Compound useful for preparing a self-flame retardant semi-aromatic polyamide

Abstract

Compound useful for preparing a self-flame retardant semi-aromatic polyamide The present invention relates to a compound of the following formula (I): its preparation process, and its use for the preparation of semi-aromatic polyamide incorporating a repeating unit derived from said compound within its polymer chain, which gives it self-flame retardant properties. The invention also relates to said semi-aromatic polyamide, an article comprising it and its preparation process. Figure for abstract: None

Description

Title of the invention: Compound useful for preparing a self-flame retardant semi-aromatic polyamide

[0001] The present invention relates to a compound comprising phosphorus atoms, its preparation process, and its use for the preparation of semi-aromatic polyamide (PASA) incorporating a repeating unit derived from said compound within its polymer chain, which gives it self-flame retardant properties.

[0002] Polyamides, particularly semi-aromatic polyamides, have exceptional performance in many applications such as transportation, energy, consumer goods such as sporting goods and consumer electronics, anti-corrosion protective coatings and objects obtained by 3D printing.

[0003] Polyamides in general, and semi-aromatic polyamides in particular, certainly possess a very high level of performance. However, they are not naturally fire resistant: they burn easily, giving off flaming drops that can spread fires. However, many applications in the electrical, electrotechnical, electronic fields, but also in transport (air, rail, electric vehicles, etc.) require flame retardant performance.

[0004] Many solutions have been developed by adding, by melt mixing, initially halogenated additives, now halogen-free, based on phosphorus, nitrogen or hydrated fillers. These additives are not integrated into the polymer chain of polyamides. For example, melamine cyanurate, melamine polyphosphate, red phosphorus and metal dialkylphosphinates are used as flame retardant additives. Some 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives are also used as additives in polymers. However, flame retardancy performance is often achieved at the expense of other material properties such as ductility, dielectric properties, thermo-oxidation resistance, dimensional stability, water uptake and rheology.

[0005] Some attempts to incorporate flame retardant repeating units have been reported, particularly with acid-derived units 3- [ 10-(9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide-10-y 1) ] itaconic acid (DOPO-ITA). However, as detailed in the article Negrell et al. Polymer Degradation and Stability 134 (2016) 10-18 (paragraph 3.3 and figure 12), this DOPO-ITA based on 4 carbon atom diacids plays a chain-limiting role in polyamidation and therefore cannot allow the synthesis of high-mass PAs molars.

[0006] Another diacid monomer has been reported in WO 17 / 021355, namely 3-(hydroxy(phenyl)phosphoryl)propanoic acid. This monomer having a carboxylic acid end and a phosphonic acid end also acts as a chain limiter and also does not allow the synthesis of high molecular weight polyamides.

[0007] 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 semi-aromatic polyamide, and capable of conferring self-flame retardant properties to said semi-aromatic polyamide.

[0008] An object of the invention is also to provide a semi-aromatic polyamide having good flame retardant properties while retaining its other properties, including those listed above.

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

[0010] For this purpose, the invention relates to a compound of the following formula (I):

[0011] [Chem.l]

[0012] in which:

[0013] - R1 represents H, a linear, branched or cyclic alkyl group comprising from 1 to 12 carbon atoms, or a cation,

[0014] - n represents an integer from 5 to 11,

[0015] - R2 and R3 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,

[0016] it being understood that, when R2 and R3 each represent a group -Ph or -O-Ph, R2 and R3 can be joined together to form a biphenyl group,

[0017] - m represents an integer from 0 to 4,

[0018] - each R4 is independently selected from hydroxyl, alkyl comprising 1 to 4 carbon atoms and an alkoxyl comprising 1 to 4 carbon atoms,

[0019] - L is a single bond or a phenylene optionally substituted by one or several substituents chosen from a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms, an alkoxyl comprising from 1 to 4 carbon atoms,

[0020] - R5 is chosen from a hydrogen, a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms, an alkoxyl comprising from 1 to 4 carbon atoms and a group of formula (I'):

[0021] [Chem.2]

[0022] in which n, R1, R2 and R3 are as defined above.

[0023] The compound of formula (I) comprises at least one phosphorus atom, which makes it capable of imparting flame retardant properties to a semi-aromatic polyamide prepared using the compound of formula (I) as a monomer.

[0024] According to advantageous aspects of the invention, the compound of formula (I) comprises one or more of the following characteristics, taken in isolation or in all technically possible combinations:

[0025] - n represents 5, 10 or 11, preferably n represents 10,

[0026] - R5 represents a group of formula (!) as defined above, the compound having thus the following formula (II'):

[0027] [Chem.3]

[0028] in which R1, R2, R3, R4, m, n and L are as above,

[0029] or R5 is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms, alkoxyl comprising from 1 to 4 carbon atoms,

[0030] - R2 is -Ph, R3 is -O-Ph and R2 and R3 together form a biphenyl, the group -(P=O)R2R3 thus having the formula (III):

[0031] [Chem.4]

[0032] or R2 is -Ph-Ph-OH and R3 is a hydroxyl, the group -(P=O)R2R3 thus having the formula (IV):

[0033] [Chem.5]

[0034] The invention also relates to the process for preparing this compound, comprising the reaction:

[0035] - of a compound A of formula (Xla) or (Xlb):

[0036] [Chem.6]

[0037] in which RI and n are as defined above,

[0038] [Chem.7] +

[0039] in which n is as defined above,

[0040] [Chem. 8] H..... o* NH m

[0041] in which n is as defined above,

[0042] - with a compound B of formula (XII):

[0043] [Chem.9]

[0044] in which:

[0045] - m, L and R4 are as defined above, and

[0046] - R7 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,

[0047] - and a compound C of formula (XIII):

[0048] [Chem. 10] (XII)

[0049] in which R2 and R3 are as defined above and R6 represents H or OH.

[0050] 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:

[0051] - compound A has the formula (Xla) or (Xlb) as defined above in which n represents 5 or 10, or compound A is laurolactam,

[0052] - compound B is chosen from benzaldehyde, vanillin and ethylvanillin, or well compound B has the formula (XII'):

[0053] [Chem. 11] H (XH5)

[0054] in which L, R4 and m are as defined above, compound B preferably being 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, dimethyl phosphite, diethyl phosphite and diphenyl phosphite, diphenyl phosphine oxide, preferably compound C is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0055] The invention also relates to the use of the compound of formula (I) as a flame retardant.

[0056] 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 semi-aromatic polyamide.

[0057] 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 semi-aromatic polyamide.

[0058] The invention also relates 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, typically one or more other aromatic comonomers.

[0059] The invention also relates to a semi-aromatic polyamide obtained by polycondensation of the compound according to the invention, optionally in the presence of one or more other comonomers, typically one or more other aromatic comonomers.

[0060] The semi-aromatic polyamide comprises a repeating unit derived from the compound of formula (I). The semi-aromatic polyamide 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 semi-aromatic polyamide. The flame retardant is thus integrated reactively and not additively. Advantageously, the semi-aromatic polyamides according to the invention are classified V0 in the UL94-vertical buming test, in particular for tests with a sample of semi-aromatic polyamide 1.6 mm thick.The invention is also based on the discovery that such semi-aromatic polyamides not only have good flame retardant properties, but also that they retain the intrinsic performance of the semi-aromatic polyamide from which they are derived (semi-aromatic polyamides free of repeating units derived from the compound of formula (I), but whose other repeating units are identical. For 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). Finally, it is possible to prepare semi-aromatic polyamides having high molar masses.

[0061] According to advantageous aspects of the invention, the semi-aromatic polyamide comprises one or more of the following characteristics, taken in isolation or in all technically possible combinations:

[0062] - the semi-aromatic polyamide is obtained by polycondensation of a compound of formula (II') with an aliphatic diamine of formula H2N-L2-NH2 in which L2 is a divalent aliphatic group comprising from 4 to 36 carbon atoms, said semi-aromatic polyamide comprising a repeating unit of formula (XXI'):

[0063] [Chem. 12]

[0064] in which m, n, L, L2, R2, R3 and R4 are as defined above.

[0065] - the semi-aromatic polyamide is obtained by polycondensation of a compound of formula (I) in which R5 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):

[0066] [Chem. 13] o (XXII)

[0067] in which m, n, R2, R3 and R4 are as defined above and R5 is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms,

[0068] - the semi-aromatic polyamide further comprises a repeating unit X2.Y2 obtained from 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,

[0069] - the semi-aromatic polyamide further comprises a repeating unit X3.Y3 obtained from from the polycondensation of at least one aliphatic, linear or diamine X3 branched or cycloaliphatic, and an aromatic dicarboxylic acid Y3, which is preferably terephthalic acid, isophthalic acid or a mixture thereof,

[0070] - the semi-aromatic polyamide 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 one lactam,

[0071] - the semi-aromatic polyamide has a mass proportion of atomic phosphorus of at least 0.1%,

[0072] - the semi-aromatic polyamide comprises fillers, reinforcing fibers, in par particular glass, additives, in particular chosen from flame retardants, antioxidants, plasticizers and mixtures thereof, or a mixture of these.

[0073] The invention also relates to the process for preparing this semi-aromatic polyamide comprising the polycondensation of a compound of formula (I), with one or more other aromatic comonomers.

[0074] The invention also relates to the use of the semi-aromatic polyamide defined above as a flame retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof.

[0075] The invention also relates to an article comprising the semi-aromatic polyamide defined above.

[0076] The invention also relates to a method for preparing an article comprising a step of extruding, molding or overmolding this semi-aromatic polyamide, whereby an article is obtained.

[0077] Definitions

[0078] An amorphous semi-aromatic polyamide, within the meaning of the application, denotes a amorphous transparent semi-aromatic polyamide having only a glass transition temperature (no melting temperature (Tm)), or a very slightly crystalline semi-aromatic polyamide having a glass transition temperature and a melting point such that the enthalpy of crystallization during the cooling step at a rate of 20K / min in differential scanning calorimetry (DSC) measured according to ISO 11357-3:2013 is less than 30 J / g, in particular less than 20 J / g, preferably less than 15 J / g. The glass transition temperature (Tg) measured by DSC at a heating rate of 20K / min according to ISO 11357-1:2009 and ISO 11357-2:2013 for these semi-aromatic 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.

[0079] A semi-crystalline semi-aromatic polyamide, within the meaning of the application, denotes a semi-aromatic polyamide which has a melting temperature (Tf) in DSC according to ISO 11357-3:2013, and an enthalpy of crystallization during the re-curing step cooling 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.

[0080] 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.

[0081] The term "polyamide" or "semi-aromatic polyamide" used in the present description covers both homopolyamides and copolyamides.

[0082] In the PA XY notation, X represents the number of carbon atoms from the diamine residues or the abbreviation of the diamine, and Y represents the number of carbon atoms from the diacid residues or the abbreviation of the diacid, conventionally.

[0083] In the PA X notation, X represents the number of carbon atoms derived from the amino acid or lactam residues.

[0084] The notations PA X / Y, PA X / Y / Z, etc. refer to semi-aromatic copolyamides in which X, Y, Z, etc. represent homopolyamide units.

[0085] The polydispersity index IP is equal to the ratio of the molar mass by weight to the molar mass by number (Mw / Mn).

[0086] 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 semi-aromatic 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.

[0087] Total acidity and total basicity are measured by potentiometry.

[0088] The acidity is measured according to the following method. A sample of semi-aromatic polyamide is dissolved in benzyl alcohol. Then, this sample is potentiometrically assayed with a 0.02N tetrabutylammonium hydroxide solution.

[0089] The basicity is measured according to the following method. A sample of semi-aromatic polyamide is dissolved in metacresol. Then, this sample is dosed potentiometrically with a 0.02N perchloric acid solution.

[0090] The inherent viscosity is measured at a semi-polyamide concentration aromatic 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.

[0091] The crystallinity rate is calculated according to the following formula:

[0092] [Math.l] x = W xl0 ° in which:

[0093] x denotes the crystallinity rate,

[0094] AHf * denotes the enthalpy of fusion of the semi-aromatic polyamide

[0095] AHf denotes the enthalpy of fusion of the 100% crystalline semi-aromatic 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.

[0096] By "linear, branched or cyclic alkyl" is meant a linear or branched saturated hydrocarbon aliphatic 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.

[0097] An alkoxyl group is an -O-alkyl radical where the alkyl group is as previously defined. Examples of alkoxyl include methoxyl, ethoxyl, or propoxyl groups.

[0098] According to a first subject, the invention relates to a compound of the following formula (I):

[0099] [Chem. 14]

[0100] in which:

[0101] - R1 represents H, a linear, branched or cyclic alkyl group comprising from 1 to 12 carbon atoms, or a cation,

[0102] - n represents an integer from 5 to 11,

[0103] - R2 and R3 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,

[0104] it being understood that, when R2 and R3 each represent a group -Ph or -O-Ph, R2 and R3 can be joined together to form a biphenyl group,

[0105] - m represents an integer from 0 to 4,

[0106] - each R4 is independently selected from a hydroxyl, an alkyl comprising 1 to 4 carbon atoms and an alkoxyl comprising 1 to 4 carbon atoms,

[0107] - L is a single bond or a phenylene optionally substituted by one or several substituents chosen from a hydroxyl, an alkyl comprising from 1 to 4 carbon atoms, an alkoxyl comprising from 1 to 4 carbon atoms,

[0108] - R5 is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms, an alkoxyl comprising from 1 to 4 carbon atoms and a group of formula (T):

[0109] [Chem. 15]

[0110] in which n, R1, R2 and R3 are as defined above.

[0111] 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 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)i0-COOR1 is then derived from amino-11-undecanoic acid, and the compound of formula (!') is particularly suitable for being incorporated into a PA 11 / X2.Y2 or PA 11 / X3.Y3.

[0112] In formula (I), R1 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, R1 represents H or a cation.

[0113] In formula (I), each R4 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, R4 represents OH, Me or OMe.

[0114] In formula (I), m represents an integer from 0 to 4, preferably 0 or 1. When m is 0, the compound is free of R4 group.

[0115] 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'):

[0116] [Chem. 16]

[0117] in which m and R4 are as defined above.

[0118] Two alternatives can be distinguished for the R5 group of formula (I).

[0119] According to a first alternative, in formula (I), R5 represents a group of formula (!) as defined above, and the compound thus has the following formula (II'):

[0120] [Chem. 17]

[0121] in which R1, R2, R3, R4, m, n and L are as above. Such a compound advantageously carries two -COOR1 functions which can serve as reactive groups to incorporate the compound of formula (II') within the polymer chain of semi-aromatic polyamides.

[0122] In a first embodiment of this first alternative, L represents a single bond. The compound then has the following formula (II'a):

[0123] (He has)

[0124] wherein R1, R2, R3, R4, n and m are as defined above.

[0125] 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):

[0126] [Chem. 19] R^OOC (Il'b)

[0127] wherein R1, R2, R3, R4, 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.

[0128] According to a second alternative, in formula (I), R5 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 -COOR1 group of the -NH(CH2)n-COOR1 group can then serve as reactive groups to incorporate the compound of formula (I) within the polymer chain of semi-aromatic polyamides. The secondary amine function is less reactive than a -COOR1 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 -COOR1 functions.

[0129] Furthermore, two alternatives can be distinguished for the groups R2 and R3 of formula (I).

[0130] According to a first alternative, in formula (I), R2 is -Ph, R3 is -O-Ph and R2 and R3 together form a biphenyl, the group -(P=O)R2R3 thus having the formula (III):

[0131] [Chem.20]

[0132] The compound then has the following formula (V):

[0133] [Chem.21]

[0134] in which R1, R4, R5, L, n and m are as defined above.

[0135] According to a second alternative, in formula (I), R2 is -Ph-Ph-OH and R3 is a hydroxyl, the group -(P=O)R2R3 thus having the formula (IV):

[0136] [Chem.22] (IV)

[0137] The compound then has the following formula (VI):

[0138] [Chem. 23] (VI)

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145] in which R1, R4, R5, 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 (Xla) or (Xlb): [Chem. 24] R "^OOC NHg (Xla) in which R1 and n are as defined above, [Chem. 25] THERE + 'OOC K MH 3

[0146]

[0147]

[0148]

[0149] (Xlb) in which n is as defined above, [Chem.26] M (XIc) in which n is as defined above, - with a compound B of formula (XII):

[0150] [Chem.27]

[0151] in which:

[0152] - m, L and R4 are as defined above, and

[0153] - R7 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,

[0154] - and a compound C of formula (XIII):

[0155] [Chem.28] / r2 P—O (XÙ!)

[0156] in which R2 and R3 are as defined above and R6 represents H or OH.

[0157] The method according to the invention is illustrated in diagram 1 which follows:

[0158] [Chem.29] (Xla)

[0159] Scheme 1: Reaction scheme of the process for preparing the compound of formula (I)

[0160] When compound A has the formula (XIc), the reaction is preferably carried out in works 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 (Xla) and / or (Xlb).

[0161] 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 PA 6 / X2.Y2 or 6 / X3.Y3, and of PA 11 / X2.Y2 or 11 / X3.Y3. Typically, compound A is amino-6-hexanoic acid, amino-11-undecanoic acid, or a salt thereof.

[0162] 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 within the polymer chain of PA 12 / X2.Y2 or 12 / X3.Y3.

[0163] According to a first preferred embodiment for compound B, compound B is chosen from benzaldehyde, vanillin and ethyl vanillin.

[0164] According to a second preferred embodiment for compound B, compound B has the formula (XII'):

[0165] [Chem.30] H (XH')

[0166] in which L, R4 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.

[0167] 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)R2R3 has the formula (III) or (IV) as defined above.

[0168] Advantageously, the starting products, namely compound A (of formulas (Xla), (Xlb), (XIc)), compound B (of formula (XII)) and compound C (of formula (XIII)) are commercially available.

[0169] Preferably, from 1.0 to 2.5 equivalents of compound A are used relative to compound B.

[0170] Preferably, from 1.0 to 2.5 equivalents of compound C are used relative to compound B.

[0171] Furthermore, the method according to the invention is simple. It is sufficient to mix three compounds.

[0172] The reaction is generally carried out in a solvent, preferably in a polar solvent, for example chosen from methanol, ethanol, isopropanol and dimethyl sulfoxide.

[0173] The mass concentration of compound A+B+C in the solvent is 20 g / L to 250 g / L.

[0174] The reaction is typically carried out at a temperature of 50 to 100°C, and / or at atmospheric pressure.

[0175] 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.

[0176] The subsequent treatment (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.

[0177] According to a third subject, the invention relates to the use of the compound of formula (I) as defined above as a flame retardant.

[0178] 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 semi-aromatic polyamide.

[0179] 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 semi-aromatic polyamide.

[0180] 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 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 alkylated diamine. romantic.

[0181] Advantageously, the compound of formula (I) does not act as a chain limiter, and it is possible to prepare semi-aromatic polyamides having a high molar mass.

[0182] 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.

[0183] The alkylaromatic diamine X2 is preferably chosen from 1,3-xylylene diamine (MXD), 1,4-xylylene diamine and their mixture.

[0184] 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 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 EP0 471 566.

[0185] As examples of preferred aliphatic Y2 dicarboxylic acids, mention may be made of butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids, and dimerized fatty acids.

[0186] When the dicarboxylic acid Y2 is cycloaliphatic, it may have the following carbon skeletons: norbomyl methane, cyclohexane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl) or di(methylcyclohexyl)propane. 1,4 Cyclohexyldicarboxylic acid is an example of a cycloaliphatic dicarboxylic acid Y2.

[0187] In one embodiment, the method comprises polycondensing a compound of formula (I) with at least one alkylaromatic diamine X2, with at least a 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.

[0188] Monomer A is preferably aliphatic.

[0189] 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 (H).

[0190] As an example of aliphatic lactam, mention may be made of those comprising, preferably, between 3 and 12 carbon atoms on the main cycle and which may be substituted. As an example of lactam, mention may be made of P,[3-dimethylpropriolactam, α,α-dimethylpropriolactam, amylolactam, ca-prolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam, the lactam preferably being caprolactam, oenantholactam and lauryllactam, in particular caprolactam (6) or lauryllactam (12).

[0191] 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.

[0192] 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.

[0193] As an example of linear or branched aliphatic diamine X3, it is possible to cite 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.

[0194] 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).

[0195] The cycloaliphatic diamine X3 may be chosen from the bis(3,5-dialkyl-4-aminocyclohexyl)-methane, bis(3,5-dialkyl-4-aminocyclohexyl)-ethane, bis(3,5-dialkyl-4-aminocyclohexyl)-propane, bis(3,5-dialkyl-4-aminocyclohexyl)-butane, l,3-bis(aminomethyl)cyclohexane (1,3-BAC), l,4-bis(aminomethyl)cyclohexane (1,4-BAC), bis-(3-methyl-4-aminocyclohexyl)-methane or 3'-dimethyl-4,4'-diamino-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.

[0196] Advantageously, the cycloaliphatic diamine X3 is chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis(aminocyclohexyl)-methane (P), l,3-bis(aminomethyl)cyclohexane (1,3-BAC) and isophoronediamine (IPD).

[0197] 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.

[0198] 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).

[0199] 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.

[0200] Monomer A is in particular as defined above for the first alternative.

[0201] According to a seventh object, the invention relates to a semi-aromatic polyamide obtained by polycondensation of the compound according to the invention, optionally in the presence of one or more other comonomers, preferably aromatic, typically an aromatic diamine, in particular an alkylaromatic diamine, or an aromatic dicarboxylic acid.

[0202] 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 semi-aromatic polyamide comprising it.

[0203] Two preferred alternatives of the semi-aromatic polyamide can be distinguished, depending on the alternative considered for the R5 group of the compound of formula (I).

[0204] According to a first alternative, the semi-aromatic polyamide is obtained by polycondensation of a compound of formula (I) in which R5 represents a group of formula (!') 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-L2-NH2 in which L2 is a divalent aliphatic group comprising from 4 to 36 carbon atoms, said semi-aromatic polyamide then comprising a repeating unit of formula (XXI'):

[0205] [Chem.31]

[0206] in which m, n, L, R2, R3 and R4 are as defined above.

[0207] Three alternatives are preferred for group L2.

[0208] Preferably, according to a first alternative for the group L2, L2 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.

[0209] According to a second alternative for the L2 group, the L2 group is a cycloaliphatic group comprising from 3 to 36 carbon atoms. For example, L2 has the following formula (L2cydo):

[0210] [Chem.32]

[0211] in which: - R11, R12, R13 and R14 independently represent a group chosen from a hydrogen atom or an alkyl of 1 to 6 carbon atoms (provided that the sum of the carbon atoms in the L2 group 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 atoms of carbon, optionally substituted by cycloaliphatic or aromatic groups of 6 to 8 carbon atoms (provided that the sum of the carbon atoms of the L2 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 L2 group is at most 36).

[0212] Typically, the -NH-L2-NH- group is then derived from a cycloaliphatic diamine chosen from bis(3,5-dialkyl-4-aminocyclohexyl)-methane, bis(3,5-dialkyl-4-aminocyclohexyl)-ethane, bis(3,5-dialkyl-4-aminocyclohexyl)-propane, bis(3,5-dialkyl-4-aminocyclohexyl)-butane, bis-(3-methyl-4-aminocyclohexyl)-methane 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).

[0213] According to a third alternative for the group L2, the group L2 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 group -NH-L2-NH- is then -NH-Ph-NH- where Ph is a phenyl and the -NHs are in the ortho, meta or para position to each other.

[0214] According to a second alternative, the semi-aromatic polyamide is obtained by polycondensation of a compound of formula (I) in which R5 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):

[0215] [Chem.33] o (XXII)

[0216] in which m, n, R2, R3 and R4 are as defined above and R5 is selected from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms and alkoxyl comprising from 1 to 4 carbon atoms.

[0217] 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.

[0218] 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.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] 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.

[0224] 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.

[0225] 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.

[0226] The embodiments described above for the amino acid or lactam monomer A are also applicable for the repeating unit A which is derived therefrom.

[0227] 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.

[0228] 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:

[0229] - A / 6T, A / 9T, A / 10T and A / 1 1T, A being as defined above, in particular 6 / 6T, 6I / 6T, MPMDT / 6T, MXDT / 6T, PA11 / 10T, 11 / 6T / 10T, MXDT / 10T, MPMDT / 10T, PA BACMT / 10T, BACMT / 6T, BACMT / 10T / 6T, 11 / BACMT / 10T, 11 / BACMT / 6T, 11 / 1.3-BAC.T, 11 / 1.4-BAC.T, 11 / MPMDT / 10T and 11 / MXDT / 10T,

[0230] and

[0231] - A / X3.Y3 in which X3 is BMACM, PACM or IPD and Y3 is T or I and A is such as defined above, in particular 11 / BMACM.T, 11 / BMACM.I, 12 / BMACM.T, 12 / BMACM.I, 11 / PACM.T, 11 / PACM.I, 12 / PACM.T, 12 / PACM.I, 11 / IPD.T, 11 / IPD.I, 12 / IPD.T and 12 / IPD.I, more particularly chosen from 11 / BMACM.T, 11 / BMACM.I, 11 / BMACM.T / BMACM.I, 12 / BMACM.T, 12 / BMACM.I, 12 / BMACM.T / BMACM.I, 11 / 1,3-BAC.T, 11 / 1,4-BAC.T, 11 / 1,3-BAC.I, 11 / 1,4-BAC.I, ll / l,3-BAC.T / 10.T, ll / l,4-BAC.T / 10.T, 11 / PACM.T, 11 / PACM.I, 12 / PACM.T, 12 / PACM.I, advantageously 11 / BMACM.T, 11 / PACM.T, 11 / PACM.I, 12 / PACM.T, 12 / PACM.I.

[0232] 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:

[0233] - 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

[0234] - a repeating unit X3.Y3 obtained from the polycondensation of at least one aliphatic, linear or branched or cycloaliphatic diamine X3 and a dicar- acid carboxylic aromatic Y3.

[0235] The following embodiments are applicable to all of the embodiments and alternatives defined above.

[0236] Preferably, the semi-aromatic 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.

[0237] Advantageously, the semi-aromatic polyamide is classified V0 in the UL94-vertical burning test, in particular for a test with a sample of semi-aromatic polyamide 1.6 mm thick.

[0238] The number-average molar mass Mn of the semi-aromatic polyamide is preferably from 5,000 to 50,000 g / mol, more preferably from 10,000 to 35,000 g / mol, even more preferably from 15,000 to 30,000 g / mol. The semi-aromatic polyamide can therefore advantageously have a high molar mass.

[0239] The weight-average molar mass Mw of the semi-aromatic 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.

[0240] The polydispersity index IP of the semi-aromatic 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.

[0241] The polydispersity index IP of the semi-aromatic polyamide is generally greater than or equal to 1.0, in particular greater than or equal to 2.0.

[0242] The absolute value of the difference between the total acidity and the total basicity of the semi-aromatic polyamide is preferably between 0 and 200 peq / g.

[0243] Preferably, the semi-aromatic polyamide has an inherent viscosity between 0.30 and 1.70.

[0244] Preferably, the semi-aromatic polyamide has a crystallinity level between 20 and 40%, in particular between 20 and 30%, measured by DSC (differential scanning calorimetry measurement) according to standard 11357-3, 1999 (2nd DSC heating at 20°C / min according to standard ISO 11357).

[0245] The semi-aromatic polyamide may be amorphous or semi-crystalline.

[0246] The semi-aromatic polyamide 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.

[0247] Among the reinforcing fibers, mention may be made of carbon or glass fibers, natural fibers or a mixture thereof.

[0248] Among the additives, mention may be made of flame retardants, limiting agents chain, impact modifiers, pigments, dyes, light (UV) and / or heat stabilizers, plasticizers, surfactants, optical brighteners, antioxidants, natural waxes, mold release agents, or mixtures thereof.

[0249] The flame retardants are in particular chosen from DOPO and its derivatives, melamine cyanurate, melamine polyphosphate, red phosphorus, metallic dialkylphosphinates and mixtures thereof.

[0250] To the extent that the semi-aromatic polyamides according to the invention are self-flame retardant, they may be free of flame retardant agent (used as an additive).

[0251] Typically, a chain-limiting agent comprises at least one, preferably at least two functions, each independently chosen from carboxylic acids and amines. This chain-limiting agent may be a dicarboxylic acid, a diamine or an amino acid. It makes it possible to react with the amide, amine or carboxylic acid functions of the semi-aromatic polyamide.

[0252] 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 semi-aromatic polyamide may comprise an impact modifier, in particular of an elastomeric nature and preferentially functionalized by maleic anhydride.

[0253] 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.

[0254] The reinforcing fibers are chosen from fibers, in particular short fibers. The fibers may be of synthetic origin, in particular glass or carbon fibers, or natural, typically of plant origin such as flax, reed, bamboo or hemp fibers. Preferably, the reinforcing fibers are glass fibers.

[0255] The usual stabilizers used are phenols, phosphites, UV absorbers, stabilizers of the HALS (Hindered Amine Light Stabilizer) type, metal iodides or thioethers. Mention may be made of Irganox 1010, 245, 1098, Irgafos 168, 126, Tinuvin 312, 770, Iodide P201 from the company Ciba, Nylostab S-EED from the company Clariant, AO 412S from the company Adeka Palmarole.

[0256] The mass proportion of the fillers is in particular from 0.5 to 50.0% relative to the weight of the semi-aromatic polyamide.

[0257] The mass proportion of the reinforcing fibers is in particular 5 to 75% relative to the weight of the semi-aromatic polyamide.

[0258] The mass proportion of the additives is in particular 0.05 to 3.00% relative to the weight of semi-aromatic polyamide.

[0259] The cumulative mass proportion of the fillers, reinforcing fibers, and additives is in particular 0.1 to 80% relative to the weight of the semi-aromatic polyamide.

[0260] According to an eighth object, the invention relates to the use of the semi-aromatic polyamide defined above as a flame-retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof.

[0261] According to a ninth object, the invention relates to a process for preparing an article comprising a step of extrusion, molding or overmolding of the semi-aromatic polyamide defined above, whereby an article is obtained.

[0262] 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 semi-aromatic polyamide according to the present invention is advantageous for the manufacture of articles, in particular articles or elements of sporting articles, which must in particular have both good impact resistance and good endurance to mechanical, chemical, UV and thermal aggression. Among these sporting articles, mention may be made of elements of sports shoes, sports utensils such as ice skates or other winter sports and mountaineering articles, ski bindings, snowshoes, sports bats, boards, horseshoes, fins, golf balls, leisure vehicles, in particular those intended for activities in cold weather.We can also mention, in general, leisure and DIY articles, tools and road equipment subject to climatic and mechanical aggression, protective articles, such as helmet visors, glasses, as well as the arms of glasses. 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.

[0263] According to a tenth object, the invention relates to the article comprising the semi-aromatic polyamide as defined above, or capable of being obtained by this process.

Claims

1. Claims Compound of the following formula (I): in which: - R1 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, - R2 and R3 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, provided that, when R2 and R3 each represent a -Ph group Or -O-Ph, R2 and R3 can be joined together to form a biphenyl group, - m represents an integer from 0 to 4, - each R4 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, - R5 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 (!): [Chem.36]

2.

3.

4. in which n, R1, R2 and R3 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 (!') as defined in claim 1, the compound thus having the following formula (II'): [Chem.37]

5.

6. wherein R1, R2, R3, R4, 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, R3 is -O-Ph and R2 and R3 together form a biphenyl, the group -(P=O)R2R3 thus having the formula (III): or in which R2 is -Ph-Ph-OH and R3 is hydroxyl, the group -(P=O)R2R3 thus having the formula (IV): gv)

7. A process for preparing a compound according to any one of claims 1 to 6, comprising reacting: - of a compound A of formula (Xla) or (Xlb): [Chem. 40] (Xla) wherein R1 and n are as defined in claim 1, [Chem.41] OOC^h^NH | (Xlb) in which n is as defined in claim 1, [Chem. 42] (XIc) in which n is as defined in claim 1, - with a compound B of formula (XII): in which: - m, L and R4 are as defined in claim 1, and - R7 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): R3 S" P=O (xni) in which R2 and R3 are as defined in claim 1 and R6 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. A method according to claim 7, wherein compound A is laurolactam.

10. A method according to any one of claims 7 to 9, wherein compound B is selected from benzaldehyde, vanillin and ethylvanillin.

11. 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'): (AH, Æ A. O h (xir) wherein L, R4 and m are as defined in claim 1.

12. A method according to claim 11, wherein compound B is selected 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. Semi-aromatic polyamide obtained by polycondensation of a compound according to any one of claims 1 to 6.

16. Semi-aromatic polyamide according to claim 15, obtained by polycondensation of a compound according to claim 5, and comprising a repeating unit of formula (XXII): (XXII)

17. wherein m, n, R2, R3 and R4 are as defined in claim 1 and R5 is as defined in claim 5. Semi-aromatic polyamide according to claim 15, obtained by polycondensation of a compound of formula (II') as defined in claim 4 with an aliphatic diamine of formula H2N-L2-NH2 in which L2 is a divalent aliphatic group comprising from 4 to 36 carbon atoms, said semi-aromatic polyamide comprising a repeating unit of formula (XXI'):

18.

19. wherein m, n, L, R2, R3 and R4 are as defined in claim 1. Semi-aromatic polyamide according to any one of claims 15 to 17, 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. Semi-aromatic polyamide according to any one of claims 15 to 18, further comprising a repeating unit X3.Y3 obtained from the polycondensation of at least one aliphatic, linear or branched or cycloaliphatic diamine X3 and a dicarboxylic acid Y3 aromatic.

20. Semi-aromatic polyamide according to claim 19, 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.

21. VI. Semi-aromatic polyamide according to any one of claims 18 to 20, 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.

22. A semi-aromatic polyamide according to any one of claims 15 to 19, having a mass proportion of atomic phosphorus of at least 0.1%.

23. Semi-aromatic polyamide according to any one of claims 15 to 20, 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.

24. Use of a semi-aromatic polyamide according to any one of claims 15 to 21 as a flame retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof.

25. A process for preparing a semi-aromatic polyamide according to any one of claims 15 to 21 comprising the polycondensation of a compound of formula (I) as defined in claim 1, with one or more other aromatic comonomers.

26. An article comprising a semi-aromatic polyamide according to any one of claims 15 to 21.

27. ​​A method of preparing an article comprising a step of extruding, molding or overmolding the semi-aromatic polyamide according to any one of claims 15 to 21, whereby an article is obtained.