Inherently flame-retardant polyamide and polyether block amide

Abstract

The present invention relates to a polyamide comprising a repeating unit of formula (I): [Chem 13] a polyether block amide (PEBA) resulting from the polycondensation of one or more polyamides as defined above with one or more polyether blocks, the uses thereof for preparing an article, and an article comprising same.

Description

[0001] DESCRIPTION

[0002] TITLE: Self-flame retardant polyamide and polyether block amide

[0003] 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.

[0004] 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 sporting goods and consumer electronics, anti-corrosion protective coatings and objects obtained by 3D printing.

[0005] 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, electronics fields, as well as in transport (air, rail, electric vehicles, etc.) require flame retardant performance.

[0006] Many solutions have been developed by adding initially halogenated, now halogen-free additives based on phosphorus, nitrogen, or hydrated fillers through melt blending. 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.

[0007] Some attempts to incorporate flame-retardant repeating units have been reported, particularly with units derived from 3-[10-(9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide-10-yl)]itaconic acid (DOPO-ITA). However, as detailed in the article Negrell et al. Polymer Degradation and Stability 134 (2016) 10-18 (paragraph 3.3 and figure 12), this DOPO-ITA based on 4-carbon diacids plays a chain-limiting role in polyamidation and therefore cannot allow the synthesis of high molar mass PAs.

[0008] Another diacid monomer was 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.

[0009] 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.

[0010] An aim of the invention is also to provide a polyamide having good flame retardant properties and which can have a high molar mass.

[0011] For this purpose, the subject of the invention is a polyamide comprising a repeating unit of formula (I): [Chem 1] in which R 1 and R 2 are independently selected from NH and C=O, the polyamide having a polydispersity index IP less than or equal to 15.0.

[0012] 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 polyamide sample 1.6 mm thick. 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 performance of the polyamide from which they are derived (polyamides free from the repeating unit 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 PA11. Finally, it is possible to prepare polyamides with high molar masses.

[0013] According to advantageous aspects of the invention, the polyamide comprises one or more of the following characteristics, taken individually or in all technically possible combinations:

[0014] R 1 and R 2 represent NH or, alternatively, R 1 and R 2represent C=O, 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, the polyamide further comprises at least one repeating unit X1,Y1 obtained from the polycondensation of at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1, and optionally 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, the polyamide is semi-crystalline or amorphous, preferably it is amorphous, the polyamide further comprises a repeating unit X2.Y2 obtained from the polycondensation of at least one alkylaromatic diamine X2 and a dicarboxylic acid Y2 chosen from aliphatic, linear or branched dicarboxylic acids and cycloaliphatic dicarboxylic acids, the polyamide further comprises 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, the repeating unit X3.Y3 being preferably 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, the polyamide further comprises 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, the polyamide has a mass proportion of atomic phosphorus of at least 0.1% and / or at most 10.0%, 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 thereof.

[0015] The invention also relates to a polyether block amide (PEBA) resulting from the polycondensation: of one or more polyamides as defined above 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.

[0016] 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: the PEBA results from one of the following polycondensations: the PEBA results from the polycondensation: of one or more polyamides as defined above and having diamine chain ends, with one or more polyether blocks with dicarboxylic acid chain ends, which is (are) preferably a polyoxyalkylene with dicarboxylic acid chain ends, or the PEBA results from the polycondensation: of one or more polyamides as defined above and having dicarboxylic acid chain ends, with one or more polyether blocks with diamine chain ends, which is (are) preferably a polyoxyalkylene with diamine chain ends,or the PEBA results from the polycondensation: of one or more polyamides as defined above and having dicarboxylic acid chain ends, with one or more polyetherdiol blocks, the polyether block amide then being a polyetheresteramide, the PEBA has a mass proportion of atomic phosphorus of at least 0.1% and / or at most 10.0%, the 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. 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.,

[0017] Definitions

[0018] An amorphous polyamide, within the meaning of the application, means a transparent amorphous polyamide having only a glass transition temperature (no melting temperature (Tm)), or a very slightly 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 the ISO 11357-3:2013 standard 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.

[0019] 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 11357-3:2013 standard of greater than 30 J / g, preferably greater than 40 J / g.

[0020] 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.

[0021] The term "polyamide" used in this description covers both homopolyamides and copolyamides.

[0022] In the PA XY notation, X represents the number of carbon atoms from diamine residues, and Y represents the number of carbon atoms from diacid residues, conventionally.

[0023] In PA X notation, X represents the number of carbon atoms from amino acid or lactam residues.

[0024] The notations PA X / Y, PA X / Y / Z, etc. refer to copolyamides in which X, Y, Z, etc. represent homopolyamide units.

[0025] The polydispersity index IP is equal to the ratio of the weight-average molar mass to the number-average molar mass (Mw / Mn). 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 particle size of 7 pm, and a 100 Å column with dimensions of 300 x 8 mm and particle size of 7 pm.Molar masses are measured by the refractive index and are expressed in PMMA equivalents, used as a calibration standard, then converted to g / mol.

[0026] 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).

[0027] Total acidity and total basicity are measured by potentiometry.

[0028] Acidity is measured using the following method. A sample of polyamide is dissolved in benzyl alcohol. This sample is then potentiometrically assayed using a 0.02N tetrabutylammonium hydroxide solution.

[0029] Basicity is measured using the following method. A sample of polyamide is dissolved in metacresol. This sample is then assayed potentiometrically using a 0.02N perchloric acid solution.

[0030] 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.

[0031] 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.

[0032] The crystallinity rate is calculated using the following formula:

[0033] [Math 1] 100 in which

[0034] X denotes the crystallinity rate,

[0035] AHf * denotes the enthalpy of fusion of polyamide 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.

[0036] According to a first subject, the invention relates to a polyamide comprising a repeating unit of formula (I):

[0037] [Chem 2] in which R 1 and R 2 are independently selected from NH and C=O, the polyamide having a polydispersity index IP less than or equal to 15.0.

[0038] 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.

[0039] 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.

[0040] In one embodiment, R 1 and R 2 represent NH and the polyamide comprises a repeating unit of formula (II): [Chem 3] In another embodiment, R 1 and R 2 represent C=O and the polyamide comprises a repeating unit of formula (III):

[0041] [Chem 4]

[0042] The polyamide comprising a repeating unit of formula (I) comprises one or more other unit(s).

[0043] 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.

[0044] 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).

[0045] Preferably, the polyamide is free from groups of formula (IV): [Chem 5]

[0046] Aliphatic polyamide

[0047] The repeating units of formula (I) may be incorporated into an aliphatic polyamide. Thus, the polyamide comprises, in addition to the repeating units of formula (I), aliphatic repeating units. 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 and at least one aliphatic dicarboxylic acid.

[0048] 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.

[0049] Examples of aliphatic lactams include those preferably comprising between 3 and 12 carbon atoms on the main ring and which may be substituted. Examples of lactams include |3,p-dimethylpropriolactam, a,a-dimethylpropriolactam, amylolactam, caprolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam, the lactam preferably being caprolactam, oenantholactam and lauryllactam.

[0050] 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, 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-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).

[0051] 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, the 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 the company OLEON, and polyoxyalkylene α,ε-diacids. Fatty acid dimers are typically 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 document EP 0 471 566.

[0052] 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.

[0053] 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, б, 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.

[0054] Cycloaliphatic polyamide, in particular cycloaliphatic homopolyamide X1Y1

[0055] The units of formula (I) may be incorporated into 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 X1 and at least one dicarboxylic acid Y1.

[0056] 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).

[0057] The cycloaliphatic diamine may be selected 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, 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-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.

[0058] 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).

[0059] In an advantageous embodiment, the cycloaliphatic diamine of the unit X1.Y1 is a bicycloaliphatic diamine, in particular chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis(aminocyclohexyl)-methane (P).

[0060] 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.

[0061] 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.

[0062] Particularly 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 MACM.10, PA MACM12, and PA MACM.14.

[0063] Preferably, the polyamide comprising the repeating unit of formula (I) and the repeating unit X1,Y1 is amorphous.

[0064] Cycloaliphatic copolyamideA / X1Y1

[0065] The units of formula (I) may be incorporated into 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. The amino acid is in particular as defined above. Preferably, the amino acid comprises from 9 to 12 carbon atoms. It may 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 (11).

[0066] The lactam is in particular as defined above, is preferably caprolactam (6) or lauryllactam (12).

[0067] Advantageously, the polyamide blocks of type A are blocks of PA 11 (polyundecanamide), PA 12 (polydodecanamide) or PA 6 (polycaprolactam).

[0068] 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.

[0069] 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.

[0070] 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

[0071] 11 / MACM.10, PA 11 / PACM.10, PA 11 / MACM.12, PA 11 / PACM.12, PA

[0072] 11 / MACM.14, PA 11 / PACM.14, PA 11 / MACM.18, PA 11 / PACM.18, PA

[0073] 12 / MACM.10, PA 12 / PACM.10, PA 12 / MACM.12, PA 12 / PACM.12, PA

[0074] 12 / MACM.14, PA 12 / PACM.14, PA 12 / MACM.18, PA 12 / PACM.18, PA

[0075] 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 / PACM.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 / MACM.14, the PA 10.12 / MACM.18, the PA 10.12 / PACM.18, the 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 / PACM.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 / MACM.14, the PA 12.12 / MACM.18, the PA 12.12 / PACM.18, the PA 10.14 / PACM.10, le PA 10.14 / MACM.12, le PA 10.14 / PACM.12, le PA 10.14 / MACM.14, le PA 10.14 / PACM.14, le PA 10.14 / MACM.18, le PA 10.14 / PACM.18, le PA 12.14 / M ACM.10, le PA 12.14 / PACM.10, le PA 12.14 / MACM.12, le PA 12.14 / PACM.12, le PA 12.14 / MACM.14, le PA 12.14 / PACM.14, le PA 12.14 / MACM.18, le PA 12.14 / PACM.18, le 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, PA 12 / PACM.12 / MACM.12, 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, the PA 11 / IPD.10, PA 12 / BMACM.10, PA 12 / IPD.10, PA 11 / BMACM.14, PA 11 / IPD.14, PA 12 / BMACM.14, PA 12 / PACM.14, and PA 12 / 1 PD.14.

[0076] 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.

[0077] The polyamide comprising the repeating units of formula (I), A and X1.Y1 may be amorphous or semi-crystalline, and is preferably amorphous.

[0078] Semi-aromatic polyamides (PASA)

[0079] 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.

[0080] 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.

[0081] The dicarboxylic acids are preferably chosen from those defined above. Examples of cycloaliphatic dicarboxylic acids include 1,4-cyclohexyldicarboxylic acid. Examples of aliphatic dicarboxylic acids include butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids and dimerized fatty acids.

[0082] The alkylaromatic diamine is preferably selected from 1,3-xylylenediamine (MXD), 1,4-xylylenediamine and their mixture. Preferably, the polyamide comprises, in addition to the repeating units of formula (I), repeating units selected from the repeating units of a PA selected from MXD6 and MXD10.

[0083] According to a second alternative, the polyamide is PASA derived from an aromatic dicarboxylic acid.

[0084] 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 an aromatic dicarboxylic acid Y3.

[0085] The aliphatic, linear or branched, or cycloaliphatic diamine of the repeating unit X3.Y3 is in particular as defined above.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] Whichever alternative is 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.

[0090] For example, the polyamide comprises, in addition to the repeating units of formula (I), repeating units A / X3.Y3 chosen from:

[0091] A / 6T, A / 9T, A / 10T and A / 11T, A being as defined above, in particular 6 / 6T, 6I / 6T, MPMDT / 6T, MXDT / 6T, PA11 / 10T, 11 / 6T / 10T, MXDT / 10T, MPMDT / 10T, a 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, and

[0092] A / X3.Y3 in which X3 is BMACM, PACM or IPD and Y3 is T or I and A is 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.1 , 11 / 1 ,4-BAC.I, 11 / 1 ,3-BAC.T / 10.T, 11 / 1,4-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.

[0093] 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).

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] Preferably, the polyamide has an inherent viscosity of between 0.70 and 1.70, advantageously of between 0.80 and 1.50.

[0100] 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 heating of DSC at 20°C / min according to standard ISO 11357). The polyamide may further comprise fillers, reinforcing fibers, additives, in particular chosen from flame retardants, antioxidants, plasticizers and mixtures thereof, or a mixture thereof.

[0101] Reinforcing fibers include carbon or glass fibers, natural fibers, or a mixture of these.

[0102] Additives include 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.

[0103] The flame retardants are notably chosen from DOPO, melamine cyanurate, melamine polyphosphate, red phosphorus, metal dialkylphosphinates and mixtures thereof.

[0104] To the extent that the polyamides according to the invention are self-flame retardant, they can be free of flame retardant agent (used as an additive).

[0105] Typically, a chain limiting agent comprises at least one, preferably at least two functions, each independently selected 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.

[0106] 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.

[0107] 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.

[0108] The reinforcing fibers are chosen from fibers, particularly short fibers. The fibers may be of synthetic origin, including 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.

[0109] The usual stabilizers used are phenols, phosphites, UV absorbers, HALS (Hindered Amine Light Stabilizer) stabilizers, metal iodides or thioethers. Examples include Irganox 1010, 245, 1098, Irgafos 168, 126, Tinuvin 312, 770, Iodide P201 from Ciba, Nylostab S-EED from Clariant, AO 412S from Adeka Palmarole.

[0110] The mass proportion of the fillers is in particular 0.5 to 50.0% relative to the weight of the polyamide.

[0111] The mass proportion of reinforcing fibers is in particular 5 to 75% relative to the weight of the polyamide.

[0112] The mass proportion of the additives is in particular 0.05 to 3.00% relative to the weight of the polyamide.

[0113] The cumulative mass proportion of fillers, reinforcing fibers, and additives is in particular 0.1 to 80% relative to the weight of the polyamide.

[0114] The polyamide according to the invention is typically obtained by polycondensation of a monomer of formula (X):

[0115] [Chem 6] in which R 3 and R 4 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.

[0116] When R 3 and R 4 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):

[0117] [Chem 7]

[0118] When R 3 and R 4 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):

[0119] [Chem 8]

[0120] 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.

[0121] The embodiments described above for the repeating units are of course applicable to the monomers from which these units are derived.

[0122] Preferably, the polyamide is not obtained from a chain branching agent of the following formula (V):

[0123] [Chem 9] in which R 10 to R 15 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 R 10 to R 15is a substituted hydrocarbon group containing a carboxyl or amine terminus.

[0124] Polycondensation can be carried out in the presence of a chain-limiting dicarboxylic acid, resulting in a polyamide with a dicarboxylic chain end. As described below, the latter can serve as a precursor for the preparation of polyether block amide.

[0125] Polycondensation can be carried out in the presence of a chain-limiting diamine, resulting in a polyamide with diamine chains. As described below, the latter can serve as a precursor for the preparation of polyether block amide.

[0126] According to a second subject, the invention relates to a polyether block amide (PEBA) resulting from the polycondensation: of one or more polyamides as defined above 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.

[0127] The polyamide(s) as defined above is(are) useful as polyamide block(s) for the preparation of PEBA.

[0128] Advantageously, the PEBAs according to the invention are classified VO in the UL94-vertical burning test, in particular for tests with a PEBA sample 1.6 mm thick.

[0129] PEBAs result from the polycondensation of polyamides with reactive ends (amine, carboxylic acid) with polyether blocks with reactive ends. At least one block of the PEBA according to the invention is derived from a polyamide according to the invention.

[0130] The polyether blocks of the PEBA copolymer (the backbone 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 trimethylene ether glycol units, and / or PTMG (polytetramethylene glycol) blocks, i.e. made up of tetramethylene glycol units, also called polytetrahydrofuran. The copolymers may include several types of polyethers in their chain, the copolyethers being able to be block or random.

[0131] Blocks obtained by oxyethylation of bisphenols, such as bisphenol A, can also be used. These latter products are described in particular in document EP 0 613 919.

[0132] Polyether blocks can also be made up of ethoxylated primary amines. Examples of ethoxylated primary amines include the products of formula (XXX): [Chem 10] 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 NORAMOX® brand from Arkema and under the GENAMIN® brand from CLARIANT.

[0133] The polyether blocks may comprise polyoxyalkylene blocks with NH2 chain ends, such blocks being obtainable by cyanoacetylation of aliphatic α,ε-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 JP 2004346274, JP 2004352794 and EP 1482011).

[0134] Polyetherdiol blocks are either used as such and copolycondensed with carboxyl-ended polyamide blocks, or aminated to be transformed into polyetherdiamines and condensed with carboxyl-ended polyamide blocks.

[0135] 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.

[0136] Preferably, the PEBA results from one of the polycondensations according to one of the three alternatives which follow.

[0137] According to a first alternative, the PEBA results from the polycondensation: of one or more polyamides as defined above and having diamine chain ends, with one or more polyether blocks with dicarboxylic acid chain ends, which is (are) preferably a polyoxyalkylene with dicarboxylic acid chain ends.

[0138] The polyamide(s) with diamine chain ends is (are) for example the polyamide with diamine chain ends described above.

[0139] According to a second alternative, the PEBA results from the polycondensation: of one or more polyamides as defined above and having dicarboxylic acid chain ends, with one or more polyether blocks with diamine chain ends, which is (are) preferably a polyoxyalkylene with diamine chain ends.

[0140] The polyamide(s) with dicarboxylic chain ends is (are) for example the polyamide with dicarboxylic chain ends described above.

[0141] According to a third alternative, PEBA results from the polycondensation: of one or more polyamides as defined above and having dicarboxylic acid chain ends, with one or more polyetherdiol blocks.

[0142] PEBA is then a polyetheresteramide.

[0143] The polyamide(s) with dicarboxylic chain ends is (are) for example the polyamide with dicarboxylic chain ends described above.

[0144] Particularly preferred PEBA copolymers are copolymers comprising:

[0145] - at least one polyamide PA 11 block comprising repeating units of formula (I) and at least one PEG block;

[0146] - at least one polyamide PA 11 block comprising repeating units of formula (I) and at least one PTMG block;

[0147] - at least one polyamide PA 12 block comprising repeating units of formula (I) and at least one PEG block;

[0148] - at least one polyamide PA 12 block comprising repeating units of formula (I) and at least one PTMG block;

[0149] - at least one polyamide PA 6.10 block comprising repeating units of formula (I) and at least one PEG block;

[0150] - at least one polyamide PA 6.10 block comprising repeating units of formula (I) and at least one PTMG block;

[0151] - at least one polyamide PA 6 block comprising repeating units of formula (I) and at least one PEG block;

[0152] - at least one polyamide PA 6 block comprising repeating units of formula (I) and at least one PTMG block; - at least one polyamide PA 6 / 12 block comprising repeating units of formula (I) and at least one PEG block;

[0153] - at least one polyamide PA 6 / 12 block comprising repeating units of formula (I) and at least one PTMG block;

[0154] - at least one polyamide PA 11 / 12 block comprising repeating units of formula (I) and at least one PEG block;

[0155] - at least one polyamide PA 11 / 12 block comprising repeating units of formula (I) and at least one PTMG block.

[0156] 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.

[0157] 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.

[0158] The number-average molar mass is generally fixed by the chain limiter content. It can be calculated according to the relationship Mn — nmonomer X Mwrepeating motif / nichain mimic + Mwichain mimic

[0159] In this formula, n m monomer represents the number of moles of monomer, chain limiter represents the number of moles of excess chain limiter, MW morepeat unit represents the molar mass of the repeat unit, and MW chain limiter represents the molar mass of the excess chain limiter.

[0160] 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%.

[0161] The PEBA may further comprise fillers, reinforcing fibers, additives, or a mixture thereof, in particular those described above. The PEBA may be free of flame retardant agent (used as an additive). According to a third subject, 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.

[0162] According to a fourth subject, the invention relates to a method for preparing an article comprising a step of extruding, molding or overmolding the polyamide defined above or the PEBA defined above, whereby an article is obtained.

[0163] 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 components, such as headlight protectors, rearview mirrors, small parts of off-road vehicles, tanks, in particular, of mopeds, motorcycles, scooters, subject to mechanical and chemical aggression, screws, cosmetic articles subject to mechanical and chemical aggression, lipsticks, pressure gauges, aesthetic protection elements such as gas bottles. We can also mention objects or parts of objects for electronics requiring compliance with dimensions, for example parts of mobile phones, computers, tablets.

[0164] According to a fifth subject, the invention relates to the article comprising the polyamide or PEBA as defined above, or capable of being obtained by this process.

[0165] The invention is illustrated with the following examples, which are provided without limitation. Example 1: Preparation of monomer of formula (X)

[0166] Synthesis of DOPO-diamine of formula (X) in which R 3 and R 4 are NH.

[0167] 0.5 g of 4.4'-diaminobenzophenone (2.36 mmol), 3.06 g of DOPO (14, 13 mmol) are stirred in a 25 mL two-necked flask under nitrogen atmosphere for 4 h at 180 ° C. The product obtained is allowed to cool to 100 ° C then 20 mL 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).

[0168] Example 2: Polyamides comprising repeating units of formula (I)

[0169] The polyamide denoted A is a PA11. 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 1 hour 30 minutes. Then, the pressure is lowered to 12 bars, while maintaining the temperature at 260 degrees centigrade. The material is then transferred to a polymerizer, under nitrogen flushing at 260 degrees centigrade. The polymerizer is placed under a vacuum of 50 mbar for 30 minutes and maintained for 1 hour. The material is then extruded, in the form of granules. This process is used for all the polyamides exemplified.

[0170] The different polyamides were characterized according to the UL94 standard in vertical combustion on injected specimens with a thickness of 1.6 mm.

[0171] [Table 1]

[0172] Table 1: Natures and proportions of monomers for the preparation of polyamides Tables 2 and 3 below provide the properties. [Table 2]

[0173] Table 2: Properties of PAs Example 3: PEBA whose polyamide block comprises repeating units of formula

[0174] (I)

[0175] 3.1. Polycondensation materials used: PEBA CE1 (counter-example): PA 11-PTMG (Mn: 1000-1000) - PEBA CE1 is a copolymer with PA11 blocks and PTMG blocks with number-average molecular masses (Mn) of 1000 - 1000 respectively.

[0176] 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 1000g / mol and COOH-terminated 11 / 1.10 blocks of number-average molecular weights (Mn) 1000g / mol; said PEBA 1 containing 1% by mass of atomic phosphorus. PEBA 1 is thus obtained by loading 28.619g of Amino11, 10.692g of the monomer of formula (X) in which R 3 and R 4 represent NH and 13.562 g of sebacic acid then 50 g of PTMG1000; Amino11 representing 1-amino undecanoic acid.

Claims

CLAIMS 1. Polyamide comprising a repeating unit of formula (I): [Chem 11] in which R 1 and R 2 are independently chosen from NH and C=O, and in addition 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, the polyamide being free from a group of formula (IV): [Chem 12] and polyamide having a polydispersity index IP less than or equal to 15.

0.

2. Polyamide according to claim 1, in which R 1 and R 2 represent NH.

3. Polyamide according to claim 1, in which R 1 and R 2 represent C=O.

4. Polyamide according to any one of claims 1 to 3, comprising at least one repeating unit X1.Y1 obtained from the polycondensation of at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1.

5. Polyamide according to claim 4, comprising 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.

6. Polyamide according to any one of claims 4 to 5, the polyamide being amorphous.

7. Polyamide according to one of claims 1 to 3, comprising 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 diacids.

8. Polyamide according to one of claims 1 to 3, 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.

9. Polyamide according to claim 8, 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.

10. Polyamide according to any one of claims 7 to 9, 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.

11. Polyether block amide (PEBA) resulting from polycondensation: of one or more polyamides as defined in any one of claims 1 to 10 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.

12. Polyether block amide according to claim 11, resulting from the polycondensation: of one or more polyamides as defined in any one of claims 1 to 10 and having diamine chain ends, with one or more polyether blocks with dicarboxylic acid chain ends.

13. Polyether block amide according to claim 11, in which the polyether block with dicarboxylic acid chain ends is a polyoxyalkylene with dicarboxylic acid chain ends.

14. Polyether block amide according to claim 11 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.

15. Polyether block amide according to claim 14, in which the polyether block with diamine chain ends is a polyoxyalkylene with diamine chain ends.

16. Polyether block amide according to claim 11, 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 polyetherdiol blocks, the polyether block amide then being a polyetheresteramide.

17. Polyamide according to any one of claims 1 to 10 or polyether block amide according to any one of claims 11 to 16, having a mass proportion of atomic phosphorus of at least 0.1%.

18. Use of a polyamide according to any one of claims 1 to 10 and 17 or of a polyether block amide according to any one of claims 11 to 17 as a flame retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof.

19. Polyamide according to any one of claims 1 to 10 and 17 or polyether block amide according to any one of claims 11 to 17, 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.

20. Process for the preparation of a polyamide according to any one of claims 1 to 10 and 17 comprising the polycondensation of a monomer of formula (X): [Chem 12] in which R 3 and R 4 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.

21. Article comprising a polyamide according to any one of claims 1 to 10 and 17, a polyether block amide according to any one of claims 11 to 17 or a mixture thereof.

22. A method of preparing an article comprising a step of extruding, molding or overmolding the polyamide according to any one of claims 1 to 10 and 17 or polyether block amide according to any one of claims 11 to 17, whereby an article is obtained.

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