enthalpy of fusion of 100% crystalline polyamide. This value can be a theoretical value obtained by mathematical models, or, if the sample is available, it is the value measured on this sample.

[0064] According to a first subject, the invention relates to a polyamide comprising a repeating unit of formula (I):

[0065] [Chem.2]

[0066] in which R1 and R2 are independently selected from NH and C=O,

[0067] the polyamide having a polydispersity index IP less than or equal to 15.0.

[0068] The polydispersity index IP of the polyamide is less than or equal to 15.0, in particular less than or equal to 10.0, preferably less than or equal to 9.0, for example less than or equal to 7.0.

[0069] The polydispersity index IP of the polyamide is generally greater than or equal to 1.0, in particular greater than or equal to 2.0, typically greater than or equal to 2.5, for example greater than or equal to 3.0.

[0070] In one embodiment, R1 and R2 represent NH and the polyamide comprises a repeating unit of formula (II):

[0071] [Chem.3]

[0072] In another embodiment, R1 and R2 represent C=O and the polyamide comprises a repeating unit of formula (III):

[0073] [Chem.4]

[0074] The polyamide comprising a repeating unit of formula (I) comprises one or more other unit(s).

[0075] In addition to the repeating unit of formula (I), the polyamide comprises one or more repeating units chosen from a unit obtained from at least one amino acid, a unit obtained from at least one lactam, a unit obtained from the polycondensation of at least one diamine and at least one dicarboxylic acid.

[0076] If the polyamide contains a unit obtained from the polycondensation of at least one diamine and at least one dicarboxylic acid, the diamine is preferably a primary diamine (two NH2 groups).

[0077] Preferably, the polyamide is free of groups of formula (IV):

[0078] [Chem.5] / ■—O v; ■ ÿ II I J-'O— P- <3 O > (IV)

[0079] Aliphatic polyamide

[0080] The repeating units of formula (I) may be incorporated within an aliphatic polyamide. Thus, the polyamide comprises, in addition to the repeating units of formula (I), aliphatic repeating units.

[0081] In addition to the repeating unit of formula (I), the polyamide may comprise one or more aliphatic repeating units chosen from a unit obtained from at least one aliphatic amino acid, a unit obtained from at least one aliphatic lactam, a unit obtained from the polycondensation of at least one aliphatic diamine phatic and at least one aliphatic dicarboxylic acid.

[0082] As an example of an aliphatic amino acid, it is possible to cite alpha-omega amino acids preferably comprising from 6 to 12 carbon atoms, such as aminocaproic, amino-7-heptanoic, amino-11-undecanoic, n-heptyl-11-aminoundecanoic and amino-12-dodecanoic acids.

[0083] As an example of aliphatic lactam, mention may be made of those comprising, preferably, between 3 and 12 carbon atoms on the main cycle and which may be substituted. As an example of lactam, mention may be made of P,[3-dimethylpropriolactam, α,α-dimethylpropriolactam, amylolactam, ca-prolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam, the lactam preferably being caprolactam, oenantholactam and lauryllactam.

[0084] The aliphatic diamine has in particular from 2 to 20, in particular from 5 to 14, preferably from 6 to 12 carbon atoms. The aliphatic group can be linear, branched and / or cyclic.Examples of aliphatic diamines include 1,4-diaminobutane, 1,5-diaminopentane, 1,9-diaminononane, hexamethylenediamine, 1,10-decamethylenediamine, piperazine (Pip), tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,5 diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols, isophorone diamine (IPD), methyl-pentamethylenediamine (MPMD, l,3-bis(aminomethyl)cyclohexane (1,3-BAC), l,4-bis(aminomethyl)cyclohexane (1,4-BAC), bis(aminocyclohexyl)methane (BACM), bis(3-methyl-4 aminocyclohexyl)methane (BMACM), 2-2-bis-(3-methyl-4-aminocyclohexyl)-propane (BMACP), methaxylyenediamine, bis-p-aminocyclohexylmethane (also called para-amino-di-cyclohexyl-methane) (PACM), trimethylhexamethylenediamine, isophoronediamine (IPDA) and 2,6-bis-(aminomethyl)-norbornane (BAMN).

[0085] The dicarboxylic acid has in particular from 4 to 36 carbon atoms, preferably those having from 6 to 18 carbon atoms. Examples of aliphatic dicarboxylic acids include succinic acid (4), pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), octanedioic acid (8), azelaic acid (9), sebacic acid (10), undecanedioic acid (11), dodecanedioic acid (12), brassylic acid (13), tetradecanedioic acid (14), hexadecanedioic acid (16), octadecanoic acid (18), octadecenedioic acid (18), eicosanedioic acid (20), docosanedioic acid (22) and dimerized fatty acids, especially those containing 36 carbons.These dimerized fatty acids preferably have a dimer content of at least 98%; preferably they are hydrogenated; these are, for example, products marketed under the brand name "PRIPOL" by the company "CRODA", or under the brand name EMPOL by the company BASF, or under the brand name. Radiacid by OLEON, and polyoxyalkylene a,co-diacids. Fatty acid dimers are typically dimerized fatty acids obtained by oligomerization or polymerization of long-chain unsaturated monobasic hydrocarbon fatty acids (such as linoleic acid and oleic acid), as described in particular in EP 0 471 566.

[0086] When the dicarboxylic acid is cycloaliphatic, it may have the following carbon skeletons: norbornyl methane, cyclohexane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl) or di(methylcyclohexyl)propane. 1,4-Cyclohexyldicarboxylic acid is an example of a cycloaliphatic dicarboxylic acid.

[0087] Preferably, the polyamide comprises, in addition to the repeating units of formula (I), repeating units chosen from the repeating units of PA 4.12, 4.14, 4.18, 6, 6.6, 6.10, 6.12, 6.13, 6.14, 6.18, 9.12, 10.10, 10.11, 10.12, 10.14, 10.18, 11, 12, 6 / 12, 6 / 66, 6 / 12 / 66, 6 / 69 / 11 / 12, 6 / 66 / 11 / 12, 69 / 12 and mixtures thereof, preferably repeating units chosen from the repeating units of PA 6, PA 11, PA 12, PA 6.10, PA 10.10, AP 10.12, AP 6 / 12, AP 11 / 12.

[0088] Cycloaliphatic polyamide, in particular cycloaliphatic homopolyamide X1Y1

[0089] The units of formula (I) may be incorporated within a cycloaliphatic polyamide X1.Y1, or even a cycloaliphatic homopolyamide X1.Y1 when all the units X1.Y1 are identical. Thus, in addition to the repeating unit of formula (I), the polyamide may comprise at least one repeating unit X1.Y1 obtained from the polycondensation of at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl.

[0090] A non-exhaustive list of these cycloaliphatic diamines is given in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405).

[0091] The cycloaliphatic diamine may be 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, l,3-bis(aminomethyl)cyclohexane (1,3-BAC), l,4-bis(aminomethyl)cyclohexane (1,4-BAC), bis-(3-methyl-4-aminocyclohexyl)methane or 3'-dimethyl-4,4'-diamino-dicyclohexylmethane (BMACM, MACM or B), bis-(4-aminocyclohexyl)methane (BACM), p-bis(aminocyclohexyl)methane (PACM or P), isopropylidenedi(cyclohexylamine) (PACP), 2-2-bis-(3-methyl-4-aminocyclohexyl)-propane (BMACP), isophorone-diamine (IPDA or IPD) and 2,6-bis(amino methyl)norbornane (BAMN) and piperazine.

[0092] Advantageously, the cycloaliphatic diamine of the X1.Y1 unit is chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis(aminocyclohexyl)-methane (P) and isophoronediamine (IPD).

[0093] In an advantageous embodiment, the cycloaliphatic diamine of the X1.Y1 unit is a bicycloaliphatic diamine, in particular chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis(aminocyclohexyl)-methane (P).

[0094] The dicarboxylic acid of the unit X1.Y1 may be chosen from linear or branched aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids and aromatic dicarboxylic acids. When it is aliphatic or cycloaliphatic, it is preferably as defined above. In an advantageous version, when it is aliphatic, the dicarboxylic acid of the unit X1.Y1 is an aliphatic dicarboxylic acid chosen from adipic acid (6), decanedioic acid (10), dodecanedioic acid (12) and tetradecanedioic acid (14). When it is aromatic, it is preferably chosen from terephthalic acid, isophthalic acid, furanedicarboxylic acid, and naphthalenic diacid, particularly preferably from terephthalic acid and isophthalic acid.

[0095] Preferably, the polyamide comprises, in addition to the repeating units of formula (I), repeating units chosen from the repeating units of a PA chosen from PA MACM.10, PA PACM.10, PA MACM.12, PA PACM.12, PA MACM.14, PA PACM.14, PA MACM.18 and PA PACM.18.

[0096] In a particularly preferred manner, the polyamide comprises, in addition to the repeating units of formula (I), repeating units chosen from the repeating units of a PA chosen from MACM.10, PA MACM12, and PA MACM.14.

[0097] Preferably, the polyamide comprising the repeating unit of formula (I) and the repeating unit XL Y1 is amorphous.

[0098] Cycloaliphatic copolyamide A / X1Y1

[0099] The units of formula (I) may be incorporated within a cycloaliphatic copolyamide A / X1.Y1. In addition to the repeating unit of formula (I) and the repeating unit X1.Y1 defined above, the polyamide may comprise an aliphatic repeating unit A1 chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam.

[0100] The amino acid is in particular as defined above. Preferably, the amino acid comprises from 9 to 12 carbon atoms. It can thus be chosen from 9-aminononanoic acid (denoted 9), 10-aminodecanoic acid (denoted 10), 11-aminoundecanoic acid (denoted 11) and 12-aminododecanoic acid (denoted 12). Preferably, the repeating unit A is obtained from 11-aminoundecanoic acid (H).

[0101] The lactam is in particular as defined above, is preferably caprolactam (6) or lauryllactam (12).

[0102] Advantageously, the polyamide blocks of type A are blocks of PA 11 (polyundecanamide), PA 12 (polydodecanamide) or PA 6 (polycaprolactam).

[0103] Preferably, the polyamide comprises, in addition to the repeating units of formula (I), repeating units chosen from the repeating units of a PA chosen from PA Z / MACM.10, PA Z / MACM.12, PA Z / MACM.14, in which Z represents 11, 12, 10.10 or 10.12.

[0104] More particularly preferably, the repeating unit A is obtained from a single amino acid or a single lactam. However, it is entirely possible to envisage using, to obtain this same unit A, a mixture of two or more aminocarboxylic acids, a mixture of two or more lactams, but also a mixture of one, two or more aminocarboxylic acids with one, two or more lactams.

[0105] Preferably, the polyamide comprises, in addition to the repeating units of formula (I), repeating units chosen from the repeating units of a PA chosen from PA 11 / MACM.10, PA 11 / PACM.10, PA 11 / MACM.12, PA 11 / PACM.12, PA 11 / MACM.14, PA 11 / PACM.14, PA 11 / MACM.18, PA 11 / PACM.18, PA 12 / MACM.10, PA 12 / PACM.10, PA 12 / MACM.12, PA 12 / PACM.12, PA 12 / MACM.14, PA 12 / PACM.14, PA 12 / MACM.18, PA 12 / PACM.18, PA 10.10 / MACM.10, the PA 10.10 / PACM.10, the PA 10.10 / MACM.12, the PA 10.10 / PACM.12, the PA 10.10 / MACM.14, the PA 10.10 / PACM.14, the PA 10.10 / MACM.18, the PA 10.10 / PACM.18, the PA 10.12 / MACM.10, the PA 10.12 / PACM.10, the PA 10.12 / MACM.12, the PA 10.12 / PACM.12, the PA 10.12 / MACM.14, the PA 10.12 / PACM.14, the PA 10.12 / MACM.18, le PA 10.12 / PACM.18, le PA 12.10 / MACM.10, the PA 12.10 / PACM.10, the PA 12.10 / MACM.12, the PA 12.10 / PACM.12, the PA 12.10 / MACM.14, the PA 12.10 / PACM.14, the PA 12.10 / MACM.18, the PA 12.10 / PACM.18, the PA 12.12 / MACM.10, the PA 12.12 / PACM.10, the PA 12.12 / MACM.12, the PA 12.12 / PACM.12, the PA 12.12 / MACM.14, the PA 12.12 / PACM.14, the PA 12.12 / MACM.18, le PA 12.12 / PACM.18, le PA 10.14 / PACM.10, PA 10.14 / MACM.12, PA 10.14 / PACM.12, PA 10.14 / MACM.14, PA 10.14 / PACM.14, PA 10.14 / MACM.18, PA 10.14 / PACM.18, PA 12.14 / MACM.10, PA 12.14 / PACM.10, PA 12.14 / MACM.12, PA 12.14 / PACM.12, PA 12.14 / MACM.14, PA 12.14 / PACM.14, PA 12.14 / MACM.18, PA 12.14 / PACM.18, PA PA PACM.10 / MACM.10, PA PACM.12 / MACM.12, PA PACM.14 / MACM.14, PA 11 / PACM.10 / MACM.10, PA 11 / PACM.12 / MACM.12, PA 11 / PACM.14 / MACM.14, PA . 12 / PACM.10 / MACM.10, the PA 12 / PACM.12 / MACM.12, the PA 12 / PACM.14 / MACM.14, PA 11 / BMACM.6, PA 11 / BMACM.6, PA 11 / PACM.6, PA 11 / IPD.6, PA 12 / BMACM.6, PA 12 / PACM.6, PA 12 / IPD.6, PA 11 / BMACM.10, PA 11 / IPD.10, PA 12 / BMACM.10, PA 12 / IPD.10, PA 11 / BMACM.14, PA 11ÆPD.14, PA 12 / BMACM.14, PA 12 / PACM.14, and PA 12 / IPD.14.

[0106] Preferably, the polyamide comprises, in addition to the repeating units of formula (I), repeating units chosen from the repeating units of a PA chosen from 11 / BMACM.6, 11 / PACM.6, 11 / IPD.6, 12 / BMACM.6, 12 / PACM.6, 12 / IPD.6, 11 / BMACM.10, 11 / PACM.10, 11 / IPD.10, 12 / BMACM.10, 12 / PACM.10, 12 / IPD.10, 11 / BMACM.14, 11 / PACM.14, 11 / IPD.14, 12 / BMACM.14, 12 / PACM.14, 12 / IPD.14.

[0107] The polyamide comprising the repeating units of formula (I), A and Xl.Y 1 may be amorphous or semi-crystalline, and is preferably amorphous.

[0108] Semi-aromatic polyamides (PASA)

[0109] The polyamide may be a semi-aromatic polyamide (SAPA). The polyamide then comprises, in addition to the units of formula (I), aromatic diamine or dicarboxylic acid units.

[0110] According to a first alternative, the polyamide is a PASA derived from an alkylaromatic diamine. In addition to the repeating unit of formula (I), the polyamide may comprise a repeating unit X2.Y2 obtained from the polycondensation of at least one alkylaromatic diamine X2 and a dicarboxylic acid Y2 chosen from linear or branched aliphatic dicarboxylic acids and cycloaliphatic dicarboxylic acids.

[0111] The dicarboxylic acids are preferably chosen from those defined above. As examples of cycloaliphatic dicarboxylic acids, mention may be made of 1,4-cyclohexyldicarboxylic acid. As examples of aliphatic dicarboxylic acids, mention may be made of butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids, and dimerized fatty acids.

[0112] The alkylaromatic diamine is preferably chosen from 1,3-xylylenediamine (MXD), 1,4-xylylenediamine and their mixture.

[0113] Preferably, the polyamide comprises, in addition to the repeating units of formula (I), repeating units chosen from the repeating units of a PA chosen from MXD6 and MXD 10.

[0114] According to a second alternative, the polyamide is PASA derived from an aromatic dicarboxylic acid.

[0115] In addition to the repeating unit of formula (I), the polyamide may comprise a repeating unit X3.Y3 obtained from the polycondensation of at least one aliphatic, linear or branched or cycloaliphatic diamine X3 and a dicarboxylic acid Y3 aromatic.

[0116] The aliphatic, linear or branched, or cycloaliphatic diamine of the repeating unit X3.Y3 is in particular as defined above.

[0117] The aromatic dicarboxylic acid of the repeating unit X3.Y3 is in particular chosen from terephthalic acid, isophthalic acid, furanedicarboxylic acid, naphthalenic diacid or a mixture thereof, preferably terephthalic acid, isophthalic acid, or a mixture thereof, terephthalic acid being particularly preferred.

[0118] Preferably, the polyamide comprises, in addition to the repeating units of formula (I), repeating units chosen from the repeating units of a PA chosen from PA 6T, PA 9T, PA 10T and PA 12T.

[0119] Preferably, the repeating unit X3.Y3 is obtained from a single aliphatic, linear or branched, or cycloaliphatic diamine and a single aromatic dicarboxylic acid. However, it is entirely possible to envisage using, to obtain this same repeating unit X3.Y3, a mixture of one, two or more aliphatic, linear or branched or cycloaliphatic diamines with one, two or more aromatic dicarboxylic acids.

[0120] Whatever the alternative considered, in addition to the repeating unit of formula (I) and the repeating unit X2.Y2 and / or the repeating unit X3.Y3 defined above, the polyamide may comprise an aliphatic repeating unit A2 chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam. For example, the polyamide comprises, in addition to the repeating units of formula (I), repeating units chosen from the repeating units of a PA 11 / MXD.10.

[0121] For example, the polyamide comprises, in addition to the repeating units of formula (I), repeating units A / X3.Y3 chosen from:

[0122] - A / 6T, A / 9T, A / 10T and A / 1 1T, A being as defined above, in particular 6 / 6T, 6I / 6T, MPMDT / 6T, MXDT / 6T, PA11 / 10T, 11 / 6T / 10T, MXDT / 10T, MPMDT / 10T, PA BACMT / 10T, BACMT / 6T, BACMT / 10T / 6T, 11 / BACMT / 10T, 11 / BACMT / 6T, 11 / 1.3-BAC.T, 11 / 1.4-BAC.T, 11 / MPMDT / 10T and 11 / MXDT / 10T,

[0123] and

[0124] - A / X3.Y3 in which X3 is BMACM, PACM or IPD and Y3 is T or I and A is such as defined above, in particular 11 / BMACM.T, 11 / BMACM.I, 12 / BMACM.T, 12 / BMACM.I, 11 / PACM.T, 11 / PACM.I, 12 / PACM.T, 12 / PACM.I, 11 / IPD.T, 11 / IPD.I, 12 / IPD.T and 12 / IPD.I, more particularly chosen from 11 / BMACM.T, 11 / BMACM.I, 11 / BMACM.T / BMACM.I, 12 / BMACM.T, 12 / BMACM.I, 12 / BMACM.T / BMACM.I, 11 / 1,3-BAC.T, 11 / 1,4-BAC.T, 11 / 1,3-BAC.I, 11 / 1,4-BAC.I, ll / l,3-BAC.T / 10.T, ll / l,4-BAC.T / 10.T, 11 / PACM.T, 11 / PACM.I, 12 / PACM.T, 12 / PACM.I, advantageously 11 / BMACM.T, 11 / PACM.T, 11 / PACM.I, 12 / PACM.T, 12 / PACM.I.

[0125] The following embodiments are applicable to all of the embodiments defined above (in particular whether the polyamide is an aliphatic polyamide, a cycloaliphatic (co)polyamide or a PASA).

[0126] Preferably, the polyamide has a mass proportion of atomic phosphorus of at least 0.1%, in particular at least 0.2%, preferably at least 0.3% and / or at most 10.0%. The mass proportion of atomic phosphorus can be determined by X-ray fluorescence.

[0127] The number-average molar mass Mn of the polyamide is preferably from 5,000 to 50,000 g / mol, more preferably from 10,000 to 35,000 g / mol, even more preferably from 15,000 to 30,000 g / mol. The polyamide according to the invention can therefore advantageously have a high molar mass.

[0128] The weight-average molar mass Mw of the polyamide is preferably from 10,000 to 300,000 g / mol, more preferably from 20,000 to 250,000 g / mol, even more preferably from 30,000 to 200,000 g / mol.

[0129] Preferably, the total acidity of the polyamide is greater than or equal to 30 peq / g, preferably greater than or equal to 40 peq / g.

[0130] The absolute value of the difference between the total acidity and the total basicity of the polyamide is preferably between 0 and 80 peq / g.

[0131] Preferably, the polyamide has an inherent viscosity of between 0.70 and 1.70, advantageously of between 0.80 and 1.50.

[0132] Preferably, the polyamide has a crystallinity rate of between 20 and 40%, in particular between 20 and 30%, measured by DSC (differential scanning calorimetry measurement) according to standard 11357-3, 1999 (2nd DSC heating at 20°C / min according to standard ISO 11357).

[0133] The polyamide may further comprise fillers, reinforcing fibers, additives, in particular chosen from flame retardants, antioxidants, plasticizers and mixtures thereof, or a mixture of these.

[0134] Among the reinforcing fibers, mention may be made of carbon or glass fibers, natural fibers or a mixture thereof.

[0135] Among the additives, mention may be made of flame retardants, chain limiting agents, impact modifiers, pigments, dyes, light (UV) and / or heat stabilizers, plasticizers, surfactants, optical brighteners, antioxidants, natural waxes, mold release agents, or mixtures thereof.

[0136] The flame retardants are notably chosen from DOPO, melamine cyanurate, melamine polyphosphate, red phosphorus, metal dialkylphosphinates and mixtures thereof.

[0137] To the extent that the polyamides according to the invention are self-flame retardant, they can be free from flame retardant (used as an additive).

[0138] Typically, a chain-limiting agent comprises at least one, preferably at least two functions, each independently chosen from carboxylic acids and amines. This chain-limiting agent may be a dicarboxylic acid, a diamine or an amino acid. It makes it possible to react with the amide, amine or carboxylic acid functions of the polyamide.

[0139] In order to ensure good properties (flexibility, burst strength, tear strength, rheology, alloy morphology, compatibilization, homogeneity, consistency, adhesion) and, in particular, good impact resistance and impact properties after aging (in particular oxidative aging at high temperature), the polyamide may comprise an impact modifier, in particular of an elastomeric nature and preferably functionalized by maleic anhydride.

[0140] The fillers envisaged include mineral fillers, such as those chosen from the group, given without limitation, comprising talc, kaolin, magnesia, slag, silica, carbon black, carbon nanotubes, expanded or non-expanded graphite, titanium oxide.

[0141] The reinforcing fibers are chosen from fibers, in particular short fibers. The fibers may be of synthetic origin, in particular glass or carbon fibers, or natural, typically of plant origin such as flax, reed, bamboo or hemp fibers. Preferably, the reinforcing fibers are glass fibers.

[0142] The usual stabilizers used are phenols, phosphites, UV absorbers, stabilizers of the HALS (Hindered Amine Light Stabilizer) type, metal iodides or thioethers. Mention may be made of Irganox 1010, 245, 1098, Irgafos 168, 126, Tinuvin 312, 770, Iodide P201 from the company Ciba, Nylostab S-EED from the company Clariant, AO 412S from the company Adeka Palmarole.

[0143] The mass proportion of the fillers is in particular from 0.5 to 50.0% relative to the weight of the polyamide.

[0144] The mass proportion of the reinforcing fibers is in particular 5 to 75% relative to the weight of the polyamide.

[0145] The mass proportion of the additives is in particular 0.05 to 3.00% relative to the weight of the polyamide.

[0146] The cumulative mass proportion of the fillers, reinforcing fibers, and additives is in particular 0.1 to 80% relative to the weight of the polyamide.

[0147] The polyamide according to the invention is typically obtained by polycondensation of a monomer of formula (X):

[0148] [Chem.6]

[0149] wherein R3 and R4 are independently selected from -NH and -(C=O)-O- with at least one other monomer selected from aliphatic amino acids, aliphatic lactams, mixtures of aliphatic diamines and aliphatic dicarboxylic acids, and mixtures thereof.

[0150] When R3 and R4 are NH, the monomer of formula (X) is typically prepared by reacting two equivalents of DOPO with one equivalent of a compound of the following formula (XI):

[0151] [Chem.7] (Xi)

[0152] When R3 and R4 are -(C=O)-O-, the monomer of formula (X) is typically prepared by reacting two equivalents of DOPO with one equivalent of a compound of the following formula (XII):

[0153] [Chem.8]

[0154] Advantageously, the monomer of formula (X) does not act as a chain limiter, and it is possible to prepare polyamides having a high molar mass.

[0155] The embodiments described above for the repeating units are of course applicable to the monomers from which these units are derived.

[0156] Preferably, the polyamide is not obtained from a chain branching agent of the following formula (V):

[0157] [Chem.9]

[0158] wherein R10 to R15 are independently selected from a hydrocarbon group containing from 1 to 20 carbon atoms and optionally substituted, and the substituted hydrocarbon group being a hydrocarbon group comprising a carboxyl-terminated group, such as a carboxylic acid-terminated group, or an amine-terminated group, it being understood that at least one of R10 to R15 is a substituted hydrocarbon group containing a carboxyl or amine terminus.

[0159] The polycondensation can be carried out in the presence of a chain-limiting dicarboxylic acid, which makes it possible to obtain a polyamide with a dicarboxylic chain end. As described below, the latter can serve as a precursor for the preparation of polyether block amide.

[0160] The polycondensation can be carried out in the presence of a chain-limiting diamine, which makes it possible to obtain a polyamide with a diamine chain end. As described below, the latter can serve as a precursor for the preparation of polyether block amide.

[0161] According to a second subject, the invention relates to a polyether block amide (PEBA) resulting from the polycondensation:

[0162] - of one or more polyamides as defined above and having ends of diamine or dicarboxylic acid chains,

[0163] - with one or more polyether blocks with chain ends capable of reacting with the ends of polyamide chains to form amide or ester functions.

[0164] The polyamide(s) as defined above is / are useful as polyamide block(s) for the preparation of PEBA.

[0165] Advantageously, the PEBAs according to the invention are classified V0 in the UL94-vertical burning test, in particular for tests with a PEBA sample 1.6 mm thick.

[0166] PEBAs result from the polycondensation of polyamides with reactive ends (amine, carboxylic acid) with polyether blocks with reactive ends. At least a PEBA block according to the invention is derived from a polyamide according to the invention.

[0167] The polyether blocks of the PEBA copolymer (the skeleton of these blocks, without taking into account whether the groups originating from the reactive ends) are made up of alkylene oxide units. The polyether blocks may in particular be PEG (polyethylene glycol) blocks, i.e. made up of ethylene oxide units, and / or PPG (polypropylene glycol) blocks, i.e. made up of propylene oxide units, and / or PO3G (polytrimethylene glycol) blocks, i.e. made up of tri-methylene ether glycol units, and / or PTMG (polytetramethylene glycol) blocks, i.e. made up of tetramethylene glycol units, also called polytetrahydrofuran. The copolymers may comprise several types of polyethers in their chain, the copolyethers being able to be block or random.

[0168] It is also possible to use blocks obtained by oxyethylation of bisphenols, such as for example bisphenol A. These latter products are described in particular in document EP 0 613 919.

[0169] The polyether blocks can also be made up of ethoxylated primary amines. As examples of ethoxylated primary amines, mention may be made of the products of formula (XXX):

[0170] [Chem. 10] H —(OCHSC^ — H—(CH3CB0%—H if (XXX)

[0171] in which m and n are integers between 1 and 20 and x an integer between 8 and 18. These products are for example commercially available under the brand NORAMOX® from the company Arkema and under the brand GENAMIN® from the company CLARIANT.

[0172] The polyether blocks may comprise polyoxyalkylene blocks with NH2 chain ends, such blocks being obtainable by cyanoacetylation of aliphatic α,β-dihydroxylated polyoxyalkylene blocks called polyetherdiols. More particularly, the commercial products Jeffamine or Elastamine may be used (for example Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products from Huntsman, also described in documents JP 2004346274, JP 2004352794 and EP 1482011).

[0173] The polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks with carboxylic ends, or aminated to be transformed into po- diamine ethers and condensed with polyamide blocks with carboxylic ends.

[0174] If the above PEBA copolymers comprise at least one polyamide block and at least one polyether block as described above, the PEBAs may also comprise three, four (or even more) different blocks chosen from those described in the present description, for example; polyester blocks, polysiloxane blocks, such as polydimethylsiloxane (or PDMS) blocks, polyolefin blocks, polycarbonate blocks, and mixtures thereof. For example, the PEBA copolymer may be a segmented block copolymer comprising three different types of blocks, which results from the condensation of several of the blocks described above.Said copolymer may for example be a copolymer comprising a polyamide block as defined above, a polyester block and a polyether block, in particular as defined above, or a copolymer comprising a polyamide block as defined above and two different polyether blocks, in particular as defined above, for example a PEG block and a PTMG block.

[0175] Preferably, the PEBA results from one of the polycondensations according to one of the three alternatives which follow.

[0176] According to a first alternative, PEBA results from polycondensation:

[0177] - of one or more polyamides as defined above and having ends of diamine chains,

[0178] - with one or more polyether blocks with dicarboxylic acid chain ends, which is(are) preferably a polyoxyalkylene with dicarboxylic acid chain ends.

[0179] The polyamide(s) with diamine chain ends is (are) for example the polyamide with diamine chain ends described above.

[0180] According to a second alternative, PEBA results from polycondensation:

[0181] - of one or more polyamides as defined above and having ends of dicarboxylic acid chains,

[0182] - with one or more polyether blocks with diamine chain ends, which is(are) preferably a polyoxyalkylene with diamine chain ends.

[0183] The polyamide(s) with dicarboxylic chain ends is (are) for example the polyamide with dicarboxylic chain ends described above.

[0184] According to a third alternative, PEBA results from polycondensation:

[0185] - of one or more polyamides as defined above and having ends of dicarboxylic acid chains,

[0186] - with one or more polyetherdiol blocks.

[0187] PEBA is then a polyetheresteramide.

[0188] The polyamide(s) with dicarboxylic chain ends is (are) for example the polyamide with dicarboxylic chain ends described above.

[0189] Particularly preferred PEBA copolymers are copolymers comprising: - at least one polyamide PA 11 block comprising repeating units of formula (I) and at least one PEG block;

[0190] - at least one polyamide PA 11 block comprising repeating units of formula (I) and at least one PTMG block;

[0191] - at least one polyamide PA 12 block comprising repeating units of formula (I) and at least one PEG block;

[0192] - at least one polyamide PA 12 block comprising repeating units of formula (I) and at least one PTMG block;

[0193] - at least one polyamide PA 6.10 block comprising repeating units of formula (I) and at least one PEG block;

[0194] - at least one polyamide PA 6.10 block comprising repeating units of formula (I) and at least one PTMG block;

[0195] - at least one polyamide PA 6 block comprising repeating units of formula (I) and at least one PEG block;

[0196] - at least one polyamide PA 6 block comprising repeating units of formula (I) and at least one PTMG block;

[0197] - at least one polyamide PA 6 / 12 block comprising repeating units of formula (I) and at least one PEG block;

[0198] - at least one polyamide PA 6 / 12 block comprising repeating units of formula (I) and at least one PTMG block;

[0199] - at least one polyamide PA 11 / 12 block comprising repeating units of formula (I) and at least one PEG block;

[0200] - at least one polyamide PA 11 / 12 block comprising repeating units of formula (I) and at least one PTMG block.

[0201] According to one embodiment, the number-average molar mass Mn of the polyamide blocks in the PEBA copolymer is preferably from 400 to 13,000 g / mol, more preferably from 500 to 10,000 g / mol, even more preferably from 600 to 9,000 g / mol or between 600 and 6,000 g / mol. In embodiments, the number average molar mass of the polyamide blocks in the PEBA copolymer is from 400 to 500 g / mol, or from 500 to 1000 g / mol, or from 1000 to 1500 g / mol, or from 1500 to 2000 g / mol, or from 2000 to 2500 g / mol, or from 2500 to 3000 g / mol, or from 3000 to 3500 g / mol, or from 3500 to 4000 g / mol, or from 4000 to 5000 g / mol, or from 5000 to 6000 g / mol, or from 6000 to 7000 g / mol, or from 7000 to 8000 g / mol, or from 8000 to 9000 g / mol, or from 9000 to 10000 g / mol, or from 10000 to 11000 g / mol, or from 11000 to 12000 g / mol, or from 12000 to 13000 g / mol.

[0202] The number-average molar mass of the polyether blocks is preferably from 100 to 3000 g / mol, preferably from 200 to 2000 g / mol. In embodiments, the number-average molar mass of the polyether blocks is from 100 to 200 g / mol, or from 200 to 500 g / mol, or from 500 to 800 g / mol, or from 800 to 1000 g / mol, or from 1000 to 1500 g / mol, or from 1500 to 2000 g / mol, or from 2000 to 2500 g / mol, or from 2500 to 3000 g / mol.

[0203] The number-average molar mass is generally fixed by the chain limiter content. It can be calculated according to the relationship: -Mn ^monomer X Mwrepeat motif / ^chain limiter-^ -Mwchain limiter

[0204] In this formula, nmonomer represents the number of moles of monomer, nichainlimiter represents the number of moles of excess chain limiter, MWrepeatingunit represents the molar mass of the repeating unit, and MWichainlimiter represents the molar mass of the excess chain limiter.

[0205] Preferably, the PEBA has a mass proportion of atomic phosphorus of at least 0.1%, in particular at least 0.2%, preferably at least 0.3% and / or at most 10.0%.

[0206] The PEBA may further comprise fillers, reinforcing fibers, additives, or a mixture thereof, including those described above. The PEBA may be free of flame retardant (used as an additive).

[0207] According to a third object, the invention relates to the use of the polyamide or PEBA defined above as a flame retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof.

[0208] According to a fourth object, the invention relates to a method for preparing an article comprising a step of extrusion, molding or overmolding of the polyamide defined above or of the PEBA defined above, whereby an article is obtained.

[0209] The article is preferably a shaped article, such as fiber, fabric, film, sheet, rod, tube, extruded part, injected part, comprising the composition as defined above. Thus, the polyamide or PEBA according to the present invention is advantageous for the manufacture of articles, in particular articles or elements of sporting articles, which must in particular have both good impact resistance and good endurance to mechanical, chemical, UV and thermal aggression. Among these sporting articles, mention may be made of elements of sports shoes, sports utensils such as ice skates or other winter sports and mountaineering articles, ski bindings, snowshoes, sports bats, boards, horseshoes, fins, golf balls, leisure vehicles, in particular those intended for activities in cold weather.We can also mention, in general, leisure and DIY articles, tools and road equipment subject to climatic and mechanical aggression, protective articles, such as helmet visors, glasses, as well as glasses arms. We can also cite, by way of non-limiting examples, car parts, such as headlight protectors, rearview mirrors, small parts. off-road vehicles, tanks, in particular, of mopeds, motorcycles, scooters, subject to mechanical and chemical attacks, screws, cosmetic articles subject to mechanical and chemical attacks, lipsticks, pressure gauges, aesthetic protection elements such as gas bottles. We can also mention objects or parts of objects for electronics requiring compliance with the dimensions, for example parts of mobile phones, computers, tablets...

[0210] According to a fifth object, the invention relates to the article comprising the polyamide or the PEBA as defined above, or capable of being obtained by this process.

[0211] The invention is illustrated with the following examples, which are provided without limitation.

[0212] Example 1: preparation of monomer of formula (X)

[0213] Synthesis of DOPO-diamine of formula (X) in which R3 and R4 are NH.

[0214] 0.5 g of 4.4'-diaminobenzophenone (2.36mmol), 3.06g of DOPO (14.13mmol) are stirred in a 25mL two-necked flask under nitrogen atmosphere for 4h at 180°C. The product obtained is allowed to cool to 100°C then 20mL of toluene is added. The mixture is filtered and the powder obtained is filtered, washed with ethanol and dried under vacuum overnight at 40°C. A white / yellow powder is obtained (72% yield).

[0215] Example 2: Polyamides comprising repeating units of formula (I)

[0216] The polyamide denoted A is a PAU. This polyamide is prepared according to the following process. After loading the components of Table 1, the autoclave reactor is placed under an inert atmosphere. The reaction medium is then raised in temperature to 260 degrees centigrade, while maintaining stirring. The reaction medium is maintained at 260 degrees centigrade, under a pressure of 20 bars for 1h30. Then, the pressure is lowered to 12 bars, while maintaining the temperature at 260 degrees centigrade. The material is then transferred into a polymerizer, under nitrogen flushing at 260 degrees centigrade. The polymerizer is placed under a vacuum of 50 mbar for 30 min and maintained for 1h00. The material is then extruded, in the form of granules. This process is used for all the polyamides exemplified.

[0217] The different polyamides were characterized according to the UL94 standard in vertical combustion on injected test pieces with a thickness of 1.6 mm.

[0218] [Tables 1] % by mass of atomic phosphorus % by mass of 11-aminoundecanoic acid % by mass of diamine of formula (X) in which R 3 = R4=NH % by mass of sebacic acid % by mass of H3PO4 PAU A (comp) 0 99.94 0 0 0.06 PAU B (inv) 0.5 93.25 1.64 5.05 0.06 PAU C (inv) 1 86.58 3.26 10.10 0.06

[0219] Table 1: Natures and proportions of monomers for the preparation of polyamides

[0220] Tables 2 and 3 below provide the properties.

[0221] [Tables2] % atomic phosphorus mass Total acidity (peq / g) Total basicity (peq / g) Mn (g / mol) Mw (g / mol) PI Burning time after 1st flame application (s) Burning time after 2nd flame application (s) PAU A (comp) 0 44 49 40000 92000 2.30 2.1 >30 sample burns to the support PAU B (inv) 0.5 84 36 34500 113100 3.3 2.9 4.9 PAU C (inv) 1 94 50 31900 151600 4.8 3.1 2.5

[0222] Table 2: Properties of PAs [Table 3] % by mass of Tf (°C) Enthalpy of fusion Te (°C) Enthalpy of crystallization atomic phosphorus (J / g) (J / g) PAU A (comp) 0 188 58 152 58 PAU B (inv) 0.5 185 56 151 56 PAU C (inv) 1 180 51 143 51

[0223] Example 3: PEBA whose polyamide block comprises repeating units of formula (I)

[0224] 3.1. Polycondensation

[0225] materials used:

[0226] PEBA CEI (counter-example): PA 11-PTMG (Mn: 1000-1000) - PEBA CEI is a copolymer with PA11 blocks and PTMG blocks with number-average molecular masses (Mn) of 1000 - 1000 respectively.

[0227] PEBA 1: PEBA 1 is a block copolymer according to the invention obtained by the zirconium butylate-catalyzed reaction of OH-terminated PTMG blocks of Mn 1000 g / mol and COOH-terminated 11 / 1.10 blocks of number-average molecular weights (Mn) 1000 g / mol; said PEBA 1 containing 1% by mass of atomic phosphorus. PEBA 1 is thus obtained by charging 28.619 g of Aminol 1, 10.692 g of the monomer of formula (X) in which R3 and R4 represent NH and 13.562 g of sebacic acid then 50 g of PTMG1000; Aminol 1 representing 1-amino undecanoic acid.

Claims

1. Claims Polyamide comprising a repeating unit of formula (I): [Chem. 11]

2.

3.

4.

5.

6.

7.

8. wherein R1 and R2 are independently selected from NH and C=O, the polyamide having a polydispersity index IP less than or equal to 15.

0. Polyamide according to claim 1, in which R1 and R2 represent NH. Polyamide according to claim 1, in which R1 and R2 represent C=O. Polyamide according to any one of claims 1 to 3, further comprising one or more aliphatic repeating units chosen from a unit obtained from at least one aliphatic amino acid, a unit obtained from at least one aliphatic lactam, a unit obtained from the polycondensation of at least one aliphatic diamine and at least one aliphatic dicarboxylic acid. Polyamide according to any one of claims 1 to 4, further comprising at least one repeating unit X1.Y1 obtained from the polycondensation of at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl. Polyamide according to claim 5, further comprising an aliphatic repeating unit Al chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam. Polyamide according to any one of claims 5 to 6, the polyamide being amorphous. Polyamide according to one of claims 1 to 3, further comprising a repeating unit X2.Y2 obtained from the polycondensation of at least an alkylaromatic diamine X2 and a dicarboxylic acid Y2 chosen from linear or branched aliphatic dicarboxylic acids and cycloaliphatic diacids.

9. Polyamide according to one of claims 1 to 3, further comprising a repeating unit X3.Y3 obtained from the polycondensation of at least one aliphatic, linear or branched or cycloaliphatic diamine X3, and an aromatic dicarboxylic acid Y3.

10. Polyamide according to claim 9, the repeating unit X3.Y3 of which is obtained from the polycondensation of at least one aliphatic, linear or branched or cycloaliphatic diamine X3 and terephthalic acid, isophthalic acid or a mixture thereof.

11. Polyamide according to any one of claims 8 to 10, further comprising an aliphatic repeating unit A2 chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam.

12. Polyether block amide (PEBA) resulting from the polycondensation: - of one or more polyamides as defined in any one of claims 1 to 11 and having diamine or dicarboxylic acid chain ends, - with one or more polyether blocks with chain ends capable of reacting with the chain ends of the polyamide to form amide or ester functions.

13. Polyether block amide according to claim 12, resulting from the polycondensation: - of one or more polyamides as defined in any one of claims 1 to 11 and having diamine chain ends, - with one or more polyether blocks with dicarboxylic acid chain ends.

14. Polyether block amide according to claim 12, in which the polyether block with dicarboxylic acid chain ends is a polyoxyalkylene with dicarboxylic acid chain ends.

15. Polyether block amide according to claim 12 resulting from the polycondensation: - of one or more polyamides as defined in any one of claims 1 to 10 and having dicarboxylic acid chain ends, - with one or more polyether blocks with diamine chain ends.

16. The polyether block amide of claim 15, wherein the block

17.

18.

19.

20.

21. polyether is with diamine chain ends is a polyoxyalkylene with diamine chain ends. Polyether block amide according to claim 12, resulting from the poly condensation: - one or more polyamides as defined in any one of claims 1 to 11 and having dicarboxylic acid chain ends, - with one or more polyetherdiol blocks, the polyether block amide then being a polyetheresteramide. Polyamide according to any one of claims 1 to 11 or polyether block amide according to any one of claims 12 to 17, having a mass proportion of atomic phosphorus of at least 0.1%. Use of a polyamide according to any one of claims 1 to 11 and 18 or a polyether block amide according to any one of claims 12 to 17 and 18 as a flame retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof. Polyamide according to any one of claims 1 to 11 and 18 or polyether block amide according to any one of claims 12 to 17 and 18, comprising fillers, reinforcing fibers, in particular glass fibers, additives, in particular chosen from flame retardants, antioxidants, plasticizers and mixtures thereof, or a mixture of these. Process for the preparation of a polyamide according to any one of the re Claims 1 to 11 and 18 comprising the polycondensation of a monomer of formula (X): (X) in which R3 and R4 are independently selected from NH and (C=O)-O-, with at least one other monomer selected from aliphatic amino acids, aliphatic lactams, mixtures of aliphatic diamines and aliphatic dicarboxylic acids, and mixtures thereof.

22. An article comprising a polyamide according to any one of claims 1 to 11 and 18, a polyether block amide according to any one of claims 12 to 17 and 18 or a mixture thereof.

23. A method of preparing an article comprising a step of extruding, molding or overmolding the polyamide according to any one of claims 1 to 11 and 18 or polyether block amide according to any one of claims 12 to 17 and 18, whereby an article is obtained.