FR3157388A1 - Compound useful for preparing a self-flame retardant polyether block amide - Google Patents

Abstract

Compound Useful for Preparing a Self-Flame-Retardant Polyether Block Amide The present invention relates to a compound of the following formula (I): a process for its preparation, and its use for preparing a polyether block amide incorporating a repeating unit derived from said compound within the polymer chain of the polyamide block(s) it contains, which gives it self-flame-retardant properties. The invention also relates to said polyether block amide, an article comprising it, and a process for its preparation. Figure for abstract: None

Description

Compound useful for preparing a self-flame retardant polyether block amide

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

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 certainly possess a very high level of performance. However, they are not naturally fire resistant: they burn easily, producing flaming drops that can spread fires. However, many applications in the electrical, electrotechnical, electronics fields, as well as in transport (air, rail, electric vehicles, etc.) require flame retardant performance.

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

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).

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 PEBA, and capable of conferring self-flame retardant properties to said PEBA.

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

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 a hydrogen, a hydroxyl, an alkoxyl comprising from 1 to 2 carbon atoms, 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 each represent a group -Ph or
–O-Ph, R ² and R ³ can be linked together to 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,

- 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 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'):

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, alkoxyl comprising from 1 to 4 carbon atoms,

- 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):

The invention also relates to the process for preparing this compound, comprising the reaction:

- of a compound A of formula (XIa) or (XIb):

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 (XII):

in which:

- m, L and R ⁴ are as defined above, and

- R ⁷ is chosen 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.

According to advantageous aspects of the invention, the process for preparing the compound of formula (I) comprises one or more of the following characteristics, taken in isolation or in all technically possible combinations:

- compound A has the formula (XIa) or (XIb) 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 (XII’):

• 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 et le diphénylphosphite, l’oxyde de diphénylphosphine, de préférence le composé C est le 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

in which L, R ⁴ and m are as defined above, compound B preferably being chosen from terephthalaldehyde and divanillin,

• 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 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 a PEBA.

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 of a PEBA.

The invention also relates to a process for preparing a PEBA comprising the polycondensation:

- 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 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 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 block(s) of the PEBA. The flame retardant is thus integrated reactively and not additively. Advantageously, the PEBAs according to the invention are classified V0 in the UL94-vertical burning test, in particular for tests with a PEBA sample 1.6 mm thick. The invention is also based on the discovery that such PEBAs not only have good flame retardant properties, but also that they retain the intrinsic performance of the PEBA from which they are derived (PEBAs whose polyamide block(s) are free of repeating units derived from the compound of formula (I), but whose other repeating units are identical. For 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 PEBAs having high molar masses.

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

- PEBA results from polycondensation:

- 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, 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 polycondensation:

- 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 H ₂ NL ² -NH ₂ 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, L ² , R ² , R ³ and R ⁴ are as defined above,

- 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 polycondensation:

- 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 polycondensation:

- 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 with diamine chain ends, which is preferably a polyoxyalkylene with diamine chain ends,

- PEBA results from polycondensation:

- 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,

PEBA then being a polyetheresteramide,

- PEBA has a mass proportion of atomic phosphorus of at least 0.1%,

- PEBA comprises fillers, reinforcing fibres, in particular glass fibres, additives, in particular chosen from flame retardants, antioxidants, plasticisers and mixtures thereof, or a mixture of these.

The invention also relates to the use of the PEBA 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 PEBA defined above.

The invention also relates to a method for preparing an article comprising a step of extruding, molding or overmolding this PEBA, whereby an article is obtained.

Definitions

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 the ISO 11357-3:2013 standard is 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 0.2μm, 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 μm, and a 100 Å column with dimensions of 300 x 8 mm and particle size of 7 μm. 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.

The 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, using a viscometer equipped with a Micro-Ubbelohde viscometer tube.

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.

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 a hydrogen, a hydroxyl, an alkoxyl comprising from 1 to 2 carbon atoms, 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 each represent a group -Ph or
–O-Ph, R ² and R ³ can be linked together to 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,

- 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 into PA6, PA11 and PA12 respectively. For example, when n is 10, the group –NH(CH ₂ ) ₁₀ -COOR ¹ is then derived from amino-11-undecanoic acid, and the compound of formula (I') is particularly suitable for being incorporated into 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.

In formula (I), 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, 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).

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 a polyamide block of a PEBA.

In a first embodiment of this first alternative, L represents a single bond. The compound then has the following formula (II’a):

(II'a)

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

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 (II’b):

(II'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 (II'b) may be attached to any position of each phenyl. Preferably, the compound of formula (II'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(CH ₂ ) _n -COOR ¹ group can then serve as reactive groups to incorporate the compound of formula (I) 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, two alternatives can be distinguished for the groups R ² and R ³ of formula (I).

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):

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 second subject, the invention relates to a process for preparing the compound of formula (I), comprising the reaction:

- of a compound A of formula (XIa) or (XIb):

(XIa)

in which R ¹ and n are as defined above,

(XIb)

in which n is as defined above,

(XIc)

in which n is as defined above,

- with a compound B of formula (XII):

in which:

- m, L and R ⁴ are as defined above, and

- R ⁷ is chosen 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 process for preparing the compound of formula (I) is illustrated in Scheme 1 below:

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

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

According to a first preferred embodiment for compound A, compound A has the formula (XIa) or (XIb), 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 PA6 or PA11. Typically, compound A is amino-6-hexanoic acid, amino-11-undecanoic acid, or a salt thereof.

According to a second preferred embodiment for compound A, compound A is laurolactam. Laurolactam is a compound of formula (XIc) 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 PA12.

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

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, 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 (XIa), (XIb), (XIc)), compound B (of formula (XII)) and compound C (of formula (XIII)) are commercially available.

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

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

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 compound A+B+C in the solvent is 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.

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 PEBA.

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 PEBA.

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 invention relates in particular to a process for preparing a PEBA comprising the polycondensation:

- 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 polycondensation:

- 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:

- 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:

- 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, 7-aminoheptanoic, 11-aminoundecanoic, n-heptyl-11-aminoundecanoic, and 12-aminododecanoic 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 β,β-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-cyclo-hexyl-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. 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,ω-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 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.

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 _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 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 cycloaliphatic, the dicarboxylic acid Y1 is preferably selected 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 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.

According to a seventh subject, the invention relates to a polyether block amide (PEBA) resulting from the polycondensation:

- 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):

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 NH ₂ chain ends, such blocks being obtainable by cyanoacetylation of aliphatic α,ω-dihydroxylated polyoxyalkylene blocks called polyetherdiols. More particularly, the commercial products Jeffamine or Elastamine may be used (for example Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products from Huntsman, also described in documents JP 2004346274, JP 2004352794 and EP 1482011).

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, PEBA results from polycondensation:

- 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:

- 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 polycondensation:

- 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).

According to a first alternative, the polyamide block of PEBA is obtained by polycondensation of a compound of formula (I) in which the R ⁵ group 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 H ₂ NL ² -NH ₂ 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'):

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

Two alternatives are preferred for group L ² .

Preferably, according to a first alternative for the group L ² , L ² represents a group –(CH ₂ ) _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-L ₂ -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 _cyclo ):

• R¹¹, R¹², R¹³et R¹⁴représentent indépendamment un groupe choisi parmi un atome d'hydrogène ou un alkyle de 1 à 6 atomes de carbone (sous réserve que la somme des atomes de carbone du groupe L²soit d’au plus 36) et
• X représente soit une liaison simple, soit un groupement divalent constitué :
• d'une chaîne aliphatique linéaire ou ramifiée comprenant de 1 à 10 atomes de carbone, éventuellement substituée par des groupements cycloaliphatiques ou aromatiques de 6 à 8 atomes de carbone (sous réserve que la somme des atomes de carbone du groupe L²soit d’au plus 36), ou
• d'un groupement cycloaliphatique de 6 à 12 atomes de carbone (sous réserve que la somme des atomes de carbone du groupe L²soit d’au plus 36).

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:
• 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
• of a cycloaliphatic group of 6 to 12 carbon atoms (provided that the sum of the carbon atoms of the ^L2 group is at most 36).

Typically, the –NH-L ₂ -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 a hydrogen, a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms and an alkoxyl comprising from 1 to 4 carbon atoms.

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, 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, 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 NH ₂ groups).

Aliphatic amino acid, aliphatic lactam, aliphatic diamine and aliphatic dicarboxylic acid are in particular as defined above.

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-(CH ₂ ) _q -NH of the repeating unit of formula (XXIII) is identical to the group(s) –CO-(CH ₂ ) _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 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.

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/IPD.14, PA 12/BMACM.14, PA 12/PACM.14, and PA 12/IPD.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 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 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.

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 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 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 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 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 1.6 mm thick PEBA sample.

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 generally set by the chain limiter content. It can be calculated according to the relationship:
M _n = n _monomer x M _{W repeating unit} / n _{chain limiter} + M _{W chain 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 _{repeat unit} represents the molar mass of the repeat unit, and MW _{chain 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 between 1.10 and 2.00.

PEBA can be amorphous or semi-crystalline.

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 notably chosen from DOPO and its derivatives, melamine cyanurate, melamine polyphosphate, red phosphorus, metal dialkylphosphinates and mixtures thereof.

Since the PEBAs according to the invention are self-flame retardant, they can 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 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 PEBA may include 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 PEBA.

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

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

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

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

According to a ninth object, the invention relates to a method for preparing an article comprising a step of extruding, molding or overmolding 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 PEBA according to the present invention is advantageous for the manufacture of articles, in particular articles or elements of sporting articles, which must in particular have both good impact resistance and good endurance to mechanical, chemical, UV and thermal aggression. Among these sporting articles, mention may be made of elements of sports shoes, sports utensils such as ice skates or other winter sports and mountaineering articles, ski bindings, snowshoes, sports bats, boards, horseshoes, fins, golf balls, recreational vehicles, in particular those intended for activities in cold weather. We can also mention, in general, leisure and DIY articles, tools and road equipment subject to climatic and mechanical aggression, protective articles, such as helmet visors, glasses, as well as glasses arms. We can also cite, by way of non-limiting examples, car components, such as headlight protectors, rearview mirrors, small parts of off-road vehicles, tanks, in particular, of mopeds, motorcycles, scooters, subject to mechanical and chemical aggression, screws, cosmetic articles subject to mechanical and chemical aggression, lipsticks, pressure gauges, aesthetic protection elements such as gas bottles. We can also mention objects or parts of objects for electronics requiring compliance with dimensions, for example parts of mobile phones, computers, tablets, etc.

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

Claims (28)

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 a hydrogen, a hydroxyl, an alkoxyl comprising from 1 to 2 carbon atoms, 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 each represent a group -Ph or
–O-Ph, R ² and R ³ can be linked together to 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 and an 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. A compound according to claim 1, wherein n represents 5, 10 or 11. A compound according to claim 2, wherein n represents 10. A compound according to any one of claims 1 to 3, wherein 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. A compound according to any one of claims 1 to 3, wherein R ⁵ is selected from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms. 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):
A process for preparing a compound according to any one of claims 1 to 6, comprising the reaction:
- of a compound A of formula (XIa) or (XIb):
(XIa)
in which R¹and n are as defined in claim 1,
(XIb)
in which n is as defined in claim 1,
(XIc)
in which n is as defined in claim 1,
- with a compound B of formula (XII):

in which:
- m, L and R⁴are as defined in claim 1, and
- R⁷is chosen 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):

in which R²and R³are as defined in claim 1 and R⁶represents H or OH. A process according to claim 7, wherein compound A has the formula (XIa) or (XIb), wherein n represents 5 or 10. The method of claim 7, wherein compound A is laurolactam. A process according to any one of claims 7 to 9, wherein compound B is selected from benzaldehyde, vanillin and ethyl vanillin. A process according to any one of claims 7 to 9 for preparing a compound according to claim 4, wherein compound B has the formula (XII'):

wherein L, R ⁴ and m are as defined in claim 1. The method of claim 11, wherein compound B is selected from terephthalaldehyde and divanillin. 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. 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. Polyether block amide (PEBA) resulting from polycondensation:
- 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. Polyether block amide according to claim 15, resulting from the polycondensation:
- 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):

wherein m, n, 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. Polyether block amide according to claim 15, resulting from the polycondensation:
- 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 H ₂ NL ² -NH ₂ 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'):
wherein m, n, L, R ² , R ³ and R ⁴ are as defined in claim 1 and L ² is as defined above,
- 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. Polyether block amide according to any one of claims 15 to 17, resulting from the polycondensation:
- 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 with dicarboxylic acid chain ends. Polyether block amide according to claim 18, in which the polyether block with dicarboxylic acid chain ends is a polyoxyalkylene with dicarboxylic acid chain ends. Polyether block amide according to any one of claims 15 to 17 resulting from polycondensation:
- 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 with diamine chain ends. Polyether block amide according to claim 20, in which the polyether block is with diamine chain ends and is a polyoxyalkylene with diamine chain ends. Polyether block amide according to any one of claims 15 to 17, resulting from the polycondensation:
- 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. Polyether block amide according to any one of claims 15 to 21, having a mass proportion of atomic phosphorus of at least 0.1%. Polyether block amide according to any one of claims 15 to 23, comprising fillers, reinforcing fibers, in particular glass fibers, additives, in particular chosen from flame retardants, antioxidants, plasticizers and mixtures thereof, or a mixture of these. Use of a polyether block amide according to any one of claims 15 to 24 as a flame retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof. Process for the preparation of a polyether block amide comprising polycondensation:
- 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. An article comprising a polyether block amide according to any one of claims 15 to 24. A process for preparing an article comprising a step of extruding, molding or overmolding the polyether block amide according to any one of claims 15 to 24, whereby an article is obtained.