WO2025133185A1 - Compound for use in the preparation of an inherently flame-retardant polyamide or polyether block amide - Google Patents

Abstract

The present invention relates to a compound of formula (I), the preparation method thereof, and the use of same for the preparation of a polyamide or a polyether block amide incorporating a repeating unit derived from the compound within its polymer chain, conferring inherent flame-retardant properties on same. The invention also relates to the polyamide and the polyether block amide, an article comprising same, and the production method thereof.

Description

DESCRIPTION

TITLE: Compound useful for preparing a self-flame retardant polyamide or polyether block amide

The present invention relates to a compound comprising phosphorus atoms, its preparation process, and its use for the preparation of polyamide (PA) incorporating a repeating unit derived from said compound within its polymer chain or polyether block amide (PEBA) whose polyamide block(s) incorporate a repeating unit derived from said compound within its polymer chain, which gives the PA or PEBA self-flame retardant properties.

Polyamides, for example polyamide 11, known worldwide under its trademark Rilsan®, have exceptional performance in many applications such as transportation, energy, consumer goods such as sporting goods, eyewear, industry and consumer electronics, anti-corrosion protective coatings and objects obtained by 3D printing. PEBAs have exceptional performance in many applications such as consumer goods such as sporting goods and consumer electronics, industry, fluid or gas separation membranes and objects obtained by 3D printing.

PEBAs and polyamides in general, and PA11 in particular, certainly possess a very high level of performance. However, they are not naturally fire resistant: they burn easily, producing flaming droplets that can spread fires. However, many applications in the electrical, electrotechnical, electronics and transport sectors (air, rail, electric vehicles, etc.) require flame retardant performance.

Many solutions have been developed by adding, by melt blending, initially halogenated additives, now halogen-free, based on phosphorus, nitrogen or hydrated fillers. These additives are not integrated into the polymer chain of polyamides or PEBAs. 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, resistance to thermo-oxidation, dimensional stability, water uptake, rheology but also transparency.

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.

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.

An aim of the invention is to provide a compound which is easy to prepare and usable as a monomer for the preparation of a polyamide (PA) or polyether block amide (PEBA), and capable of conferring self-flame retardant properties to said polyamide (PA) or polyether block amide (PEBA).

An aim of the invention is also to provide a polyamide (PA) or polyether block amide (PEBA) having good flame retardant properties while retaining its other properties, in particular those listed above.

An aim of the invention is also to provide a polyamide (PA) or polyether block amide (PEBA) having good flame retardant properties and which can have a high molar mass.

dans laquelle : For this purpose, the invention relates to a compound of the following formula (I):

in which:

R ¹ represents H, a linear, branched or cyclic alkyl group comprising from 1 to 12 carbon atoms, or a cation, n represents an integer from 5 to 11, R ² and R ³ independently represent hydrogen, hydroxyl, alkoxyl comprising from 1 to 2 carbon atoms, a group -Ph, -Ph-Ph or -O-Ph, where Ph is phenyl optionally substituted by hydroxyl, provided that when R ² and R ³ each represent a group -Ph or -O-Ph, R ² and R ³ may be joined together to together form a biphenyl group, m represents an integer from 0 to 4, each R ⁴ is independently selected from hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms,

L is a single bond or a phenylene optionally substituted by one or more substituents chosen from a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms, an alkoxyl comprising from 1 to 4 carbon atoms,

dans laquelle n, R¹, R² et R³ sont tels que définis ci-dessus. R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms, alkoxyl comprising from 1 to 4 carbon atoms and a group of formula (I'):

in which n, R ¹ , R ² and R ³ are as defined above.

The compound of formula (I) comprises at least one phosphorus atom, which makes it capable of conferring flame retardant properties to a polyamide prepared using the compound of formula (I) as a monomer or to a PEBA whose polyamide block(s) are prepared using the compound of formula (I) as a monomer.

According to advantageous aspects of the invention, the compound of formula (I) comprises one or more of the following characteristics, taken alone or in all technically possible combinations: n represents 5, 10 or 11, preferably n represents 10,

R ⁵ represents a group of formula (I') as defined above, the compound thus having the following formula (II'):

dans laquelle R¹, R², R³, R⁴, m, n et L sont tels que ci-dessus, ou bien R⁵ est choisi parmi un hydrogène, un hydroxyle, un alkyle comprenant de 1 à

in which R ¹ , R ² , R ³ , R ⁴ , m, n and L are as above, or R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to

4 carbon atoms, an alkoxyl comprising from 1 to 4 carbon atoms,

ou R² est -Ph-Ph-OH et R³ est un hydroxyle, le groupe -(P=O)R²R³ ayant ainsi la formule (IV) :

R ² is -Ph, R ³ is -O-Ph and R ² and R ³ together form a biphenyl, the group - (P=O)R ² R ³ thus having the formula (III):

or R ² is -Ph-Ph-OH and R ³ is a hydroxyl, the group -(P=O)R ² R ³ thus having the formula (IV):

dans laquelle R1 et n sont tels que définis ci-dessus,

dans laquelle n est tel que défini ci-dessus,

dans laquelle n est tel que défini ci-dessus, avec un composé B de formule (

dans laquelle : m, L et R⁴ sont tels que définis ci-dessus, et The invention also relates to the process for preparing this compound, comprising the reaction: of a compound A of formula (

in which R1 and n are as defined above,

in which n is as defined above,

in which n is as defined above, with a compound B of formula (

in which: m, L and R ⁴ are as defined above, and

dans laquelle R² et R³ sont tels que définis ci-dessus et R⁶ représente H ou OH.R ⁷ is selected from a group -(C=O)H, a hydrogen, a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms, an alkoxyl comprising from 1 to 4 carbon atoms, and a compound C of formula (XIII):

wherein R ² and R ³ are as defined above and R ⁶ represents H or OH.

dans laquelle L, R⁴ et m sont tels que définis ci-dessus, le composé B étant de préférence choisi parmi le téréphthalaldéhyde et la divanilline, le composé C est choisi parmi le 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- oxide, l’acide hypophosphoreux, l’acide phényl phosphoreux, l’acide phosphorique, le diméthylphosphite, le diéthylphosphite, l’oxyde de diphénylphosphine et le diphénylphosphite, de préférence le composé C est le 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide. According to advantageous aspects of the invention, the process for preparing the compound comprises one or more of the following characteristics, taken in isolation or in all technically possible combinations: compound A has the formula (Xla) or (Xlb) as defined above in which n represents 5 or 10, or compound A is laurolactam, compound B is chosen from benzaldehyde, vanillin and ethylvanillin, or compound B has the formula (

in which L, R ⁴ and m are as defined above, compound B being preferably chosen from terephthalaldehyde and divanillin, compound C is chosen from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, hypophosphorous acid, phenyl phosphorous acid, phosphoric acid, dimethylphosphite, diethylphosphite, diphenylphosphine oxide and diphenylphosphite, preferably compound C is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

The invention also relates to the use of the compound of formula (I) as a flame retardant.

The invention also relates to the use of the compound of formula (I) as monomer or as comonomer, typically for the preparation of a (co)polymer, in particular of a polyether block amide (PEBA) or of a polyamide (PA), in particular of an aliphatic, transparent, or semi-aromatic polyamide.

The invention also relates to the use of the compound of formula (I) for improving the flame retardant properties of a (co)polymer, in particular a polyether block amide (PEBA) or a polyamide (PA), in particular an aliphatic, transparent, or semi-aromatic polyamide.

The invention also relates to a process for preparing a polyamide (PA) comprising the polycondensation of a compound of formula (I) optionally in the presence of one or more other comonomers. When the polyamide prepared is an aliphatic polyamide, the one or more other comonomers present during the polycondensation are typically chosen from aliphatic amino acids, aliphatic lactams, mixtures of aliphatic diamines and aliphatic dicarboxylic acids, and mixtures thereof. When the polyamide prepared is a semi-aromatic polyamide, the one or more other comonomers present during the polycondensation are typically one or more other aromatic comonomers. When the polyamide prepared is a transparent polyamide, the one or more other comonomers present during the polycondensation are typically at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1.

The invention also relates to a polyamide, in particular an aliphatic, transparent, or semi-aromatic polyamide, obtained by polycondensation of the compound according to the invention, optionally in the presence of one or more other comonomers. One or more other comonomers are typically as described above.

The invention also relates to a process for preparing a PEBA comprising the polycondensation: of one or more polyamides obtained by polycondensation of a compound of formula (I) 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.

The invention also relates to a PEBA resulting from such polycondensation. The polyamide comprises a repeating unit derived from the compound of formula (I). The polyamide block of the PEBA (or at least one block or each block if the PEBA comprises several) comprises a repeating unit derived from the compound of formula (I). The polyamide (PA) or polyether block amide (PEBA) is therefore rich in phosphorus atoms. The compound of formula (I) is used as a flame retardant and is incorporated as a unit within the polymer chain of the polyamide or within the polymer chain of the polyamide block(s) of the PEBA. The flame retardant is thus integrated by a reactive and not additive route. Advantageously, the polyamides and PEBA according to the invention are classified VO in the UL94-vertical burning test, in particular for tests with a sample of polyamide (PA) or polyether block amide (PEBA) 1.6 mm thick. The invention is also based on the discovery that such polyamides and PEBAs not only have good flame retardant properties, but also that they retain the intrinsic performance of the polyamide (PA) or polyether block amide (PEBA) from which they are derived (aliphatic polyamides free of repeating units derived from the compound of formula (I), but whose other repeating units are identical. For example, an aliphatic copolyamide PA11 whose polymer chain includes repeating units derived from the compound of formula (I) has good flame retardant properties, but retains the properties of PA11. According to another example, a semi-aromatic copolyamide PA MXD.10 whose polymer chain includes repeating units derived from the compound of formula (I) has good flame retardant properties, but retains the properties of PA MXD.10. According to another example, a transparent copolyamide PA MACM.10 whose polymer chain includes repeating units derived from the compound of formula (I) has good flame retardant properties, but retains the properties of PA MACM.10. according to another example, a PEBA prepared by polycondensation of a PA11 whose polymer chain includes repeating units derived from the compound of formula (I) with one or more polyether blocks has good flame retardant properties, and retains the properties of the PEBA prepared by polycondensation of PA11 with the same polyether block(s). Finally, it is possible to prepare polyamides and PEBA having high molar masses.

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et L² est un groupe divalent aliphatique comprenant de 4 à 36 atomes de carbone. le polyamide aliphatique ou semi-aromatique est obtenu par polycondensation d’un composé de formule (I) dans lequel R⁵ est choisi parmi un hydrogène, un hydroxyle, un alkyle comprenant de 1 à 4 atomes de carbone et un alcoxyle comprenant de 1 à 4 atomes de carbone, le polyamide aliphatique ou semi-aromatique comprenant motif répétitif de formule (XXII) :

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et R⁵ est choisi parmi un hydrogène, un hydroxyle, un alkyle comprenant de 1 à 4 atomes de carbone et un alcoxyle comprenant de 1 à 4 atomes de carbone, le polyamide est aliphatique et comprend en outre un ou plusieurs autre(s) motif(s), typiquement choisi(s) parmi un motif obtenu à partir d'au moins un aminoacide aliphatique, un motif obtenu à partir d'au moins un lactame aliphatique, un motif obtenu à partir de la polycondensation d'au moins une diamine aliphatique et d'au moins un acide dicarboxylique aliphatique, le polyamide est aliphatique et comprend en outre un motif répétitif de formule (XXIII) :

(XXIII) dans laquelle q représente un nombre entier de 5 à 11 , le polyamide est semi-aromatique et comprend en outre un motif répétitif X2.Y2 obtenu à partir de la polycondensation d'au moins une diamine alkylaromatique X2 et d’un acide dicarboxylique Y2 choisi parmi les acides dicarboxyliques aliphatiques, linéaires ou ramifiés et les acides dicarboxyliques cycloaliphatiques, le polyamide est semi-aromatique et comprend en outre un motif répétitif X3.Y3 obtenu à partir de la polycondensation d'au moins une diamine X3 aliphatique, linéaire ou ramifiée ou cycloaliphatique, et d’un acide dicarboxylique Y3 aromatique, qui est de préférence d’acide téréphthalique, d’acide isophthalique ou d’un mélange de ceux-ci, le polyamide est semi-aromatique et comprend, en plus du motif répétitif X2.Y3 et/ou X3.Y3, un motif répétitif aliphatique A choisi parmi un motif obtenu à partir d'au moins un aminoacide et un motif obtenu à partir d'au moins un lactame, le polyamide est transparent et comprend au moins un motif répétitif X1.Y1 obtenu à partir de la polycondensation d'au moins une diamine cycloaliphatique X1 et d'au moins un acide dicarboxylique Y1 , le polyamide pouvant alors comprendre en outre un motif répétitif aliphatique A choisi parmi un motif obtenu à partir d'au moins un aminoacide et un motif obtenu à partir d'au moins un lactame, le polyamide est transparent et est obtenu par polycondensation d’un composé de formule (II’) avec une diamine aliphatique de formule H2N-L²-NH2 dans laquelle L² est un groupe divalent aliphatique comprenant de 4 à 36 atomes de carbone, et, lorsque L² n’est pas un groupe divalent cycloaliphatique, avec au moins une diamine cycloaliphatique X1 et au moins un acide dicarboxylique Y1 , ledit polyamide transparent comprenant un motif répétitif de formule (XXI’) :

dans laquelle : m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus, et According to advantageous aspects of the invention, the polyamide (PA) comprises one or more of the following characteristics, taken in isolation or in all technically possible combinations: the polyamide is aliphatic, the polyamide is transparent, the polyamide is semi-aromatic, the polyamide is aliphatic or semi-aromatic and is obtained by polycondensation of a compound of formula (II') with an aliphatic diamine of formula H2N-L ² -NH2 in which L ² is an aliphatic divalent group comprising from 4 to 36 atoms of carbon, said aliphatic or semi-aromatic polyamide comprising a repeating unit of formula (

in which m, n, L, R ² , R ³ and R ⁴ are as defined above and L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms. the aliphatic or semi-aromatic polyamide is obtained by polycondensation of a compound of formula (I) in which R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms, the aliphatic or semi-aromatic polyamide comprising a repeating unit of formula (XXII):

in which m, n, L, R ² , R ³ and R ⁴ are as defined above and R ⁵ is selected from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms, the polyamide is aliphatic and further comprises one or more other unit(s), typically selected 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 is aliphatic and further comprises a repeating unit of formula (XXIII):

(XXIII) in which q represents an integer from 5 to 11, the polyamide is semi-aromatic and 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 is semi-aromatic and 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, which is preferably terephthalic acid, isophthalic acid or a mixture thereof, the polyamide is semi-aromatic and comprises, in addition to the repeating unit X2.Y3 and/or X3.Y3, an aliphatic repeating unit A chosen from a unit obtained from at least one amino acid and a unit obtained from at least a lactam, the polyamide is transparent and 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, the polyamide then being able to further comprise an aliphatic repeating unit A chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam, the polyamide is transparent and is obtained by polycondensation of a compound of formula (II') with an aliphatic diamine of formula H2N-L ² -NH2 in which L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, and, when L ² is not a divalent cycloaliphatic group, with at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1, said transparent polyamide comprising a repeating unit of formula (XXI'):

in which: m, n, L, R ² , R ³ and R ⁴ are as defined above, and

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et R⁵ est choisi parmi un hydrogène, un hydroxyle, un alkyle comprenant de 1 à 4 atomes de carbone et un alcoxyle comprenant de 1 à 4 atomes de carbone, et au moins un motif répétitif X1.Y1 obtenu à partir de la polycondensation d'au moins une diamine cycloaliphatique X1 et d'au moins un acide dicarboxylique Y1 , le polyamide (PA) a une proportion massique en phosphore atomique d’au moins 0, 1 %, le polyamide (PA) comprend des charges, des fibres de renfort, en particulier de verre, des additifs, en particulier choisis parmi les agents ignifugeants, les anti-oxydants, les plastifiants et les mélanges de ceux-ci, ou un mélange de ceux-ci. L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, it being understood that, when L ² is not a divalent cycloaliphatic group, then the transparent 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, the polyamide is transparent and is obtained by polycondensation of a compound of formula (I), in which R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms, with at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1, said transparent polyamide comprising: a repeating unit of formula (XXII):

in which m, n, L, R ² , R ³ and R ⁴ are as defined above and R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms, and 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 , the polyamide (PA) has a mass proportion of atomic phosphorus of at least 0.1%, the polyamide (PA) comprises fillers, reinforcing fibers, in particular glass fibers, additives, in particular chosen from flame retardants, antioxidants, plasticizers and mixtures thereof, or a mixture thereof.

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et R⁵ choisi parmi un hydrogène, un hydroxyle, un alkyle comprenant de 1 à 4 atomes de carbone et un alcoxyle comprenant de 1 à 4 atomes de carbone, avec un ou plusieurs blocs polyéthers à bouts de chaines capables de réagir avec les bouts de chaines du polyamide pour former des fonctions amide ou ester. le PEBA résulte de la polycondensation : d’un ou plusieurs polyamides ayant des bouts de chaines diamines ou acides dicarboxyliques et obtenus par polycondensation d’un composé de formule (II’) telle que définie ci-dessus avec une diamine aliphatique de formule H2N-L²-NH2 dans laquelle L² est un groupe divalent aliphatique comprenant de 4 à 36 atomes de carbone, ledit polyamide comprenant un motif répétitif de formule (XXI’) :

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et L² est un groupe divalent aliphatique comprenant de 4 à 36 atomes de carbone, avec un ou plusieurs blocs polyéthers à bouts de chaines capables de réagir avec les bouts de chaines du polyamide pour former des fonctions amide ou ester. le PEBA résulte de la polycondensation : d’un ou plusieurs polyamides ayant des bouts de chaines diamines et obtenus par polycondensation d’un composé de formule (I), avec un ou plusieurs blocs polyéthers à bouts de chaines acides dicarboxyliques, qui est de préférence un polyoxyalkylène à bouts de chaines acides dicarboxyliques, le PEBA résulte de la polycondensation : d’un ou plusieurs polyamides ayant des bouts de chaines acides dicarboxyliques et obtenus par polycondensation d’un composé de formule (I), avec un ou plusieurs blocs polyéthers à bouts de chaines diamines, qui est de préférence un polyoxyalkylène à bouts de chaînes diamines, le PEBA résulte de la polycondensation : d’un ou plusieurs polyamides ayant des bouts de chaines acides dicarboxyliques et obtenus par polycondensation d’un composé de formule (I), avec un ou plusieurs blocs polyétherdiols, le PEBA étant alors un polyétheresteramide, le PEBA a une proportion massique en phosphore atomique d’au moins 0,1 %, le PEBA comprend des charges, des fibres de renfort, en particulier de verre, des additifs, en particulier choisis parmi les agents ignifugeants, les anti-oxydants, les plastifiants et les mélanges de ceux-ci, ou un mélange de ceux-ci. 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 the polycondensation: of one or more polyamides having diamine or dicarboxylic acid chain ends and obtained by polycondensation of a compound of formula (I) in which R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms, and comprising a repeating unit of formula (XXII):

in which m, n, L, R ² , R ³ and R ⁴ are as defined above and R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms, 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. PEBA results from the polycondensation: of one or more polyamides having diamine or dicarboxylic acid chain ends and obtained by polycondensation of a compound of formula (II') as defined above with an aliphatic diamine of formula H2N-L ² -NH2 in which L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, said polyamide comprising a repeating unit of formula (XXI'):

in which m, n, L, R ² , R ³ and R ⁴ are as defined above and L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, 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. PEBA results from the polycondensation: of one or more polyamides having diamine chain ends and obtained by polycondensation of a compound of formula (I), with one or more polyether blocks with dicarboxylic acid chain ends, which is preferably a polyoxyalkylene with dicarboxylic acid chain ends, PEBA results from the polycondensation: of one or more polyamides having dicarboxylic acid chain ends and obtained by polycondensation of a compound of formula (I), with one or more polyether blocks having diamine chain ends, which is preferably a polyoxyalkylene having diamine chain ends, the PEBA results from the polycondensation: of one or more polyamides having dicarboxylic acid chain ends and obtained by polycondensation of a compound of formula (I), with one or more polyetherdiol blocks, the PEBA then being a polyetheresteramide, the PEBA has a mass proportion of atomic phosphorus of at least 0.1%, 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 polyether block amide (PEBA) defined above or of the polyamide (PA) defined above, in particular of the aliphatic, transparent, or semi-aromatic polyamide, defined above as a flame retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof.

The invention also relates to an article comprising the polyamide (PA) defined above, in particular the aliphatic, transparent, or semi-aromatic polyamide defined above, or the polyether block amide (PEBA) defined above.

The invention also relates to a method for preparing an article comprising a step of extruding, molding or overmolding this polyamide (PA), in particular this aliphatic, transparent, or semi-aromatic polyamide, or this polyether block amide (PEBA), whereby an article is obtained.

Definitions

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 the ISO 11357-1:2009 and ISO 11357-2:2013 standards for these polyamides is greater than 75°C, in particular greater than or equal to 100°C, in particular greater than or equal to 12°C, preferably greater than or equal to 140°C.

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.

A transparent polyamide, within the meaning of the invention, is a polyamide which, when in the form of a 2 mm thick plate, has a transmittance, measured at a wavelength of 560 nm according to standard ISO 13468-2 of 2021, at least equal to 80%, preferably at least 85%, or even at least 90%.

The term "transmittance" refers to the fraction of a luminous flux of a material in the form of a 2 mm thick plate for a given wavelength. Unless otherwise stated, transmittance is measured on a Konica-Minolta CM-3610A spectrophotometer according to ISO 13468-2 (Illuminant D65, 10°) on 100 x 100 mm plates with a thickness of 2 mm, at a wavelength of 560 nm.

The term "Haze value" is used to describe the transparency of a material in terms of light scattering at an angle greater than 2.5° from the observed normal due to the interaction of light with inhomogeneities present in the material. Unless otherwise stated, the Haze value is measured using a Konica-Minolta CM-3610A spectrophotometer according to D1003 standard on 100 x 100 mm plates with a thickness of 2 mm.

An amorphous PEBA, within the meaning of the application, means a PEBA having only one or more glass transition temperatures (no melting temperatures (Tf)), or a very slightly crystalline PEBA having one or more glass transition temperatures and one or more melting points, it being understood that this melting point is such that (if there is only one melting point), or each melting point is such that (if there are several), 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.

A semi-crystalline PEBA, within the meaning of the application, means a PEBA which has a melting temperature or temperatures (Tf) in DSC according to the ISO 11357-3:2013 standard, it being understood that the melting point is such that (if there is only one melting point), or at least one melting point is such that (if there are several) is such that the enthalpy of crystallization during the cooling step at a rate of 20K/min in DSC measured according to ISO 11357-3 of 2013 greater than 30 J/g, preferably greater than 40 J/g.

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.

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

In the PA X.Y notation, X represents the number of carbon atoms from diamine residues or the abbreviation for diamine, and Y represents the number of carbon atoms from diacid residues or the abbreviation for diacid, conventionally.

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

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

The polydispersity index IP is equal to the ratio of the molar mass by weight to the molar mass by number (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. 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.

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).

Total acidity and total basicity are measured by potentiometry.

Acidity is measured using the following method. A sample of polyamide or PEBA is dissolved in benzyl alcohol. This sample is then potentiometrically assayed using a 0.02N tetrabutylammonium hydroxide solution. Basicity is measured using the following method. A sample of polyamide or PEBA is dissolved in metacresol. This sample is then potentiometrically assayed using a 0.02N perchloric acid solution.

Inherent viscosity is measured at a polyamide or PEBA concentration of 0.5% by weight in solution in metacresol on the total weight of the solution, at 20°C, according to ISO 307:2007, typically using a viscometer equipped with a Micro-Ubbelohde viscometer tube. To be considered as a polyamide or as a

PEBA, the inherent viscosity must be greater than or equal to 0.5. Below this value, it is considered that there has not been sufficient polymerization and therefore that a polyamide or a PEBA within the meaning of the invention has not been formed.

The crystallinity rate of a polyamide is calculated using the following formula:

[Math 1]

dans laquelle : 100

in which:

X denotes the crystallinity rate,

AHf * denotes the enthalpy of fusion of the 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.

By "linear, branched or cyclic alkyl" is meant a linear or branched saturated aliphatic hydrocarbon group or a cyclic alkyl group. The linear or branched alkyl comprises from 1 to 12, in particular from 1 to 8, preferably from 1 to 6, in particular from 1 to 4 carbon atoms. Examples of linear or branched alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl or pentyl groups. The cyclic alkyl comprises from 3 to 12, in particular from 3 to 8, preferably from 3 to 6, in particular from 3 to 4 carbon atoms. Examples of cyclic alkyl include cyclopropyl, methylcyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl groups.

An alkoxyl group is an -O-alkyl radical where the alkyl group is as previously defined. Examples of alkoxyl include methoxyl, ethoxyl, or propoxyl. [Compound]

dans laquelle : According to a first subject, the invention relates to a compound of the following formula (I):

in which:

R ¹ represents H, a linear, branched or cyclic alkyl group comprising from 1 to 12 carbon atoms, or a cation, n represents an integer from 5 to 11,

R ² and R ³ independently represent hydrogen, hydroxyl, alkoxyl comprising from 1 to 2 carbon atoms, a group -Ph, -Ph-Ph or -O-Ph, where Ph is phenyl optionally substituted by hydroxyl, provided that when R ² and R ³ each represent a group -Ph or -O-Ph, R ² and R ³ may be joined together to together form a biphenyl group, m represents an integer from 0 to 4, each R ⁴ is independently selected from hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms,

L is a single bond or a phenylene optionally substituted by one or more substituents chosen from a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms, an alkoxyl comprising from 1 to 4 carbon atoms,

dans laquelle n, R¹, R² et R³ sont tels que définis ci-dessus. R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms, alkoxyl comprising from 1 to 4 carbon atoms and a group of formula (I'):

in which n, R ¹ , R ² and R ³ are as defined above.

Preferably, in formula (I), n represents 5, 10 or 11, particularly preferably, n represents 10. These compounds are in fact particularly suitable for being incorporated within: respectively of aliphatic polyamide PA6, PA11 and PA12. For example, when n is 10, the group -NH(CH2) -COOR ¹ is then derived from amino-11-undecanoic acid, and the compound of formula (I') is particularly suitable for incorporation into a PA11. of semi-aromatic polyamide PA A/X2.Y2 or PA A/X3.Y3 where A is respectively the unit of a PA6, PA11 and PA12. For example, when n is 10, the group -NH(CH2) - COOR ¹ is then derived from amino-11-undecanoic acid, and the compound of formula (I') is particularly suitable for incorporation into a PA 11/X2.Y2 or PA 11/X3.Y3. of transparent polyamide PA A.X1. Y1 where A is respectively the unit of a PA6, PA11 and PA12. For example, when n is 10, the group -NH(CH2) -COOR ¹ is then derived from amino-11-undecanoic acid, and the compound of formula (I') is particularly suitable for incorporation into a transparent polyamide PA A.X1.Y1 where A is the repeating unit of a PA11.

In formula (I), R ¹ represents H, a linear, branched or cyclic alkyl group comprising from 1 to 12 carbon atoms, or a cation. The cation is preferably an alkaline earth or alkali cation. Preferably, R ¹ represents H or a cation.

In formula (I), each R ⁴ is independently selected from hydroxyl, alkyl comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and alkoxyl comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms. Preferably, R ⁴ represents OH, Me or OMe.

In formula (I), m represents an integer from 0 to 4, preferably 0 or 1. When m is 0, the compound is free of R ⁴ group.

dans laquelle m et R⁴ sont tels que définis ci-dessus. In formula (I), L is a single bond or a phenylene optionally substituted by one or more substituents selected from a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and an alkoxyl comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms. Preferably, L represents a single bond or a divalent phenylene of formula (L'):

in which m and R ⁴ are as defined above.

Two alternatives can be distinguished for the R ⁵ group of formula (I).

dans laquelle R¹, R², R³, R⁴, m, n et L sont tels que ci-dessus. Un tel composé est avantageusement porteur de deux fonctions -COOR¹ qui peuvent servir de groupes réactifs pour incorporer le composé de formule (II’) au sein de la chaine polymérique de polyamides, de préférence de polyamides aliphatiques ou semi-aromatiques, ou au sein de la chaine polymérique d’un bloc polyamide d’un PEBA. According to a first alternative, in formula (I), R ⁵ represents a group of formula (I') as defined above, and the compound thus has the following formula (II'):

in which R ¹ , R ² , R ³ , R ⁴ , m, n and L are as above. Such a compound advantageously carries two -COOR ¹ functions which can serve as reactive groups to incorporate the compound of formula (II') within the polymer chain of polyamides, preferably aliphatic or semi-aromatic polyamides, or within the polymer chain of a polyamide block of a PEBA.

dans laquelle R¹, R², R³, R⁴, n et m sont tels que définis ci-dessus. In a first embodiment of this first alternative, L represents a single bond. The compound then has the following formula (I la):

in which R ¹ , R ² , R ³ , R ⁴ , n and m are as defined above.

dans laquelle R¹, R², R³, R⁴, n et m sont tels que définis ci-dessus. Les deux groupes phényle du composé de formule (H’b) peuvent être reliés à n’importe quelle position de chaque phényle. De préférence, le composé de formule (H’b) est symétrique. Selon une seconde alternative, dans la formule (I), R⁵ est choisi parmi un hydrogène, un hydroxyle, un alkyle comprenant de 1 à 4 atomes de carbone et un alcoxyle comprenant de 1 à 4 atomes de carbone. La fonction amine secondaire et le groupe -COOR¹ du groupe -NH(CH2)n-COOR¹ peuvent alors servir de groupe réactifs pour incorporer le composé de formule (I) au sein de la chaine polymérique de polyamides ou au sein de la chaine polymérique d’un bloc polyamide d’un PEBA. La fonction amine secondaire est moins réactive qu’une fonction -COOR¹. Ainsi, le composé selon cette seconde alternative est généralement moins réactif que celui de formule (II’) selon la première alternative ci-dessus, qui est porteur de deux fonctions -COOR¹. Par ailleurs, trois alternatives peuvent être distinguées pour les groupes R² et R³ de la formule (I). In a second embodiment of this first alternative, L represents the divalent phenylene of formula (L') defined above. The compound then has the following formula (H'b):

wherein R ¹ , R ² , R ³ , R ⁴ , n and m are as defined above. The two phenyl groups of the compound of formula (H'b) may be attached to any position of each phenyl. Preferably, the compound of formula (H'b) is symmetrical. According to a second alternative, in formula (I), R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms. The secondary amine function and the -COOR ¹ group of the -NH(CH2)n-COOR ¹ group can then serve as reactive groups to incorporate the compound of formula (I) within the polymer chain of polyamides or within the polymer chain of a polyamide block of a PEBA. The secondary amine function is less reactive than a -COOR ¹ function. Thus, the compound according to this second alternative is generally less reactive than that of formula (II') according to the first alternative above, which carries two -COOR ¹ functions. Furthermore, three alternatives can be distinguished for the R ² and R ³ groups of formula (I).

Le composé a alors la formule (V) suivante :

dans laquelle R¹, R⁴, R⁵, L, n et m sont tels que définis ci-dessus. According to a first alternative, in formula (I), R ² is -Ph, R ³ is -O-Ph and R ² and R ³ together form a biphenyl, the group -(P=O)R ² R ³ thus having the formula (III):

The compound then has the following formula (V):

in which R ¹ , R ⁴ , R ⁵ , L, n and m are as defined above.

According to a second alternative, in formula (I), R ² is -Ph-Ph-OH and R ³ is a hydroxyl, the group -(P=O)R ² R ³ thus having the formula (IV):

dans laquelle R¹, R⁴, R⁵, L, n et m sont tels que définis ci-dessus. The compound then has the following formula (VI):

in which R ¹ , R ⁴ , R ⁵ , L, n and m are as defined above.

The compound of formula (VI) corresponds to the open form of the compound of formula (V). In practice, the two compounds can coexist. The invention therefore also relates to a mixture of the compounds of formula (V) and (VI).

According to a third alternative, in formula (I), R ² and R ³ are identical and represent a group -Ph, -Ph-Ph or -O-Ph, where Ph is a phenyl optionally substituted by a hydroxyl, it being understood that: when R ² and R ³ both represent -Ph, R ² and R ³ may be linked together to form together a biphenyl group, or when R ² and R ³ both represent -O-Ph, R ² and R ³ may be linked together to form together a biphenyl group.

In a particularly preferred embodiment of this third alternative, R ² and R ³ each represent a -Ph group, the -(P=O)R ² R ³ group thus having the formula (VII):

dans laquelle R¹, R⁴, R⁵, L, n et m sont tels que définis ci-dessus. The compound then has the following formula (VIII):

in which R ¹ , R ⁴ , R ⁵ , L, n and m are as defined above.

[Process for preparing the compound]

dans laquelle R¹ et n sont tels que définis ci-dessus,

dans laquelle n est tel que défini ci-dessus,

dans laquelle n est tel que défini ci-dessus, avec un composé B de formule (

dans laquelle : m, L et R⁴ sont tels que définis ci-dessus, et According to a second subject, the invention relates to a process for preparing the compound of formula (I), comprising the reaction: of a compound A of formula (

in which R ¹ and n are as defined above,

in which n is as defined above,

in which n is as defined above, with a compound B of formula (

in which: m, L and R ⁴ are as defined above, and

dans laquelle R² et R³ sont tels que définis ci-dessus et R⁶ représente H ou OH.R ⁷ is selected from a group -(C=O)H, a hydrogen, a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms, an alkoxyl comprising from 1 to 4 carbon atoms, and a compound C of formula (XIII):

wherein R ² and R ³ are as defined above and R ⁶ represents H or OH.

The method according to the invention is illustrated in diagram 1 below:

Scheme 1: Reaction scheme of the process for the preparation of the compound of formula (I)

When compound A has the formula (Xlc), the reaction is preferably carried out in the presence of an acid. This allows the opening of the lactam of formula (Xlc), whereby the compound of formula (Xlc) is transformed into a compound of formula (Xla) and/or (Xlb).

According to a first preferred embodiment for compound A, compound A has the formula (Xla) or (Xlb), in which n represents 5 or 10. This embodiment makes it possible to prepare compounds of formula (I) in which n represents 5 or 10, which are particularly suitable for being incorporated respectively within: the polymer chain of aliphatic polyamide PA6 or PA11, the polymer chain of semi-aromatic polyamide PA 6/X2.Y2 or 6/X3.Y3, and PA 11/X2.Y2 or 11/X3.Y3, or the polymer chain of a PA A/X1.Y1 where A is the unit of a PA6 or a PA11.

Typically, compound A is 6-aminohexanoic acid, 11-aminoundecanoic acid, or a salt thereof.

According to a second preferred embodiment for compound A, compound A is laurolactam. Laurolactam is a compound of formula (Xlc) in which n represents 11. This embodiment makes it possible to prepare a compound of formula (I) in which n represents 11, which is particularly suitable for incorporation into the polymer chain: of aliphatic polyamide PA12, of semi-aromatic polyamide PA 12/X2.Y2 or 12/X3.Y3, or of a transparent polyamide PA A/X1.Y1 where A is the unit of a PA12.

According to a first preferred embodiment for compound B, compound B is chosen from benzaldehyde, vanillin and ethyl vanillin.

dans laquelle L, R⁴ et m sont tels que définis ci-dessus. Le composé préparé par le procédé a alors la formule (II’) définie ci-dessus. De préférence, le composé B est choisi parmi le téréphthalaldéhyde et la divanilline. According to a second preferred embodiment for compound B, compound B has the formula (XII'):

in which L, R ⁴ and m are as defined above. The compound prepared by the process then has the formula (II') defined above. Preferably, compound B is chosen from terephthalaldehyde and divanillin.

According to a preferred embodiment for compound C, compound C is selected from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, hypophosphorous acid, phenyl phosphorous acid, phosphoric acid, dimethylphosphite, diethylphosphite and diphenylphosphite, diphenylphosphine oxide, preferably compound C is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. The compound prepared then has the formula (I) in which the group -(P=O)R ² R ³ has the formula (III) or (IV) as defined above.

Advantageously, the starting products, namely compound A (of formulas (Xla), (Xlb), (Xlc)), compound B (of formula (XII)) and compound C (of formula (XIII)) are commercially available.

Preferably, from 1.0 to 2.5 equivalents of compound A are used relative to compound B.

Preferably, from 1.0 to 2.5 equivalents of compound C are used relative to compound B.

Moreover, the process according to the invention is simple. It is sufficient to mix three compounds.

The reaction is generally carried out in a solvent, preferably in a polar solvent, for example chosen from methanol, ethanol, isopropanol and dimethyl sulfoxide. The mass concentration of compounds A + B + C in the solvent is generally 20 g/L to 250 g/L.

The reaction is typically carried out at a temperature of 50 to 100°C, and/or at atmospheric pressure.

Typically, the reaction is carried out in two stages, a first stage where compounds A and B and a solvent are added to a reactor, generally equipped with a condenser. The reaction medium is heated to solvent reflux and left stirring until the end of the first synthesis stage, then for the second stage, the reaction medium is cooled, for example to 60°C, and compound C is added. The reaction is continued with stirring until the end of the second synthesis stage. At the end of the reaction, the reaction medium is cooled to room temperature (20°C) until a white precipitate appears.

The further work-up to recover the compound of formula (I) is also simple. After reaction, the reaction medium is filtered and rinsed with the solvent. The solid obtained is dried under vacuum to remove the excess solvent. In particular, the compound of formula (I) is obtained directly in neutral form, and it is therefore not necessary to acidify and/or basify the reaction medium. The process is therefore preferably free of an acidification or basification step.

[Uses of the compound]

According to a third subject, the invention relates to the use of the compound of formula (I) as defined above as a flame retardant.

According to a fourth subject, the invention relates to the use of the compound of formula (I) for improving the flame retardant properties of a (co)polymer, in particular of a polyether block amide (PEBA) or of a polyamide (PA), in particular an aliphatic, semi-aromatic or transparent polyamide.

According to a fifth object, the invention relates to the use of the compound of formula (I) as monomer or as comonomer, typically for the preparation of a (co)polymer, in particular a polyether block amide (PEBA) or a polyamide (PA), in particular an aliphatic, semi-aromatic or transparent polyamide.

[Process for preparing a PA or PEBA (co)polymer]

According to a sixth subject, the invention relates to a process for preparing a (co)polymer comprising the polycondensation of a compound of formula (I), optionally in the presence of one or more other comonomers. The (co)polymer is preferably a PEBA or a polyamide, preferably an aliphatic, semi-aromatic or transparent polyamide.

Advantageously, the compound of formula (I) does not act as a chain limiter, and it is possible to prepare polyamides or polyether block amides having a high molar mass.

• Process for the preparation of an aliphatic polyamide

According to a first aspect of this sixth subject, the invention relates in particular to a process for preparing an aliphatic polyamide comprising the polycondensation of a compound of formula (I), optionally in the presence of one or more other aliphatic comonomers, typically chosen from an aliphatic amino acid, an aliphatic lactam, or a mixture of at least one aliphatic diamine and at least one aliphatic dicarboxylic acid.

• Process for the preparation of a semi-aromatic polyamide

According to a second aspect of this sixth subject, the invention relates in particular to a process for preparing a semi-aromatic polyamide comprising the polycondensation of a compound of formula (I), optionally in the presence of one or more other comonomers, preferably aromatic, typically an aromatic dicarboxylic acid or an aromatic diamine, in particular an alkylaromatic diamine.

According to a first alternative, the process for preparing the semi-aromatic polyamide comprises the polycondensation of a compound of formula (I) with at least one alkylaromatic diamine X2 and one dicarboxylic acid Y2 chosen from linear or branched aliphatic dicarboxylic acids and cycloaliphatic dicarboxylic acids.

The alkylaromatic diamine X2 is preferably selected from 1,3-xylylenediamine (MXD), 1,4-xylylenediamine and their mixture.

The dicarboxylic acid Y2 has in particular from 4 to 36 carbon atoms, preferably those having from 6 to 18 carbon atoms. Examples of aliphatic dicarboxylic acid Y2 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 "Cargill", or under the brand name EMPOL by the company BASF, or under the brand name Radiacid by the company OLEON, and polyoxyalkylene a,co-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.

Examples of preferred aliphatic Y2 dicarboxylic acids include butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids, and dimerized fatty acids.

When the dicarboxylic acid Y2 is cycloaliphatic, it can 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 Y2.

In one embodiment, the method comprises the polycondensation of a compound of formula (I) with at least one alkylaromatic diamine X2, with at least one dicarboxylic acid Y2 chosen from linear or branched aliphatic dicarboxylic acids and cycloaliphatic dicarboxylic acids, and with at least one monomer A chosen from an amino acid or at least one lactam.

Monomer A is preferably aliphatic.

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. Preferably, the amino acid comprises from 9 to 12 carbon atoms. It can thus be chosen from 9-aminononanoic acid (noted 9), 10-aminodecanoic acid (noted 10), 11-aminoundecanoic acid (noted 11) and 12-aminododecanoic acid (noted 12). Preferably, the repeating unit A is obtained from 11-aminoundecanoic acid (11).

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, α,α-dimethylpropriolactam, amylolactam, caprolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam, the lactam preferably being caprolactam, oenantholactam and lauryllactam, in particular caprolactam (6) or lauryllactam (12). According to a second alternative, the process for preparing a semi-aromatic polyamide comprises the polycondensation of a compound of formula (I) with at least one aliphatic, linear or branched or cycloaliphatic diamine X3 and an aromatic dicarboxylic acid Y3.

The aliphatic diamine X3 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 linear or branched aliphatic diamine X3 include 1,4-diaminobutane, 1,5-diaminopentane, hexamethylenediamine, 1,10-decamethylenediamine, tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols, methyl-pentamethylenediamine (MPMD), methaxylyenediamine, trimethylhexamethylenediamine.

A non-exhaustive list of cycloaliphatic diamine X3 is given in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405).

The cycloaliphatic diamine X3 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.

Advantageously, the cycloaliphatic diamine X3 is chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis(aminocyclohexyl)-methane (P), 1,3-bis(aminomethyl)cyclohexane (1,3-BAC) and isophoronediamine (IPD).

The aromatic dicarboxylic acid 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.

In one embodiment, the semi-aromatic polyamide comprises more than 55 mol% of one of these aromatic diacids Y3 or a mixture thereof, preferably terephthalic acid, isophthalic acid or a mixture thereof. It is then a polyphthalamide (PPA). In one embodiment, the method comprises the polycondensation of a compound of formula (I) with at least one aliphatic, linear or branched or cycloaliphatic diamine X3, with an aromatic dicarboxylic acid Y3, and with at least one monomer A chosen from an amino acid or at least one lactam.

Monomer A is in particular as defined above for the first alternative.

• Process for preparing a transparent polyamide

According to a third aspect of this sixth subject, the invention relates in particular to a process for preparing a transparent polyamide comprising the polycondensation of a compound of formula (I), optionally in the presence of one or more other comonomers, in particular in the presence of one or more other cycloaliphatic comonomers.

The process for preparing a transparent polyamide typically comprises the polycondensation of a compound of formula (I), at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1.

A non-exhaustive list of these cycloaliphatic diamines X1 is given in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405).

The cycloaliphatic diamine X1 is preferably a primary diamine (two NH2 groups).

The cycloaliphatic diamine X1 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.

Advantageously, the cycloaliphatic diamine X1 is chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis(aminocyclohexyl)-methane (P), 1,3-bis(aminomethyl)cyclohexane (1,3-BAC) and isophoronediamine (IPD).

In an advantageous embodiment, the cycloaliphatic diamine X1 is a bicycloaliphatic diamine, in particular chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis(aminocyclohexyl)-methane (P). The dicarboxylic acid Y1 may be selected from linear or branched aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids and aromatic dicarboxylic acids.

The dicarboxylic acid Y1 has in particular from 4 to 36 carbon atoms, preferably those having from 6 to 18 carbon atoms.

Examples of aliphatic dicarboxylic acid Y1 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 "Cargill", 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.

In an advantageous version, when it is aliphatic, the dicarboxylic acid Y1 is an aliphatic dicarboxylic acid chosen from adipic acid (6), decanedioic acid (10), dodecanedioic acid (12) and tetradecanedioic acid (14).

When the dicarboxylic acid Y1 is cycloaliphatic, it can 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.

When the dicarboxylic acid Y1 is aromatic, it is preferably chosen from terephthalic acid, isophthalic acid, furanedicarboxylic acid, and naphthalenic diacid, particularly preferably from terephthalic acid and isophthalic acid.

In one embodiment, the process for preparing a transparent polyamide comprises the polycondensation of a compound of formula (I), at least one cycloaliphatic diamine X1, at least one dicarboxylic acid Y1 and at least one monomer A chosen from an amino acid and a lactam. Monomer A is preferably aliphatic.

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. Preferably, the amino acid comprises from 9 to 12 carbon atoms. It can thus be chosen from 9-aminononanoic acid (noted 9), 10-aminodecanoic acid (noted 10), 11-aminoundecanoic acid (noted 11) and 12-aminododecanoic acid (noted 12). Preferably, the repeating unit A is obtained from 11-aminoundecanoic acid (11).

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, α,α-dimethylpropriolactam, amylolactam, caprolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam, the lactam preferably being caprolactam, oenantholactam and lauryllactam, in particular caprolactam (6) or lauryllactam (12).

• Process for preparing a PEBA

According to a fourth aspect of this sixth subject, the invention relates in particular to a process for preparing a PEBA comprising the polycondensation: of one or more polyamides having diamine or dicarboxylic acid chain ends and obtained by polycondensation of a compound of formula (I), 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.

Preferably, the process comprises one of the polycondensations according to one of the following three alternatives.

According to a first alternative, the process comprises the polycondensation: of one or more polyamides obtained by polycondensation of a compound of formula (I) 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.

According to a second alternative, the process comprises polycondensation: of one or more polyamides obtained by polycondensation of a compound of formula (I) 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.

According to a third alternative, the process comprises polycondensation: of one or more polyamides obtained by polycondensation of a compound of formula

(I) and having dicarboxylic acid chain ends, with one or more polyetherdiol blocks.

The process then leads to the preparation of a polyetheresteramide.

The process may include, before the step of polycondensation of one or more polyamides with one or more polyether blocks, a prior step of preparation of the polyamide block(s) by polycondensation of a compound of formula (I).

The polycondensation of the compound of formula (I) to form the polyamide block can be carried out in the presence of a chain-limiting dicarboxylic acid, thereby obtaining a polyamide with dicarboxylic chain ends. The latter can serve as a precursor for the preparation of PEBA. Alternatively, the polycondensation of the compound of formula (I) to form the polyamide block can be carried out in the presence of a chain-limiting diamine, thereby obtaining a polyamide with diamine chain ends. The latter can serve as a precursor for the preparation of PEBA.

The step of preparing the polyamide block(s) by polycondensation of a compound of formula (I) is detailed below depending on the nature of the polyamide block.

The polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) can be a homopolyamide or copolyamide.

Typically, the polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) is obtained by polycondensation of a compound of formula (I) as defined above, optionally with at least one amino acid, and/or at least one lactam and/or at least one aliphatic, cycloaliphatic or alkylaromatic diamine and at least one aliphatic, cycloaliphatic or aromatic dicarboxylic acid.

* Preparation of an aliphatic polyamide block

In one embodiment, the polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) is an aliphatic polyamide block. The method may then comprise a step of preparing an aliphatic polyamide block by polycondensation of a compound of formula (I) in the presence of one or more other aliphatic comonomers, typically chosen from an aliphatic amino acid, an aliphatic lactam, or a mixture of at least one aliphatic diamine and at least one aliphatic dicarboxylic acid. Advantageously, the compound of formula (I) does not act as a chain limiter, and it is possible to prepare aliphatic polyamide blocks having a high molar mass. 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. Preferably, the amino acid comprises from 9 to 12 carbon atoms. It can thus be chosen from 9-aminononanoic acid (noted 9), 10-aminodecanoic acid (noted 10), 11-aminoundecanoic acid (noted 11) and 12-aminododecanoic acid (noted 12). Preferred aliphatic amino acids are aminocaproic, amino-7-heptanoic, amino-11-undecanoic, n-heptyl-11-aminoundecanoic and amino-12-dodecanoic acids.

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, α,α-dimethylpropriolactam, amylolactam, caprolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam, the lactam preferably being caprolactam, oenantholactam and lauryllactam.

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, 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).

The dicarboxylic acid has in particular from 4 to 36 carbon atoms, preferably those having from 6 to 18 carbon atoms. As examples of aliphatic dicarboxylic acid, it is possible to cite 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 "Cargill", 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.

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.

* Preparation of a cycloaliphatic polyamide block

In one embodiment, the polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) is a cycloaliphatic polyamide block. The method may then comprise a step of preparing a cycloaliphatic polyamide block by polycondensation of a compound of formula (I), at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1.

A non-exhaustive list of these cycloaliphatic diamines X1 is given in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405).

The cycloaliphatic diamine X1 is preferably a primary diamine (two NHL groups).

The cycloaliphatic diamine X1 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. Advantageously, the cycloaliphatic diamine X1 is chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis(aminocyclohexyl)-methane (P), 1,3-bis(aminomethyl)cyclohexane (1,3-BAC) and isophoronediamine (IPD).

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

The dicarboxylic acid Y1 can be chosen from aliphatic, linear or branched dicarboxylic acids, cycloaliphatic dicarboxylic acids and aromatic dicarboxylic acids.

The dicarboxylic acid Y1 has in particular from 4 to 36 carbon atoms, preferably those having from 6 to 18 carbon atoms. When it is aliphatic, the dicarboxylic acid Y1 is preferably chosen from the aliphatic dicarboxylic acids described above. In an advantageous version, when it is aliphatic, the dicarboxylic acid Y1 is an aliphatic dicarboxylic acid chosen from adipic acid (6), decanedioic acid (10), dodecanedioic acid (12) and tetradecanedioic acid (14).

When it is cycloaliphatic, the dicarboxylic acid Y1 is preferably chosen from the cycloaliphatic dicarboxylic acids described above. 1,4-Cyclohexyldicarboxylic acid is an example of a cycloaliphatic dicarboxylic acid Y1.

When the dicarboxylic acid Y1 is aromatic, it is preferably chosen from terephthalic acid, isophthalic acid, furanedicarboxylic acid, and naphthalenic diacid, particularly preferably from terephthalic acid and isophthalic acid.

In one embodiment, the method comprises a step of preparing a cycloaliphatic polyamide block by polycondensation of a compound of formula (I), at least one cycloaliphatic diamine X1, at least one dicarboxylic acid Y1 and at least one monomer A1 chosen from an amino acid and a lactam.

Monomer A1 is preferably aliphatic.

The monomer A1 may be an aliphatic amino acid, in particular as defined above. Preferably, the repeating unit A1 is obtained from 11-aminoundecanoic acid (11).

The monomer A1 may be an aliphatic lactam, in particular as defined above. Preferably, the repeating unit A1 is obtained from caprolactam, oenantholactam or lauryllactam, in particular caprolactam (6) or lauryllactam (12).

* Preparation of a semi-aromatic polyamide block In one embodiment, the polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) is a semi-aromatic polyamide block. The method may then comprise a step of preparing a semi-aromatic polyamide block by polycondensation of a compound of formula (I) with one or more other aromatic comonomers, typically an aromatic dicarboxylic acid or an aromatic diamine, in particular an alkylaromatic diamine.

According to a first alternative, the preparation of the semi-aromatic polyamide block comprises the polycondensation of a compound of formula (I) with at least one alkylaromatic diamine X2 and one dicarboxylic acid Y2 chosen from linear or branched aliphatic dicarboxylic acids and cycloaliphatic dicarboxylic acids.

The alkylaromatic diamine X2 is preferably selected from 1,3-xylylenediamine (MXD), 1,4-xylylenediamine and their mixture.

The dicarboxylic acid Y2 has in particular from 4 to 36 carbon atoms, preferably those having from 6 to 18 carbon atoms. When it is aliphatic, the dicarboxylic acid Y2 is preferably chosen from the aliphatic dicarboxylic acids described above. In an advantageous version, when it is aliphatic, the dicarboxylic acid Y2 is an aliphatic dicarboxylic acid chosen from butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids, dimerized fatty acids.

When it is cycloaliphatic, the dicarboxylic acid Y2 is preferably selected from the cycloaliphatic dicarboxylic acids described above. 1,4-Cyclohexyldicarboxylic acid is an example of a cycloaliphatic dicarboxylic acid Y2.

In one embodiment, the method comprises a step of preparing a semi-aromatic polyamide block by polycondensation of a compound of formula (I) with at least one alkylaromatic diamine X2, with at least one dicarboxylic acid Y2 chosen from linear or branched aliphatic dicarboxylic acids and cycloaliphatic dicarboxylic acids, and with at least one monomer A2 chosen from an amino acid or at least one lactam.

Monomer A2 is preferably aliphatic.

The monomer A2 may be an aliphatic amino acid, in particular as defined above. Preferably, the repeating unit A2 is obtained from 11-aminoundecanoic acid (11).

The monomer A2 may be an aliphatic lactam, in particular as defined above. Preferably, the repeating unit A2 is obtained from caprolactam, oenantholactam or lauryllactam, in particular caprolactam (6) or lauryllactam (12).

According to a second alternative, the preparation of the semi-aromatic polyamide block comprises the polycondensation of a compound of formula (I) with at least one aliphatic, linear or branched or cycloaliphatic diamine X3 and an aromatic dicarboxylic acid Y3.

The aliphatic diamine X3 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.

When the diamine X3 is aliphatic, it is in particular as defined above.

When the diamine X3 is cycloaliphatic, it is in particular as defined above for the cycloaliphatic diamines X1. Advantageously, the cycloaliphatic diamine X3 is chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis(aminocyclohexyl)-methane (P), 1,3-bis(aminomethyl)cyclohexane (1,3-BAC) and isophoronediamine (IPD).

The aromatic dicarboxylic acid 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.

In one embodiment, the preparation of the semi-aromatic polyamide block comprises the polycondensation of a compound of formula (I) with at least one aliphatic, linear or branched or cycloaliphatic diamine X3, with an aromatic dicarboxylic acid Y3, and with at least one monomer A3 chosen from an amino acid or at least one lactam.

Monomer A3 is in particular as defined above for monomer A2.

[polyamide (PA) or polyether block amide (PEBA)]

According to a seventh subject, the invention relates to a polyamide (PA) or polyether block amide (PEBA) obtained by polycondensation of the compound according to the invention, optionally in the presence of one or more other comonomers.

The embodiments described above for the compound of formula (I) are of course applicable for the repeating unit derived from the compound of formula (I), and for the polyamide (PA) or polyether block amide (PEBA) comprising it. • Aliphatic polyamide

According to a first aspect of this seventh object, the polyamide is an aliphatic polyamide.

When the polyamide is an aliphatic polyamide, one or more other comonomers present during the polycondensation of the compound according to the invention are typically chosen from an aliphatic amino acid, an aliphatic lactam, or a mixture of at least one aliphatic diamine and at least one aliphatic dicarboxylic acid.

Two preferred alternatives of the aliphatic polyamide can be distinguished, depending on the alternative considered for the R ⁵ group of the compound of formula (I).

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et L² est un groupe divalent aliphatique comprenant de 4 à 36 atomes de carbone. According to a first alternative, the aliphatic polyamide is obtained by polycondensation of a compound of formula (II') as defined above with an aliphatic diamine of formula H2N-L ² -NH2 in which L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, said aliphatic polyamide then comprising a repeating unit of formula (XXI'):

wherein m, n, L, R ² , R ³ and R ⁴ are as defined above and L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms.

Preferably, L ² represents a group -(CH2) _P - in which p represents an integer from 4 to 36, in particular from 4 to 24, preferably from 5 to 12, the particularly preferred p being 4, 5, 6, 10 and 12. The group -NH-L2-NH- is then derived from a linear and aliphatic diamine.

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et R⁵ est choisi parmi un hydrogène, un hydroxyle, un alkyle comprenant de 1 à 4 atomes de carbone et un alcoxyle comprenant de 1 à 4 atomes de carbone. According to a second alternative for the aliphatic polyamide, the aliphatic polyamide is obtained by polycondensation of a compound of formula (I) in which R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms, the aliphatic polyamide comprising a repeating unit of formula (XXII):

wherein m, n, L, R ² , R ³ and R ⁴ are as defined above and R ⁵ is selected from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms.

dans laquelle q représente un nombre entier de 5 à 11 , de préférence 5, 10 ou 11. De manière particulièrement préférée, q est égal à n tel que défini ci-dessus, si bien que le groupe -CO-(CH2)_q-NH du motif répétitif de formule (XXIII) est identique au(x) groupe(s) - CO-(CH2)n-NH du motif répétitif de formule(XXI’) ou (XXII). Regardless of the alternative considered, the aliphatic polyamide generally comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), one or more other aliphatic unit(s). In addition to the repeating unit derived from the compound of formula (I) (typically in addition to the units of formula (XXI') or (XXII)), the aliphatic polyamide generally comprises one or more other unit(s), typically 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. If the aliphatic polyamide contains a unit obtained from the polycondensation of at least one aliphatic diamine and at least one aliphatic dicarboxylic acid, the diamine is preferably a primary diamine (two NH2 groups). In particular, the aliphatic polyamide may further comprise a repeating unit of formula (XXIII):

in which q represents an integer from 5 to 11, preferably 5, 10 or 11. Particularly preferably, q is equal to n as defined above, so that the group -CO-(CH2) _q -NH of the repeating unit of formula (XXIII) is identical to the group(s) -CO-(CH2)n-NH of the repeating unit of formula (XXI') or (XXII).

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.

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 p,p- dimethylpropriolactam, α,α-dimethylpropriolactam, amylolactam, caprolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam, the lactam preferably being caprolactam, oenantholactam and lauryllactam.

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 diamine include 1,4-diaminobutane, 1,5-diaminopentane, hexamethylenediamine, 1,10-decamethylenediamine, tetramethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 1,5-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, diamine polyols, methyl-pentamethylenediamine (MPMD), and trimethylhexamethylenediamine.

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 "Cargill", or under the brand name EMPOL by the company BASF, or under the brand name Radiacid by the company OLEON, and polyoxyalkylene α,β-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.

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.

Preferably, the aliphatic polyamide comprises, in addition to the repeating units derived from the compound 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 their mixtures, preferably repeating units chosen from the repeating units of PA 6, PA 11, PA 12, PA 6.10, PA 10.10, PA 10.12, PA 6/12, PA 11/12.

• Semi-aromatic polyamide

According to a second aspect of this seventh subject, the polyamide is semi-aromatic. When the polyamide is a semi-aromatic polyamide, one or more other comonomers present during the polycondensation of the compound according to the invention are typically one or more other aromatic comonomers.

Two preferred alternatives of the semi-aromatic polyamide can be distinguished, depending on the alternative considered for the R ⁵ group of the compound of formula (I).

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et L² est un groupe divalent aliphatique comprenant de 4 à 36 atomes de carbone. According to a first alternative, the semi-aromatic polyamide is obtained by polycondensation of a compound of formula (I) in which R ⁵ represents a group of formula (I') as defined above. The semi-aromatic polyamide is then obtained by polycondensation of a compound of formula (II') as defined above with an aliphatic diamine of formula H2N-L ² -NH2 in which L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, said semi-aromatic polyamide then comprising a repeating unit of formula (XXI'):

wherein m, n, L, R ² , R ³ and R ⁴ are as defined above and L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms.

Three alternatives are preferred for group L ² .

Preferably, according to a first alternative for the group L ² , L ² represents a group -(ChLjp- in which p represents an integer from 4 to 36, in particular from 4 to 24, preferably from 5 to 12, the particularly preferred p being 4, 5, 6, 10 and 12. The group -NH-L2-NH- is then derived from a linear and aliphatic diamine.

dans laquelle : According to a second alternative for the L ² group, the L ² group is a cycloaliphatic group comprising from 3 to 36 carbon atoms. For example, L ² has the following formula (L ² _cy cio):

in which:

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently represent a group selected from a hydrogen atom or an alkyl of 1 to 6 carbon atoms (provided that the sum of the carbon atoms of the group L ² is at most 36) and

- X represents either a single bond or a divalent group consisting of: a linear or branched aliphatic chain comprising from 1 to 10 carbon atoms, optionally substituted by cycloaliphatic or aromatic groups of 6 to 8 carbon atoms (provided that the sum of the carbon atoms of the L ² group is at most 36), or a cycloaliphatic group of 6 to 12 carbon atoms (provided that the sum of the carbon atoms of the L ² group is at most 36).

Typically, the -NH-L2-NH- group is then derived from a cycloaliphatic diamine 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, bis-(3-methyl-4-aminocyclohexyl)-methane or 3’-dimethyl-4,4’-diamino-dicyclohexyl-methane (BMACM, MACM or B), bis-(4-aminocyclohexyl)-methane (BACM), p-bis(aminocyclohexyl)-methane (PACM or P), isopropylidenedi(cyclohexylamine) (PACP) and 2-2-bis-(3-methyl-4-aminocyclohexyl)-propane (BMACP), isophorone-diamine (IPDA or IPD), and 1,3-bis(aminomethyl)cyclohexane (1,3-BAC).

According to a third alternative for the ^L2 group, the ^L2 group is an aromatic or alkylaromatic group, preferably an unsubstituted phenylene or substituted by one or more alkyls comprising independently from 1 to 6, in particular from 1 to 3 carbon atoms. Preferably, the -NH-L2-NH- group is then -NH-Ph-NH- where Ph is a phenyl and the -NHs are in the ortho, meta or para position to each other.

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et R⁵ est choisi parmi un hydrogène, un hydroxyle, un alkyle comprenant de 1 à 4 atomes de carbone et un alcoxyle comprenant de 1 à 4 atomes de carbone. According to a second alternative, the semi-aromatic polyamide is obtained by polycondensation of a compound of formula (I) in which R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms, the semi-aromatic polyamide comprising a repeating unit of formula (XXII):

wherein m, n, L, R ² , R ³ and R ⁴ are as defined above and R ⁵ is selected from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms.

Whatever the alternative considered, the semi-aromatic polyamide generally comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), one or more other unit(s), preferably units derived from aromatic diamine or dicarboxylic acid.

According to a first alternative, the semi-aromatic polyamide is derived from an alkylaromatic diamine. In addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), the semi-aromatic 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.

The embodiments described above for the alkylaromatic diamine X2 and for the dicarboxylic acid Y2 are also applicable for the repeating unit X2.Y2 which is derived therefrom.

Preferably, the semi-aromatic polyamide comprises, in addition to the repeating units derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), repeating units chosen from the repeating units of a PA chosen from MXD6 and MXD10.

According to a second alternative, the semi-aromatic polyamide is derived from an aromatic dicarboxylic acid. In addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), the semi-aromatic 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.

The embodiments described above for the diamine X3 and for the aromatic dicarboxylic acid Y3 are also applicable for the repeating unit X3.Y3 which is derived therefrom. Preferably, the semi-aromatic polyamide comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), repeating units chosen from the repeating units of a PA chosen from PA 6T, PA 9T, PA 10T and PA 12T.

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.

Whatever the alternative considered, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and the repeating unit X2.Y2 and/or the repeating unit X3.Y3 defined above, the semi-aromatic polyamide may comprise an aliphatic repeating unit A chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam.

The embodiments described above for the amino acid or lactam monomer A are also applicable for the repeating unit A derived therefrom.

For example, the semi-aromatic polyamide comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), repeating units chosen from the repeating units of a PA 11/MXD.10.

For example, the semi-aromatic polyamide comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), repeating units A/X3.Y3 chosen from:

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

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.I, 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. According to a third alternative, the semi-aromatic polyamide is derived from an alkylaromatic diamine and an aromatic dicarboxylic acid. For example, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), the semi-aromatic 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 diacids, and

- 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.

• Transparent polyamide

According to a third aspect of this seventh object, the polyamide is transparent.

* Transparent polyamide X1 .Y 1

In particular, the invention relates to a transparent polyamide obtained by polycondensation of the compound of formula (I) according to the invention, of at least one cycloaliphatic diamine X1 and of at least one dicarboxylic acid Y1. It then comprises, in addition to the repeating unit derived from the compound of formula (I), a repeating unit X1.Y1 derived from the polycondensation of the cycloaliphatic diamine X1 and the dicarboxylic acid Y1.

The embodiments described above for the compound of formula (I) are of course applicable for the repeating unit derived from the compound of formula (I), and for the transparent polyamide comprising it. Similarly, the embodiments described above for the cycloaliphatic diamine X1 and for the dicarboxylic acid Y1 are also applicable for the repeating unit X1.Y1 derived therefrom.

Two preferred alternatives of the transparent polyamide can be distinguished, depending on the alternative considered for the R ⁵ group of the compound of formula (I).

dans laquelle : m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus, et According to a first alternative, the transparent polyamide is obtained by polycondensation of a compound of formula (I) in which R ⁵ represents a group of formula (I') as defined above. The transparent polyamide is then obtained by polycondensation of a compound of formula (II') as defined above with an aliphatic diamine of formula H2N-L ² -NH2 in which L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, and, when L ² is not a divalent cycloaliphatic group, with at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1, said transparent polyamide then comprising a repeating unit of formula (XXI'):

in which: m, n, L, R ² , R ³ and R ⁴ are as defined above, and

L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, it being understood that when L ² is not a divalent cycloaliphatic group, then the transparent 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.

Two alternatives can be distinguished depending on whether the ^L2 group is cycloaliphatic or not.

According to a first alternative for the group L ² of the formula (XXI'), L ² is a divalent cycloaliphatic group. The transparent polyamide is then obtained by polycondensation of a compound of formula (II') as defined above with an aliphatic diamine of formula H2N-L ² -NH2 in which L ² is a divalent cycloaliphatic group comprising from 4 to 36 carbon atoms, said transparent polyamide comprising a repeating unit of formula (XXI') as defined above. Since the group L ² is itself cycloaliphatic, the transparent polyamide may be free of any repeating unit other than that of formula (XXI'), or comprise one or more other repeating units, which may be cycloaliphatic (in particular the unit X1.Y1 as defined above) or not. The polyamide may be free of or 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.

Preferably, in this first alternative for the ^L2 group, the ^L2 group is a cycloaliphatic group comprising from 3 to 36 carbon atoms.

Preferably, in formula (XXI'), the group -NH-L2-NH- is derived from a cycloaliphatic diamine 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-dicyclohexyl-methane (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.

dans laquelle : Typically, in formula (XXI'), L ² corresponds to the following formula (L ² _cy cio):

in which:

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently represent a group selected from a hydrogen atom or an alkyl of 1 to 6 carbon atoms (provided that the sum of the carbon atoms of the group L ² is at most 36) and

- X represents either a single bond or a divalent group consisting of: a linear or branched aliphatic chain comprising from 1 to 10 carbon atoms, optionally substituted by cycloaliphatic or aromatic groups of 6 to 8 carbon atoms (provided that the sum of the carbon atoms of the L ² group is at most 36), or a cycloaliphatic group of 6 to 12 carbon atoms (provided that the sum of the carbon atoms of the L ² group is at most 36).

For example, in formula (XXI’), the group -NH-L2-NH- is derived from a cycloaliphatic diamine 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, bis-(3-methyl-4-aminocyclohexyl)-methane or 3’-dimethyl-4,4’-diamino-dicyclohexyl-methane (BMACM, MACM or B), bis-(4-aminocyclohexyl)-methane (BACM), p-bis(aminocyclohexyl)-methane (PACM or P), isopropylidenedi(cyclohexylamine) (PACP) and 2-2-bis-(3-methyl-4-aminocyclohexyl)-propane (BMACP), 1,3-bis(aminomethyl)cyclohexane (1,3-BAC) and isophorone-diamine (IPDA or IPD).

According to a second alternative for the group L ² of the formula (XXI'), L ² is not cycloaliphatic. The transparent polyamide is obtained by polycondensation of a compound of formula (II') as defined above with an aliphatic diamine of formula H2N-L ² - NH2 in which L ² is a divalent aliphatic group, not being cycloaliphatic, and comprising from 4 to 36 carbon atoms, with at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1, said transparent polyamide comprising: a repeating unit of formula (XXI') as defined above, and 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.

Preferably, in this second alternative, in formula (XXI'), L ² represents a group -(CH2) _P - in which p represents an integer from 4 to 36, in particular from 4 to 24, preferably from 5 to 12, the particularly preferred p being 4, 5, 6, 10 and 12. The group -NH-L2-NH- then comes from a linear and aliphatic diamine. In this second alternative for the group L ² , the transparent polyamide 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.

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et R⁵ est choisi parmi un hydrogène, un hydroxyle, un alkyle comprenant de 1 à 4 atomes de carbone et un alcoxyle comprenant de 1 à 4 atomes de carbone, et au moins un motif répétitif X1.Y1 obtenu à partir de la polycondensation d'au moins une diamine cycloaliphatique X1 et d'au moins un acide dicarboxylique Y1. According to a second alternative, the transparent polyamide is obtained by polycondensation of a compound of formula (I) in which R ⁵ is chosen from a hydrogen, a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms and an alkoxyl comprising from 1 to 4 carbon atoms with at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1, the transparent polyamide comprising: a repeating unit of formula (

in which m, n, L, R ² , R ³ and R ⁴ are as defined above and R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms, and 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.

Whatever the alternative/embodiment considered, the transparent polyamide generally comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII) defined above), one or more other unit(s), and in particular an X1.Y1 unit as defined above.

In particular, the invention relates to a transparent polyamide obtained by polycondensation of the compound of formula (I) according to the invention, of at least one cycloaliphatic diamine X1 and of at least one dicarboxylic acid Y1.

Preferably, the transparent polyamide comprises, in addition to the repeating units derived from the compound 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, PA PACM.18, MACM.I, MACM.T and a mixture of these, e.g. PA MACM.I/MACM.T.

In a particularly preferred manner, the polyamide comprises, in addition to the repeating units derived from the compound of formula (I), repeating units chosen from the repeating units of a PA chosen from MACM.10, PA MACM.12, and PA MACM.14.

Preferably, the polyamide comprising the repeating unit derived from the compound of formula

(I) and the repeating unit X1.Y1 is amorphous.

* Transparent copolyamide A/X1.Y 1

In one embodiment, the transparent polyamide is obtained by polycondensation of the compound of formula (I) according to the invention, of at least one cycloaliphatic diamine X1, of at least one dicarboxylic acid Y1 and of at least one monomer A chosen from an amino acid and a lactam.

The embodiments described above for monomer A are applicable.

The transparent polyamide therefore comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), at least one repeating unit X1.Y 1 and at least one repeating unit A 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 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.

(I I).

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

Advantageously, the type A units are PA 11 (polyundecanamide), PA 12 (polydodecanamide) or PA 6 (polycaprolactam) units.

Preferably, the polyamide comprises, in addition to the repeating unit derived from the compound 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.

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.

Preferably, the polyamide comprises, in addition to the repeating unit derived from the compound 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, PA 10.10/PACM.10, PA 10.10/MACM.12, PA 10.10/PACM.12, PA 10.10/MACM.14, PA 10.10/PACM.14, PA 10.10/MACM.18, PA 10.10/PACM.18, PA 10.12/MACM.10, PA 10.12/PACM.10, PA 10.12/MACM.12, PA 10.12/PACM.12, PA 10.12/MACM.14, PA 10.12/PACM.14, PA 10.12/MACM.18, AP 10.12/PACM.18, AP 12.10/MACM.10, PA 12.10/PACM.10, PA 12.10/MACM.12, PA 12.10/PACM.12, PA 12.10/MACM.14, PA 12.10/PACM.14, PA 12.10/MACM.18, PA 12.10/PACM.18, PA 12.12/MACM.10, PA 12.12/PACM.10, PA 12.12/MACM.12, PA 12.12/PACM.12, PA 12.12/MACM.14, PA 12.12/PACM.14, PA 12.12/MACM.18, PA 12.12/PACM.18, 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, the PA PACM.10/MACM.10, the 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 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 11/IPD.14, PA 12/BMACM.14, PA 12/PACM.14, and PA 12/1 PD.14.

Preferably, the polyamide comprises, in addition to the repeating unit derived from the compound 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.

The polyamide comprising the repeating unit derived from the compound of formula (I), the unit A and the unit X1.Y1 may be amorphous or semi-crystalline, and is preferably amorphous. The transparent polyamide according to the invention generally has a transmittance greater than 80%, advantageously greater than 85%, in particular greater than or equal to 90%.

In one embodiment, the transparent polyamide according to the invention has a Haze value of less than 15%, advantageously less than 10%, preferably less than 5%.

The embodiments described below are applicable for any polyamide according to the invention (in particular whether it is transparent, aliphatic or semi-crystalline).

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.

Advantageously, the polyamide is classified V0 in the UL94-vertical burning test, in particular for a test with a 1.6 mm thick polyamide sample.

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

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.

The polydispersity index IP of the polyamide is generally 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.

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.

The absolute value of the difference between the total acidity and the total basicity of the polyamide is preferably between 0 and 200 peq/g.

Preferably, the aliphatic polyamide has an inherent viscosity of between 0.40 and 1.70, advantageously between 0.70 and 1.50. Preferably, the semi-aromatic polyamide has an inherent viscosity of between 0.30 and 1.70. Preferably, the transparent polyamide has an inherent viscosity of between 0.40 and 1.70.

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

Polyamide can be amorphous or semi-crystalline.

• PEBA

According to a fourth aspect of this seventh subject, the invention relates to a polyether block amide (PEBA) resulting from the polycondensation: of one or more polyamides having diamine or dicarboxylic acid chain ends and obtained by polycondensation of a compound of formula (I), 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.

The polyamide(s) obtained by polycondensation of a compound of formula (I) is (are) useful as polyamide block(s) for the preparation of PEBA.

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 is derived from a polyamide obtained by polycondensation of a compound of formula (I).

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.

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.

Polyether blocks can also be made up of ethoxylated primary amines. Examples of ethoxylated primary amines include the products of formula (XXX):

H - (OCH ₂ CH ₂ ) _m — N — (CH ₂ CH ₂ O) _n — H

(CH ₂ ) _X

^CH 3 (XXX) 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.

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).

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.

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 (or "triblock"), which results from the condensation of several of the blocks described above. Said triblock 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.

Preferably, the PEBA results from one of the polycondensations according to one of the three alternatives described above for the process for preparing a PEBA. Thus, preferably, the PEBA results from one of the polycondensations according to one of the following three alternatives.

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.

According to a second alternative, PEBA results from 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.

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.

PEBA is then a polyetheresteramide.

The embodiments described above for the compound of formula (I) are of course applicable for the repeating unit derived from the compound of formula (I) of the polyamide block (or at least one block or each block if the PEBA comprises several) of the PEBA, and for the PEBA comprising it.

Two preferred alternatives of the (or each when there are several) polyamide block of PEBA can be distinguished, depending on the alternative considered for the R ⁵ group of the compound of formula (I).

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et L² est un groupe divalent aliphatique comprenant de 4 à 36 atomes de carbone. According to a first alternative, the polyamide block of the PEBA is obtained by polycondensation of a compound of formula (I) in which the group R ⁵ has the formula (I'). The polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) is then obtained by polycondensation of a compound of formula (II') as defined above with an aliphatic diamine of formula H2N-L ² -NH2 in which L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, said polyamide block then comprising a repeating unit of formula (XXI'):

wherein m, n, L, R ² , R ³ and R ⁴ are as defined above and L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms.

Two alternatives are preferred for group L ² .

dans laquelle : Preferably, according to a first alternative for the group L ² , L ² represents a group -(CH2) _P - in which p represents an integer from 4 to 36, in particular from 4 to 24, preferably from 5 to 12, the particularly preferred p being 4, 5, 6, 10 and 12. The group -NH-L2-NH- then comes from a linear and aliphatic diamine. According to a second alternative for the L ² group, the L ² group is a cycloaliphatic group comprising from 3 to 36 carbon atoms. For example, L ² has the following formula (L ² _cy cio):

in which:

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently represent a group selected from a hydrogen atom or an alkyl of 1 to 6 carbon atoms (provided that the sum of the carbon atoms of the group L ² is at most 36) and

- X represents either a single bond or a divalent group consisting of: a linear or branched aliphatic chain comprising from 1 to 10 carbon atoms, optionally substituted by cycloaliphatic or aromatic groups of 6 to 8 carbon atoms (provided that the sum of the carbon atoms of the L ² group is at most 36), or a cycloaliphatic group of 6 to 12 carbon atoms (provided that the sum of the carbon atoms of the L ² group is at most 36).

Typically, the -NH-L2-NH- group is then derived from a cycloaliphatic diamine 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, bis-(3-methyl-4-aminocyclohexyl)-methane or 3’-dimethyl-4,4’-diamino-dicyclohexyl-methane (BMACM, MACM or B), bis-(4-aminocyclohexyl)-methane (BACM), p-bis(aminocyclohexyl)-methane (PACM or P), isopropylidenedi(cyclohexylamine) (PACP) and 2-2-bis-(3-methyl-4-aminocyclohexyl)-propane (BMACP), 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), and isophorone-diamine (IPDA or IPD).

According to a second alternative, the polyamide block of PEBA is obtained by polycondensation of a compound of formula (I) in which the group R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms.

dans laquelle m, n, L, R², R³ et R⁴ sont tels que définis ci-dessus et R⁵ est choisi parmi un hydrogène, un hydroxyle, un alkyle comprenant de 1 à 4 atomes de carbone et un alcoxyle comprenant de 1 à 4 atomes de carbone. The polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) is then obtained by polycondensation of a compound of formula (I) in which R ⁵ is chosen from a hydrogen, a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms and an alkoxyl comprising from 1 to 4 carbon atoms of carbon, the polyamide block (or at least one polyamide block or each polyamide block if the PEBA comprises several) comprising a repeating unit of formula (XXII):

wherein m, n, L, R ² , R ³ and R ⁴ are as defined above and R ⁵ is selected from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms.

Whatever the alternative considered, the polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) generally comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), one or more other unit(s) derived from one or more other (co)monomer(s).

* PEBA comprising one or more aliphatic polyamide blocks

The polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) may be an aliphatic polyamide block.

The polyamide block of PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) can be obtained by polycondensation of the compound of formula (I) in the presence of one or more other comonomers chosen from an aliphatic amino acid, an aliphatic lactam, or a mixture of at least one aliphatic diamine and at least one aliphatic dicarboxylic acid.

In addition to the repeating unit derived from the compound of formula (I) (typically in addition to the units of formula (XXI') or (XXII)), the polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) may comprise one or more other unit(s) 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. If the polyamide block (or if at least one block or if each block if the PEBA comprises several) contains a unit obtained from the polycondensation of at least one aliphatic diamine and at least one aliphatic dicarboxylic acid, the diamine is preferably a primary diamine (two NH2 groups). Aliphatic amino acid, aliphatic lactam, aliphatic diamine and aliphatic dicarboxylic acid are in particular as defined above.

dans laquelle q représente un nombre entier de 5 à 11 , de préférence 5, 10 ou 11. De manière particulièrement préférée, q est égal à n tel que défini ci-dessus, si bien que le groupe -CO-(CH2)_q-NH du motif répétitif de formule (XXIII) est identique au(x) groupe(s) - CO-(CH2)n-NH du motif répétitif de formule(XXI’) ou (XXII). In particular, the polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) may further comprise a repeating unit of formula (XXIII):

in which q represents an integer from 5 to 11, preferably 5, 10 or 11. Particularly preferably, q is equal to n as defined above, so that the group -CO-(CH2) _q -NH of the repeating unit of formula (XXIII) is identical to the group(s) -CO-(CH2)n-NH of the repeating unit of formula (XXI') or (XXII).

Preferably, the polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) comprises, in addition to the repeating units derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), 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, PA 10.12, PA 6/12, PA 11/12.

Particularly preferred PEBAs are copolymers comprising:

- at least one polyamide PA 11 block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PEG block;

- at least one polyamide PA 11 block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PTMG block;

- at least one polyamide PA 12 block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PEG block;

- at least one polyamide PA 12 block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PTMG block;

- at least one polyamide PA 6.10 block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PEG block; - at least one polyamide PA 6.10 block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PTMG block;

- at least one polyamide PA 6 block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PEG block;

- at least one polyamide PA 6 block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PTMG block;

- at least one polyamide PA 6/12 block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PEG block;

- at least one PA 6/12 polyamide block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PTMG block;

- at least one polyamide PA 11/12 block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PEG block;

- at least one PA 11/12 polyamide block comprising a repeating unit derived from a compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and at least one PTMG block.

* PEBA comprising one or more cycloaliphatic polyamide blocks X1.Y1

The polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) may be a cycloaliphatic polyamide block.

The polyamide block of PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) can be obtained by polycondensation of the compound of formula (I), at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1.

The cycloaliphatic polyamide block of the PEBA (or at least one cycloaliphatic polyamide block or each cycloaliphatic polyamide block if the PEBA comprises several) therefore comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), at least one repeating unit X1.Y1 derived from the polycondensation of the cycloaliphatic diamine X1 and the dicarboxylic acid Y1. The embodiments described above for the cycloaliphatic diamine X1 and for the dicarboxylic acid Y1 are also applicable for the repeating unit X1.Y1 which is derived therefrom.

Preferably, the polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) comprises, in addition to the repeating units derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), 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.

In a particularly preferred manner, the polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) comprises, in addition to the repeating units derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), repeating units chosen from the repeating units of a PA chosen from MACM.10, PA MACM.12, and PA MACM.14.

Preferably, the polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) comprising the repeating unit derived from the compound of formula (I) and the repeating unit X1.Y1 is amorphous.

In one embodiment, the cycloaliphatic polyamide block (or at least one polyamide block or each polyamide block if the PEBA comprises several) is obtained by polycondensation of the compound of formula (I), at least one cycloaliphatic diamine X1, at least one dicarboxylic acid Y1 and at least one monomer A1 chosen from an amino acid and a lactam.

The cycloaliphatic polyamide block of the PEBA (or at least one cycloaliphatic polyamide block or each cycloaliphatic polyamide block if the PEBA comprises several) therefore comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), at least one repeating unit X1.Y1 and at least one repeating unit A1 chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam.

The embodiments described above for monomer A1 are applicable.

The amino acid is in particular as defined above. Preferably, the amino acid is 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 A1 is obtained from 11-aminoundecanoic acid (11).

The lactam is in particular as defined above, and is preferably caprolactam (6) or lauryllactam (12). Advantageously, the units of type A1 are units of PA 11 (polyundecanamide), PA 12 (polydodecanamide) or PA 6 (polycaprolactam).

Preferably, the cycloaliphatic polyamide block (or at least one cycloaliphatic polyamide block or each cycloaliphatic polyamide block if the PEBA comprises several) comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), 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.

More particularly preferably, the repeating unit A1 is obtained from a single amino acid or a single lactam. However, it is entirely possible to envisage using, to obtain this same unit A1, 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.

Preferably, the cycloaliphatic polyamide block (or at least one cycloaliphatic polyamide block or each cycloaliphatic polyamide block if the PEBA comprises several) comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), 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, PA 10.10/PACM.10, PA

10.10/MACM.12, PA 10.10/PACM.12, PA 10.10/MACM.14, PA 10.10/PACM.14, PA 10.10/MACM.18, PA 10.10/PACM.18, PA 10.12/MACM.10, PA 10.12/PACM.10, PA 10.12/MACM.12, PA 10.12/PACM.12, PA 10.12/MACM.14, PA 10.12/PACM.14, PA 10.12/MACM.18, PA 10.12/PACM.18, PA 12.10/MACM.10, PA 12.10/PACM.10, PA 12.10/MACM.12, PA 12.10/PACM.12, PA 12.10/MACM.14, PA 12.10/PACM.14, PA 12.10/MACM.18, PA 12.10/PACM.18, PA 12.12/MACM.10, PA 12.12/PACM.10, PA 12.12/MACM.12, PA 12.12/PACM.12, PA 12.12/MACM.14, PA 12.12/PACM.14, PA 12.12/MACM.18, PA 12.12/PACM.18, 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 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, PA 11/IPD.10, PA 12/BMACM.10, PA 12/IPD.10, PA 11/BMACM.14, PA 11/1 PD.14, PA 12/BMACM.14, PA 12/PACM.14, and PA 12/1 PD.14.

Preferably, the cycloaliphatic polyamide block (or at least one cycloaliphatic polyamide block or each cycloaliphatic polyamide block if the PEBA comprises several) comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), 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.

The cycloaliphatic polyamide block (or at least one cycloaliphatic polyamide block or each cycloaliphatic polyamide block if the PEBA comprises several) comprising the repeating unit derived from the compound of formula (I), the unit A1 and the unit X1.Y1 may be amorphous or semi-crystalline, and is preferably amorphous.

* PEBA comprising one or more semi-aromatic polyamide blocks.

The polyamide block of the PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) may be a semi-aromatic polyamide block.

The polyamide block of PEBA (or at least one polyamide block or each polyamide block if the PEBA comprises several) can be obtained by polycondensation of the compound of formula (I) with one or more other aromatic comonomers, typically an aromatic diamine, in particular an alkylaromatic diamine, or an aromatic dicarboxylic acid.

According to a first alternative, the semi-aromatic polyamide block of the PEBA (or at least one semi-aromatic polyamide block or each semi-aromatic polyamide block if the PEBA comprises several) is derived from an alkylaromatic diamine. In addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), the semi-aromatic polyamide block (or at least one semi-aromatic polyamide block or each semi-aromatic polyamide block if the PEBA comprises several) 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 the acids aliphatic, linear or branched dicarboxylic acids and cycloaliphatic dicarboxylic acids.

The embodiments described above for the alkylaromatic diamine X2 and for the dicarboxylic acid Y2 are also applicable for the repeating unit X2.Y2 which is derived therefrom.

Preferably, the semi-aromatic polyamide block of the PEBA (or at least one semi-aromatic polyamide block or each semi-aromatic polyamide block if the PEBA comprises several) comprises, in addition to the repeating units derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), repeating units chosen from the repeating units of a PA chosen from MXD6 and MXD10.

According to a second alternative, the semi-aromatic polyamide block of the PEBA (or at least one semi-aromatic polyamide block or each semi-aromatic polyamide block if the PEBA comprises several) is derived from an aromatic dicarboxylic acid. In addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), the semi-aromatic polyamide block of the PEBA (or at least one semi-aromatic polyamide block or each semi-aromatic polyamide block if the PEBA comprises several) 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.

The embodiments described above for the diamine X3 and for the aromatic dicarboxylic acid Y3 are also applicable for the repeating unit X3.Y3 which is derived therefrom.

Preferably, the semi-aromatic polyamide block of the PEBA (or at least one semi-aromatic polyamide block or each semi-aromatic polyamide block if the PEBA comprises several) comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), repeating units chosen from the repeating units of a PA chosen from PA 6T, PA 9T, PA 10T and PA 12T.

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.

Whichever alternative is considered, in addition to the repeating unit from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)) and the unit repeating unit X2.Y2 and/or the repeating unit X3.Y3 defined above, the semi-aromatic polyamide block of the PEBA (or at least one semi-aromatic polyamide block or each semi-aromatic polyamide block if the PEBA comprises several) may comprise an aliphatic repeating unit A2 or A3 respectively chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam.

The embodiments described above for the amino acid or lactam monomer A2 or A3 are also applicable for the repeating unit A2 or A3 derived therefrom.

For example, the semi-aromatic polyamide block of the PEBA (or at least one semi-aromatic polyamide block or each semi-aromatic polyamide block if the PEBA comprises several) comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), repeating units chosen from the repeating units of a PA 11/MXD.10.

For example, the semi-aromatic polyamide block of the PEBA (or at least one semi-aromatic polyamide block or each semi-aromatic polyamide block if the PEBA comprises several) comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), repeating units A3/X3.Y3 chosen from:

A3/6T, A3/9T, A3/10T and A3/11T, A3 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

A3/X3.Y3 in which X3 is BMACM, PACM or IPD and Y3 is T or I and A3 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.I, 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.

According to a third alternative, the semi-aromatic polyamide block of the PEBA (or at least one semi-aromatic polyamide block or each semi-aromatic polyamide block if the PEBA comprises several) is derived from an alkylaromatic diamine and an aromatic dicarboxylic acid. For example, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII)), the semi-aromatic polyamide block of the PEBA (or at least one semi-aromatic polyamide block or each semi-aromatic polyamide block if the PEBA includes several) may include:

- 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 diacids, and

- 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 embodiments described below are applicable to any PEBA according to the invention.

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%. The mass proportion of atomic phosphorus can be determined by X-ray fluorescence.

Advantageously, PEBA is classified V0 in the UL94-vertical burning test, in particular for a test with a PEBA sample 1.6 mm thick.

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.

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.

The number-average molar mass is usually set by the chain limiter content. It can be calculated according to the relationship Mn ^— nmonomer X Mwrepeating unit / chain limiter + Mwichain limiter

In this formula, n _monomer represents the number of moles of monomer, n chain limiter represents the number of moles of excess chain limiter, MW repeating _unit represents the molar mass of the repeating unit, and MWhchain limiter represents the molar mass of the excess chain limiter.

The polydispersity index IP of the polyamide block (or of at least one polyamide block or of each polyamide block if the PEBA comprises several) is generally 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.

The polydispersity index IP of the polyamide block (or of at least one polyamide block or of each polyamide block if the PEBA comprises several) is generally greater than or equal to 1.0, in particular greater than or equal to 2.0.

Preferably, the PEBA has an inherent viscosity of between 1.10 and 2.00.

PEBA can be amorphous or semi-crystalline.

The embodiments described below are applicable for any PEBA or any polyamide according to the invention (in particular whether it is aliphatic, semi-crystalline or transparent).

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

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

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.

The flame retardants are chosen in particular from DOPO and its derivatives, melamine cyanurate, melamine polyphosphate, red phosphorus, metal dialkylphosphinates and mixtures thereof.

To the extent that the polyamides according to the invention and the PEBAs according to the invention are self-flame retardant, they may be free of flame retardant agent (used as an additive).

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 allows it to react with the amide, amine or carboxylic acid functions of the polyamide or PEBA. 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 or PEBA may comprise an impact modifier, in particular of an elastomeric nature and preferably functionalized by maleic anhydride.

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.

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.

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.

The mass proportion of the fillers is in particular 0.5 to 50.0% relative to the weight of the polyamide or PEBA.

The mass proportion of reinforcing fibers is in particular 5 to 75% relative to the weight of polyamide or PEBA.

The mass proportion of additives is in particular 0.05 to 3.00% relative to the weight of polyamide or PEBA.

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

[Use of PA or PEBA]

According to an eighth subject, the invention relates to the use of the polyamide defined above or of the PEBA defined above as a flame retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof.

[Process of preparing an article] According to a ninth 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. 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 the 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. These sporting goods include sports footwear components, sports utensils such as ice skates or other winter sports and mountaineering articles, ski bindings, snowshoes, sports bats, boards, horseshoes, flippers, golf balls, recreational vehicles, particularly those intended for cold weather activities. Mention may also be made, in general, of leisure and DIY articles, road tools and equipment subject to climatic and mechanical aggression, protective articles, such as helmet visors, glasses, as well as the arms of glasses. Non-limiting examples include car components such as headlight guards, rearview mirrors, small parts for off-road vehicles, tanks, in particular, for mopeds, motorcycles, scooters, subject to mechanical and chemical attack, screws, cosmetic items subject to mechanical and chemical attack, lipsticks, pressure gauges, aesthetic protection elements such as gas bottles. Mention may also be made of objects or parts of objects for electronics requiring compliance with dimensions, for example parts for mobile phones, computers, tablets, etc.

[Article]

According to a tenth subject, the invention relates to the article comprising the polyamide as defined above or the PEBA as defined above, or the polyamide capable of being obtained by the process described above or the PEBA capable of being obtained by the process described above.

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

Example 1: Preparation of compound of formula (1) 2.0 equivalents of 11-aminoundecanoic acid and 1.0 equivalent of terephthalaldehyde are added to a glass reactor equipped with mechanical stirring and a condenser. Absolute ethanol is added to the reactor so as to have a concentration of 25 g/L of terephthalaldehyde in ethanol. The reaction medium is heated to 90°C, i.e. reflux of ethanol, and left stirring for 1 h. The reaction medium is then cooled to 60°C and 2.0 equivalents of DOPO are added. The reaction is continued with stirring for 8 h. At the end of the reaction, the reaction medium is cooled to room temperature (20°C) until a white precipitate appears. The reaction medium is filtered and the solid is rinsed with ethanol and then dried under vacuum at 60°C.

A compound of the following formula was thus prepared:

Example 2: preparation of aliphatic polyamide by polycondensation of a compound of formula (1) and properties of the aliphatic polyamide obtained

Polyamides labeled A and B are 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 heated to 260 degrees centigrade, while maintaining stirring. The reaction medium is maintained at 260 degrees centigrade, under autogenous pressure for 1 hour 30 minutes. Then, the reactor is released to atmospheric pressure while maintaining the temperature at 260 degrees centigrade. A nitrogen flushing phase is carried out for 1 hour before emptying the reactor.

The properties of polyamide are given in Tables 2 and 3. Example 3: Preparation of a compound of formula (I)

2.0 equivalents of 11-aminoundecanoic acid and 1.0 equivalent of terephthalaldehyde are added to a glass reactor equipped with mechanical stirring and a condenser. Absolute ethanol is added to the reactor so as to have a concentration of 25 g/L of terephthalaldehyde in ethanol. The reaction medium is heated to 80°C, i.e. reflux of ethanol, and left stirring for 3 hours. 2.0 equivalents of DPPO (diphenylphosphine oxide) are then added. The reaction is continued with stirring for 8 hours. At the end of the reaction, the reaction medium is cooled with an ice bath until a white precipitate appears. The reaction medium is filtered and the solid is rinsed with cold isopropanol and then dried under vacuum at 60°C.

A compound of the following formula (2) was thus prepared:

Example 4: preparation of aliphatic polyamide by polycondensation of the compound of formula (2) and properties of the aliphatic polyamide obtained

Polyamide C 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 heated to 200 degrees centigrade, while maintaining stirring. The reaction medium is maintained at 200 degrees centigrade, under autogenous pressure for 1 hour 30 minutes. Then, the reactor is released to atmospheric pressure while maintaining the temperature at 200 degrees centigrade. A nitrogen flushing phase is carried out for 1 hour before emptying the reactor.

The properties of polyamide are given in Table 2.

Example 5 (comparative): preparation of a phosphorus monomer not included in formula (I)

2.0 equivalents of vanillin and 1.0 equivalent of p-phenylenediamine are added to a glass reactor equipped with mechanical stirring and a condenser. Absolute ethanol is added to the reactor to give a concentration of 71 g/L of p-phenylenediamine. in ethanol. The reaction medium is heated to 40°C for 1 hour. 0.055 equivalents of ZnCh and 2.00 equivalents of dimethyl phosphonate are then added. The reaction is continued with stirring at 80°C for 3 hours. At the end of the reaction, the solvent is evaporated, an orange solid is recovered and this is then dried under vacuum at 60°C. A compound of the following formula (3) was thus prepared:

Example 6 (comparative): Test of preparation of an aliphatic polymer by polycondensation of a compound of formula (3) and properties of the polymer obtained

Polymer D 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 heated to 240 degrees centigrade, while maintaining stirring. The reaction medium is maintained at 240 degrees centigrade, under autogenous pressure for 1 hour 30 minutes. Then, the reactor is released to atmospheric pressure while maintaining the temperature at 240 degrees centigrade. A nitrogen flushing phase is carried out for 1 hour before emptying the reactor.

The polymer properties are provided in Table 2.

[Table 1]

Table 1: Natures and proportions of monomers for the preparation of polymers

The inherent viscosity of the compositions obtained after polymerization was tested according to the method described above and is provided in Table 2.

Table 2: Inherent viscosity of the compositions obtained after polymerization

Tableau 3 : propriétés feu des polyamides The inherent viscosity of polymer D is less than 0.5. It is therefore not a polyamide within the meaning of the invention. Such a low viscosity value indicates that polymerization has not taken place or at least that it is insufficient. The different polyamides were characterized according to the UL94 standard in vertical combustion on injected specimens with a thickness of 1.6 mm, and their combustion times were determined. The combustion times are provided in Table 3. [Table 3]

Table 3: Fire properties of polyamides

Claims

1. Compound of the following formula (I):

in which: R ¹ represents H, a linear, branched or cyclic alkyl group comprising from 1 to 12 carbon atoms, or a cation, n represents an integer from 5 to 11, R ² and R ³ independently represent hydrogen, hydroxyl, alkoxyl comprising from 1 to 2 carbon atoms, a group -Ph, -Ph-Ph or -O-Ph, where Ph is phenyl optionally substituted by hydroxyl, provided that when R ² and R ³ each represent a group -Ph or -O-Ph, R ² and R ³ may be joined together to together form a biphenyl group, m represents an integer from 0 to 4, each R ⁴ is independently selected from hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms, L is a single bond or phenylene optionally substituted by one or more substituents chosen from hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms, R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms, alkoxyl comprising from 1 to 4 carbon atoms and a group of formula (I'):

in which n, R ¹ , R ² and R ³ are as defined above. 2. Compound according to claim 1, in which n represents 5, 10 or 11. 3. Compound according to claim 2, in which n represents 10. 4. Compound according to any one of claims 1 to 3, in which R ⁵ represents a group of formula (I') as defined in claim 1, the compound thus having the following formula (II'):

wherein R ¹ , R ² , R ³ , R ⁴ , m, n and L are as defined in claim 1. 5. Compound according to any one of claims 1 to 3, in which R ⁵ is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms. 6. A compound according to any one of claims 1 to 5, wherein R ² is -Ph, R ³ is -O-Ph and R ² and R ³ together form a biphenyl, the group -(P=O)R ² R ³ thus having the formula (III):

or in which R ² is -Ph-Ph-OH and R ³ is a hydroxyl, the group - (P=O)R ² R ³ thus having the formula (IV):

or in which R ² and R ³ are identical and represent a -Ph group, the -(P=O)R ² R ³ group thus having the formula (VII):

(VII). 7. A process for preparing a compound according to any one of claims 1 to 6, comprising the reaction: of a compound A of formula (Xla) or (Xlb):

wherein R ¹ and n are as defined in claim 1,

in which n is as defined in claim 1,

in which n is as defined in claim 1, with a compound B of formula (XII):

wherein: m, L and R ⁴ are as defined in claim 1, and R ⁷ is selected from a group -(C=O)H, a hydrogen, a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms, an alkoxyl comprising from 1 to 4 carbon atoms, and a compound C of formula (XIII):

wherein R ² and R ³ are as defined in claim 1 and R ⁶ represents H or OH. 8. A method according to claim 7, wherein compound A has the formula (Xla) or (Xlb), wherein n represents 5 or 10. 9. The method of claim 7, wherein compound A is laurolactam. 10. Process according to any one of claims 7 to 9, in which compound B is chosen from benzaldehyde, vanillin and ethyl vanillin. 11. A process according to any one of claims 7 to 9, for preparing a compound according to claim 4, in which compound B has the formula (XII'):

wherein L, R ⁴ and m are as defined in claim 1. 12. Method according to claim 11, in which compound B is chosen from terephthalaldehyde and divanillin. 13. A method according to any one of claims 7 to 12, wherein compound C is selected from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, hypophosphorous acid, phenyl phosphorous acid, phosphoric acid, dimethylphosphite, diethylphosphite and diphenylphosphite. 14. A process according to claim 13 for preparing the compound according to claim 6, wherein compound C is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. 15. Polyamide obtained by polycondensation of a compound according to any one of claims 1 to 6. 16. Polyamide according to claim 15, the polyamide being aliphatic. 17. Polyamide according to claim 15, the polyamide being semi-aromatic. 18. Aliphatic or semi-aromatic polyamide according to claim 16 or 17, obtained by polycondensation of a compound according to claim 5, and comprising a repeating unit of formula (XXII):

wherein m, n, L, R ² , R ³ and R ⁴ are as defined in claim 1 and R ⁵ is as defined in claim 5. 19. Aliphatic or semi-aromatic polyamide according to claim 16 or 17, obtained by polycondensation of a compound of formula (II') as defined in claim 4 with an aliphatic diamine of formula H2N-L ² -NH2 in which L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, said aliphatic or semi-aromatic polyamide comprising a repeating unit of formula (XXI'):

wherein m, n, L, R ² , R ³ and R ⁴ are as defined in claim 1 and L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms. 20. Aliphatic polyamide according to any one of claims 16, 18 and 19, further comprising one or more other unit(s) 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. 21. Aliphatic polyamide according to claim 20, further comprising a repeating unit of formula (XXIII):

in which q represents an integer from 5 to 11. 22. Semi-aromatic polyamide according to any one of claims 17 to 19, further 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 dicarboxylic acids. 23. Semi-aromatic polyamide according to any one of claims 17 to 19, 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. 24. Semi-aromatic polyamide according to claim 23, 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. 25. Semi-aromatic polyamide according to any one of claims 22 to 24, further comprising an aliphatic repeating unit A chosen from a motif obtained from at least one amino acid and a motif obtained from at least one lactam. 26. Polyamide according to claim 15, the polyamide being transparent. 27. Transparent polyamide according to claim 26, 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. 28. Transparent polyamide according to claim 27, further comprising an aliphatic repeating unit A chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam. 29. Transparent polyamide according to any one of claims 26 to 28, obtained by polycondensation of a compound according to claim 5 with at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1, said transparent polyamide comprising: a repeating unit of formula (XXII):

wherein m, n, L, R ² , R ³ and R ⁴ are as defined in claim 1 and R ⁵ is as defined in claim 5, and 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. 30. Transparent polyamide according to any one of claims 26 to 28, obtained by polycondensation: - of a compound of formula (II’) as defined in claim 4, - with an aliphatic diamine of formula H2N-L ² -NH2, in which L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, and, - when L ² is not a divalent cycloaliphatic group, with at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1, said transparent polyamide comprising a repeating unit of formula (XXI'):

in which: - m, n, L, R ² , R ³ and R ⁴ are as defined in claim 1 , and - L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, it being understood that, when L ² is not a divalent cycloaliphatic group, then the transparent 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. 31. Polyether block amide (PEBA) resulting from the polycondensation: of one or more polyamides having diamine or dicarboxylic acid chain ends and obtained by polycondensation of a compound according to any one of claims 1 to 6, 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. 32. Polyether block amide according to claim 31, resulting from the polycondensation: of one or more polyamides having diamine or dicarboxylic acid chain ends and obtained by polycondensation of a compound according to claim 5, and comprising a repeating unit of formula (XXII):

in which m, n, L, R ² , R ³ and R ⁴ are as defined in claim 1 and R ⁵ is as defined in claim 5, 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. 33. Polyether block amide according to claim 31, resulting from the polycondensation: of one or more polyamides having diamine or dicarboxylic acid chain ends and obtained by polycondensation of a compound of formula (II') as defined in claim 4 with an aliphatic diamine of formula H2N-L ² -NH2 in which L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, said polyamide comprising a repeating unit of formula (XXI'):

in which m, n, L, R ² , R ³ and R ⁴ are as defined in claim 1 and L ² is a divalent aliphatic group comprising from 4 to 36 carbon atoms, 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. 34. Polyether block amide according to any one of claims 31 to 33, resulting from the polycondensation: of one or more polyamides having diamine chain ends and obtained by polycondensation of a compound according to any one of claims 1 to 6, and with one or more polyether blocks having dicarboxylic acid chain ends. 35. Polyether block amide according to claim 34, in which the polyether block with dicarboxylic acid chain ends is a polyoxyalkylene with dicarboxylic acid chain ends. 36. Polyether block amide according to any one of claims 31 to 33 resulting from the polycondensation: of one or more polyamides having dicarboxylic acid chain ends and obtained by polycondensation of a compound according to any one of claims 1 to 6, and with one or more polyether blocks having diamine chain ends. 37. Polyether block amide according to claim 36, in which the polyether block is with diamine chain ends and is a polyoxyalkylene with diamine chain ends. 38. Polyether block amide according to any one of claims 31 to 33, resulting from the polycondensation: of one or more polyamides having dicarboxylic acid chain ends and obtained by polycondensation of a compound according to any one of claims 1 to 6, and with one or more polyetherdiol blocks, the polyether block amide then being a polyetheresteramide. 39. Polyamide according to any one of claims 15 to 30 or polyether block amide according to any one of claims 31 to 38, having a mass proportion of atomic phosphorus of at least 0.1%. 40. Polyamide according to any one of claims 15 to 30 and 39, or polyether block amide according to any one of claims 31 to 39, comprising fillers, reinforcing fibers, in particular glass fibers, additives, in particular chosen from flame retardants, antioxidants, plasticizers and mixtures thereof, or a mixture thereof. 41. Use of a polyamide according to any one of claims 15 to 30, 39 and 40 or of a polyether block amide according to any one of claims 31 to 40 as a flame retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof. 42. Process for the preparation of a polyamide according to any one of claims 15 to 30 comprising the polycondensation of a compound of formula (I) as defined in claim 1, optionally in the presence of one or more other comonomers. 43. Preparation process according to claim 42 of an aliphatic polyamide, comprising the polycondensation of a compound of formula (I) as defined in claim 1, with at least one other monomer chosen from aliphatic amino acids, aliphatic lactams, mixtures of aliphatic diamines and aliphatic dicarboxylic acids, and mixtures thereof. 44. Preparation process according to claim 42 of a semi-aromatic polyamide, comprising the polycondensation of a compound of formula (I) as defined in claim 1, with one or more other aromatic comonomers. 45. Preparation process according to claim 42 of a transparent polyamide, comprising the polycondensation of a compound of formula (I) as defined in claim 1, with at least one cycloaliphatic diamine X1 and at least one dicarboxylic acid Y1. 46. Process for the preparation of a polyether block amide comprising the polycondensation: of one or more polyamides obtained by polycondensation of a compound according to any one of claims 1 to 6 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. 47. Article comprising a polyamide according to any one of claims 15 to 30, 39 and 40 or a polyether block amide according to any one of claims 31 to 40. 48. Process for preparing an article comprising a step of extruding, molding or overmolding the polyamide according to any one of claims 15 to 30, 39 and 40 or the polyether block amide according to any one of claims 31 to 40, whereby an article is obtained.