Compound useful for preparing a self-flame retardant transparent polyamide

Abstract

Compound useful for preparing a self-flame retardant transparent polyamide The present invention relates to a compound of the following formula (I): its preparation process, and its use for the preparation of transparent 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 transparent 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 transparent polyamide

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

[0002] Polyamides have exceptional performance in many applications such as transportation, energy, consumer goods such as

[0003] sporting goods, eyewear, industry and consumer electronics.

[0004] Polyamides 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.

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

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

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

[0008] An aim of the invention is to provide a compound which is easy to prepare and usable as a monomer for the preparation of a transparent polyamide, and capable of conferring self-flame retardant properties to said transparent polyamide.

[0009] An aim of the invention is also to provide a polyamide having good flame-retardant properties while retaining its other properties, in particular those listed above, in particular transparency.

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

[0011] For this purpose, the invention relates to a compound of the following formula (I):

[0012] [Chem.l]

[0013] in which:

[0014] - R1 represents H, a linear, branched or cyclic alkyl group comprising from 1 to 12 carbon atoms, or a cation,

[0015] - n represents an integer from 5 to 11,

[0016] - 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,

[0017] 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,

[0018] - m represents an integer from 0 to 4,

[0019] - each R4 is independently selected from hydroxyl, alkyl comprising 1 to 4 carbon atoms and an alkoxyl comprising 1 to 4 carbon atoms,

[0020] - 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,

[0021] - 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'):

[0022] [Chem.2]

[0023] in which n, R1, R2 and R3 are as defined above.

[0024] The compound of formula (I) comprises at least one phosphorus atom, which makes it capable of imparting flame retardant properties to a transparent polyamide prepared using the compound of formula (I) as a monomer.

[0025] 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:

[0026] - n represents 5, 10 or 11, preferably n represents 10,

[0027] - R5 represents a group of formula (!) as defined above, the compound having thus the following formula (II'):

[0028] [Chem.3]

[0029] in which R1, R2, R3, R4, m, n and L are as above,

[0030] or R5 is chosen from hydrogen, hydroxyl, alkyl comprising from 1 to 4 carbon atoms, alkoxyl comprising from 1 to 4 carbon atoms,

[0031] - 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):

[0032] [Chem. 4]

[0033]

[0034] or R2 is -Ph-Ph-OH and R3 is a hydroxyl, the group -(P=O)R2R3 thus having the formula (IV): [Chem. 5] (IV)

[0035]

[0036]

[0037]

[0038]

[0039] The invention also relates to the process for preparing this compound, comprising the reaction: - of a compound A of formula (Xla) or (Xlb): [Chem. 6] R^OOC in which RI and n are as defined above, [Chem. 7]

[0040]

[0041] in which n is as defined above, [Chem. 8]

[0042]

[0043] ■ iXlç) in which n is as defined above, - with a compound B of formula (XII):

[0044] [Chem.9]

[0045] in which:

[0046] - m, L and R4 are as defined above, and

[0047] - 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,

[0048] - and a compound C of formula (XIII):

[0049] [Chem. 10] P—O R* (XH1>

[0050] in which R2 and R3 are as defined above and R6 represents H or OH.

[0051] 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:

[0052] - compound A has the formula (Xla) or (Xlb) as defined above in which n represents 5 or 10, or compound A is laurolactam,

[0053] - compound B is chosen from benzaldehyde, vanillin and ethylvanillin, or well compound B has the formula (XII'):

[0054] [Chem. 11] H (X1F)

[0055] in which L, R4 and m are as defined above, compound B being preferably chosen from terephthalaldehyde and divanillin, - compound C is chosen from 9,10-dihydro-9-oxa- 10-phosphaphenanthrene- 10-oxide, hypophosphorous acid, phenyl phosphorous acid, phosphoric acid, dimethyl- phosphite, diethylphosphite and diphenylphosphite, diphenylphosphine oxide, preferably compound C is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0056] The invention also relates to the use of the compound of formula (I) as a flame retardant.

[0057] 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 transparent polyamide.

[0058] 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 transparent polyamide.

[0059] The invention also relates to a process for preparing a transparent polyamide comprising the polycondensation of a compound of formula (I), optionally in the presence of one or more other comonomers, typically at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl.

[0060] The invention also relates to a transparent polyamide obtained by polycondensation of the compound according to the invention, optionally in the presence of one or more other comonomers, typically at least one cycloaliphatic diamine XI and at least one dicarboxylic acid YL.

[0061] The transparent polyamide comprises a repeating unit derived from the compound of formula (I). The transparent 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 transparent polyamide. The flame retardant is thus integrated reactively and not additively. Advantageously, the transparent polyamides according to the invention are classified V0 in the UL94-vertical buming test, in particular for tests with a transparent polyamide sample 1.6 mm thick. The invention is also based on the discovery that such transparent polyamides not only have good flame retardant properties, but also that they retain the intrinsic performance of the transparent polyamide from which they are derived (transparent polyamides free of a repeating unit derived from the compound of formula (I), but whose other repeating units are identical.For example, a transparent copolyamide PA MACM. 10 whose polymer chain includes repeating units derived from the compound of formula (I) has good flame retardant properties, but retains the properties of PA MACM. 10). Finally, it is possible to prepare transparent polyamides having high molar masses.

[0062] According to advantageous aspects of the invention, the transparent polyamide comprises one or more of the following characteristics, taken in isolation or in all technically possible combinations:

[0063] - the transparent polyamide comprises at least one repeating unit X1.Y1 obtained from from the polycondensation of at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl, the polyamide then being able to further comprise an aliphatic repeating unit A chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam,

[0064] - the transparent 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, and,

[0065] when L2 is not a divalent cycloaliphatic group, with at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl,

[0066] said transparent polyamide comprising a repeating unit of formula (XXI'):

[0067] [Chem. 12] u O (XXQ

[0068] in which:

[0069] - m, n, L, R2, R3 and R4 are as defined above, and

[0070] - L2 is a divalent aliphatic group comprising from 4 to 36 carbon atoms,

[0071] it being understood that, when L2 is not a divalent cycloaliphatic group, then the transparent polyamide further comprises at least one repeating unit X1.Y1 obtained from the polycondensation of at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl,

[0072] - the transparent 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, with at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl,

[0073] said transparent polyamide comprising:

[0074] - a repeating pattern of formula (XXII):

[0075] [Chem. 13]

[0076] in which m, n, L, 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, and

[0077] - at least one repeating unit X1.Y1 obtained from the polycondensation of at least at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl,

[0078] - the transparent polyamide has a mass proportion of atomic phosphorus of at less than 0.1%,

[0079] - the transparent polyamide comprises fillers, reinforcing fibers, in particular glass, additives, in particular chosen from flame retardants, antioxidants, plasticizers and mixtures thereof, or a mixture of these.

[0080] The invention also relates to the use of the transparent polyamide defined above as a flame-retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof.

[0081] The invention also relates to an article comprising the transparent polyamide defined above.

[0082] The invention also relates to a method for preparing an article comprising a step of extruding, molding or overmolding this transparent polyamide, whereby an article is obtained.

[0083] Definitions

[0084] An amorphous polyamide, within the meaning of the application, denotes an amorphous transparent polyamide having only a glass transition temperature (no melting temperature (Tf)), or a very slightly crystalline polyamide having a glass transition temperature and a melting point such that the crystallization enthalpy during the cooling step at a rate of 20K / min in differential scanning calorimetry (DSC) measured according to the ISO 11357-3:2013 standard is less than 30 J / g, in particular less than 20 J / g, preferably less than 15 J / g. The glass transition temperature (Tg) measured by DSC at a heating rate of 20K / min according to the ISO 11357-1:2009 and ISO 11357-2:2013 standards for these polyamides is greater than 75°C, in particular greater than or equal to 100°C, in particular greater than or equal to 12°C, preferably greater than or equal to 140°C.

[0085] A semi-crystalline polyamide (PA), within the meaning of the application, designates a polyamide which has a melting temperature (Tf) in DSC according to the ISO 11357-3:2013 standard, and an enthalpy of crystallization during the cooling step at a rate of 20K / min in DSC measured according to the ISO 11357-3 of 2013 standard greater than 30 J / g, preferably greater than 40 J / g.

[0086] A transparent polyamide, within the meaning of the invention, is a polyamide which, when in the form of a 2 mm thick plate, has a transmittance, measured at a wavelength of 560 nm according to the ISO 13468-2 standard of 2021, at least equal to 80%, preferably at least 85%, or even at least 90%.

[0087] The term "transmittance" is understood to mean the fraction of a luminous flux of a material in the form of a plate with a thickness of 2 mm for a given wavelength. Unless otherwise stated, the transmittance is measured on a Konica-Minolta CM-3610A spectrophotometer according to ISO 13468-2 (Illuminant D65, 10°) on 100 x 100 mm plates with a thickness of 2 mm, at a wavelength of 560 nm.

[0088] The term "Haze value" is understood to describe the transparency of a material in terms of light scattering at an angle greater than 2.5° from the observed normal following the interaction of light with inhomogeneities present in the material. Unless otherwise stated, the Haze value is measured using a Konica-Minolta CM-3610A spectrophotometer according to standard D1003 on 100 x 100 mm plates with a thickness of 2 mm.

[0089] 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.

[0090] The term "polyamide" used in the present description covers both homopolyamides and copolyamides.

[0091] In the PA XY notation, X represents the number of carbon atoms from the diamine residues or the abbreviation for the diamine, and Y represents the number of carbon atoms from the diacid residues or the abbreviation for the diacid, conventionally.

[0092] In the PA X notation, X represents the number of carbon atoms derived from the amino acid or lactam residues.

[0093] The notations PA X / Y, PA X / Y / Z, etc. refer to copolyamides in which X, Y, Z, etc. represent homopolyamide units.

[0094] The polydispersity index IP is equal to the ratio of the molar mass by weight to the molar mass by number (Mw / Mn).

[0095] The number-average molar masses Mn and weight-average molar masses Mw are measured by size exclusion chromatography (or gel permeation chromatography) according to ISO 16014-1:2019. Typically, the polyamide is solubilized in hexafluoroisoproponol stabilized with 0.05 M potassium trifluoroacetate for 24 h at room temperature (20°C) at a concentration of 1 g / L. The solution obtained is then filtered through a PTFE membrane with a porosity of 0.2 pm, then injected at a flow rate of 1 mL / min into a liquid chromatography system equipped with a set of PFG columns from Polymer Standards Service consisting of a pre-column with dimensions of 50 x 8 mm, a 1000 Å column with dimensions of 300 x 8 mm and particle size of 7 pm, and a 100 Å column with dimensions of 300 x 8 mm and particle size of 7 pm. The molar masses are measured by the refractive index and are expressed in PMMA equivalents, used as a calibration standard, then converted to g / mol.

[0096] Total acidity and total basicity are measured by potentiometry.

[0097] The acidity is measured according to the following method. A sample of polyamide is dissolved in benzyl alcohol. Then, this sample is dosed potentiometrically with a 0.02N tetrabutylammonium hydroxide solution.

[0098] The basicity is measured according to the following method. A sample of polyamide is dissolved in metacresol. Then, this sample is dosed potentiometrically with a 0.02N perchloric acid solution.

[0099] The inherent viscosity is measured at a polyamide concentration of 0.5% by weight in solution in metacresol on the total weight of the solution, at 20°C, using a viscometer equipped with a Micro-Ubbelohde viscometer tube.

[0100] The crystallinity rate is calculated according to the following formula:

[0101] [Math.l] X=W xW0 in which:

[0102] x denotes the crystallinity rate,

[0103] AHf * denotes the enthalpy of fusion of the polyamide

[0104] AHf denotes the enthalpy of fusion of 100% crystalline polyamide. This value can be a theoretical value obtained by mathematical models, or if the sample is available, it is the value measured on this sample.

[0105] 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, tertbutyl 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.

[0106] 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.

[0107] According to a first subject, the invention relates to a compound of the following formula (I):

[0108] [Chem. 14]

[0109] in which:

[0110] - R1 represents H, a linear, branched or cyclic alkyl group comprising from 1 to 12 carbon atoms, or a cation,

[0111] - n represents an integer from 5 to 11,

[0112] - 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,

[0113] 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,

[0114] - m represents an integer from 0 to 4,

[0115] - 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,

[0116] - 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,

[0117] - 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):

[0118] [Chem. 15] s3 R" \ / P—O i—( ” COOR1 (Q.

[0119] in which n, R1, R2 and R3 are as defined above.

[0120] 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 polyamide PA A.X1.Y 1 where A is respectively the unit of a PA6, PA11 and PA12. For example, when n is 10, the group -NH(CH2)10-COOR1 is then derived from amino-11-undecanoic acid, and the compound of formula (!') is particularly suitable for being incorporated into a polyamide PA A.X1.Y 1 where A is the repeating unit of a PAU.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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'):

[0125] [Chem. 16] i—CaL (L?

[0126] in which m and R4 are as defined above.

[0127] Two alternatives can be distinguished for the R5 group of formula (I).

[0128] 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):

[0129] [Chem. 17]

[0130] 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 transparent polyamides.

[0131] In a first embodiment of this first alternative, L represents a single bond. The compound then has the following formula (II'a):

[0132] [Chem. 18] (He has)

[0133] in which R1, R2, R3, R4, n and m are as defined above.

[0134] 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):

[0135] [Chem. 19] r'ooc (Il'b)

[0136] 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.

[0137] 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 transparent 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.

[0138] Furthermore, two alternatives can be distinguished for the groups R2 and R3 of formula (I).

[0139] 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):

[0140] [Chem.20]

[0141] The compound then has the following formula (V):

[0142] [Chem.21]

[0143] in which R1, R4, R5, L, n and m are as defined above.

[0144] 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):

[0145] [Chem.22] (IV)

[0146] The compound then has the following formula (VI):

[0147] [Chem.23]

[0148] in which R1, R4, R5, L, n and m are as defined above.

[0149] 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).

[0150] According to a second object, the invention relates to a process for preparing the compound of formula (I), comprising the reaction:

[0151] - of a compound A of formula (Xla) or (Xlb):

[0152] [Chem.24] r'oOC'^^NHs ; (Xla)

[0153] in which R1 and n are as defined above,

[0154] [Chem.25] (Xlb)

[0155] in which n is as defined above,

[0156] [Chem.26] (XIc)

[0157] in which n is as defined above,

[0158] - with a compound B of formula (XII):

[0159] [Chem.27]

[0160] in which:

[0161] - m, L and R4 are as defined above, and

[0162] - 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,

[0163] - and a compound C of formula (XIII):

[0164] [Chem.28] R" \ / P~O (XHI)

[0165] in which R2 and R3 are as defined above and R6 represents H or OH.

[0166] The method according to the invention is illustrated in the following diagram:

[0167] [Chem.29]

[0168] Reaction scheme of the process for preparing the compound of formula (I)

[0169] 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).

[0170] 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 a PA A / X1.Y 1 where A is the unit of a PA6 or a PAU. Typically, compound A is amino-6-hexanoic acid, amino-11-undecanoic acid, or a salt thereof.

[0171] 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 a PA A / X1.Y 1 where A is the unit of a PA 12.

[0172] According to a first preferred embodiment for compound B, compound B is chosen from benzaldehyde, vanillin and ethyl vanillin.

[0173] According to a second preferred embodiment for compound B, compound B has the formula (XII'):

[0174] [Chem.30]

[0175] 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.

[0176] 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)R2R3 has the formula (III) or (IV) as defined above.

[0177] 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.

[0178] Preferably, from 1.0 to 2.5 equivalents of compound A are used relative to compound B.

[0179] Preferably, from 1.0 to 2.5 equivalents of compound C are used relative to compound B.

[0180] Furthermore, the method according to the invention is simple. It is sufficient to mix three compounds.

[0181] The reaction is generally carried out in a solvent, preferably in a polar solvent, for example chosen from methanol, ethanol, isopropanol and diethyl sulfoxide.

[0182] The mass concentration of compounds A+B+C in the solvent is generally 20 g / L to 250 g / L.

[0183] The reaction is typically carried out at a temperature of 50 to 100°C and / or at atmospheric pressure.

[0184] 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.

[0185] The subsequent treatment (work-up in English) 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 base the reaction medium. The process is therefore preferably free from an acidification or basification step.

[0186] According to a third subject, the invention relates to the use of the compound of formula (I) as defined above as a flame retardant.

[0187] 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 transparent polyamide.

[0188] According to a fifth subject, the invention relates to the use of the compound of formula (I) as a monomer or as a comonomer, typically for the preparation of a (co)polymer, in particular a transparent polyamide. The invention relates to a process for the preparation of 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 the preparation of a transparent polyamide comprising the polycondensation of a compound of formula (I), optionally in the presence of one or more other comonomers, in particular in the presence of one or more other cycloaliphatic comonomers. Advantageously, the compound of formula (I) does not act as a chain limiter, and it is possible to prepare transparent polyamides having a high molar mass.

[0189] The process for preparing a transparent polyamide typically comprises the polycondensation of a compound of formula (I), at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl.

[0190] A non-exhaustive list of these cycloaliphatic diamines XI is given in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405).

[0191] The cycloaliphatic diamine XI is preferably a primary diamine (two NH2 groups).

[0192] The cycloaliphatic diamine XI may be chosen from bis(3,5-dialkyl-4-aminocyclohexyl)methane, bis(3,5-dialkyl-4-aminocyclohexyl)ethane, bis(3,5-dialkyl-4-aminocyclohexyl)propane, bis(3,5-dialkyl-4-aminocyclohexyl)butane, l,3-bis(aminomethyl)cyclohexane (1,3-BAC), l,4-bis(aminomethyl)cyclohexane (1,4-BAC), bis-(3-methyl-4-aminocyclohexyl)methane or 3'-dimethyl-4,4'-diamino-dicyclohexylmethane (BMACM, MACM or B), bis-(4-aminocyclohexyl)methane (BACM), p-bis(aminocyclohexyl)methane (PACM or P), isopropylidenedi(cyclohexylamine) (PACP), 2-2-bis-(3-methyl-4-aminocyclohexyl)-propane (BMACP), isophorone-diamine (IPDA or IPD) and 2,6-bis(amino methyl)norbornane (BAMN) and piperazine.

[0193] Advantageously, the cycloaliphatic diamine XI 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).

[0194] In an advantageous embodiment, the cycloaliphatic diamine XI is a bicycloaliphatic diamine, in particular chosen from 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane (B), p-bis(aminocyclohexyl)-methane (P).

[0195] The dicarboxylic acid Y1 may be chosen from linear or branched aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids and aromatic dicarboxylic acids.

[0196] The dicarboxylic acid Y1 has in particular from 4 to 36 carbon atoms, preferably those having from 6 to 18 carbon atoms.

[0197] As an example of aliphatic dicarboxylic acid Y1, it is possible to cite succinic acid (4), pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), octanedioic acid (8), azelaic acid (9), sebacic acid (10), undecanedioic acid (11), dodecanedioic acid (12), brassylic acid (13), tetradecanedioic acid (14), hexadecanedioic acid (16), octadecanoic acid (18), octadecenedioic acid (18), eicosanedioic acid (20), docosa-nedioic acid (22) and dimerized fatty acids, in particular those containing 36 carbons. These dimerized fatty acids preferably have a dimer content of at least 98%; preferably they are hydrogenated; these are, for example, the products marketed under the brand name "PRIPOL" by the company "Cargill", or under the brand name EMPOL by the company BASF, or under the brand name Radiacid by the company OLEON, and polyoxyalkylene a,co-diacids.Fatty acid dimers are typically dimerized fatty acids obtained by oligomerization or polymerization of long-chain unsaturated monobasic hydrocarbon fatty acids (such as linoleic acid and oleic acid), as described in particular in EP 0 471 566.

[0198] 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).

[0199] When the dicarboxylic acid Y1 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.

[0200] When the dicarboxylic acid Y1 is aromatic, it is preferably chosen from terephthalic acid, isophthalic acid, furanedicarboxylic acid, and diacid naphthalenic acid, particularly preferably among terephthalic acid and isophthalic acid.

[0201] In one embodiment, the process for preparing a transparent polyamide comprises the polycondensation of a compound of formula (I), at least one cycloaliphatic diamine XI, at least one dicarboxylic acid Yl and at least one monomer A chosen from an amino acid and a lactam.

[0202] Monomer A is preferably aliphatic.

[0203] 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).

[0204] 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).

[0205] According to a sixth subject, the invention relates to a transparent polyamide obtained by polycondensation of the compound of formula (I) according to the invention, optionally in the presence of one or more other comonomers, typically one or more other cycloaliphatic comonomers.

[0206] Transparent polyamide X1.Y1

[0207] In particular, the invention relates to a transparent polyamide obtained by polycondensation of the compound of formula (I) according to the invention, of at least one cycloaliphatic diamine XI and of at least one dicarboxylic acid Yl. It then comprises, in addition to the repeating unit derived from the compound of formula (I), a repeating unit Xl.Y 1 derived from the polycondensation of the cycloaliphatic diamine XI and the dicarboxylic acid Yl.

[0208] The embodiments described above for the compound of formula (I) are of course applicable for the repeating unit derived from the compound of formula (I), and for the transparent polyamide comprising it. Similarly, the embodiments described above for the cycloaliphatic diamine XI and for the dicarboxylic acid Y1 are also applicable for the repeating unit X1.Y1 derived therefrom.

[0209] Two preferred alternatives of the transparent polyamide can be distinguished, depending on the alternative considered for the R5 group of the compound of formula (I).

[0210] According to a first alternative, the transparent polyamide is obtained by polycondensation of a compound of formula (I) in which R5 represents a group of formula (!') as defined above. The transparent polyamide is then obtained by polycondensation of a compound of formula (II') as defined above with an aliphatic diamine of formula H2N-L2-NH2 in which L2 is a divalent aliphatic group comprising from 4 to 36 carbon atoms,

[0211] and, when L2 is not a divalent cycloaliphatic group, with at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl,

[0212] said transparent polyamide then comprising a repeating unit of formula (XXI'):

[0213] [Chem.31]

[0214] in which m, n, L, L2, R2, R3 and R4 are as defined above,

[0215] it being understood that when L2 is not a divalent cycloaliphatic group, then the transparent polyamide further comprises at least one repeating unit X1.Y1 obtained from the polycondensation of at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl.

[0216] Two alternatives can be distinguished depending on whether the L2 group is cycloaliphatic or not.

[0217] According to a first alternative for the group L2 of the formula (XXI'), L2 is a divalent cycloaliphatic group. The transparent polyamide is then obtained by polycondensation of a compound of formula (II') as defined above with an aliphatic diamine of formula H2N-L2-NH2 in which L2 is a divalent cycloaliphatic group comprising from 4 to 36 carbon atoms, said transparent polyamide comprising a repeating unit of formula (XXI') as defined above. As the group L2 is itself cycloaliphatic, the transparent polyamide may be free of any repeating unit other than that of formula (XXI'), or comprise one or more other repeating units, which may be cycloaliphatic (in particular the unit X1.Y1 as defined above) or not. The polyamide may be free of or comprise at least one repeating unit X1.Y1 obtained from the polycondensation of at least a cycloaliphatic diamine XI and at least one dicarboxylic acid Yl.

[0218] Preferably, in this first alternative for the L2 group, the L2 group is a cycloaliphatic group comprising from 3 to 36 carbon atoms.

[0219] Preferably, in formula (XXI'), the group -NH-L2-NH- is 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, 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.

[0220] Typically, in formula (XXI'), L2 corresponds to the following formula (L2cydo):

[0221] [Chem.32]

[0222] 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).

[0223] For example, in formula (XXI'), the group -NH-L2-NH- is 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), l,3-bis(aminomethyl)cyclohexane (1,3-BAC) and isophorone-diamine (IPDA or IPD).

[0224] According to a second alternative for the group L2 of the formula (XXI'), L2 is not cycloaliphatic. The transparent polyamide is obtained by polycondensation of a compound of formula (II') as defined above with an aliphatic diamine of formula H2N-L2-NH2 in which L2 is a divalent aliphatic group, not being cycloaliphatic, and comprising from 4 to 36 carbon atoms, with at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl, said transparent polyamide comprising:

[0225] - a repeating unit of formula (XXI') as defined above, and

[0226] - at least one repeating unit X1.Y1 obtained from the polycondensation of at least at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl.

[0227] Preferably, in this second alternative, in formula (XXI'), 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- then comes from a linear and aliphatic diamine. In this second alternative for the group L2, the transparent polyamide comprises at least one repeating unit XL Y1 obtained from the polycondensation of at least one cycloaliphatic diamine XI and at least one dicarboxylic acid YL

[0228] According to a second alternative, the transparent 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 with at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl, the transparent polyamide comprising:

[0229] - a repeating pattern of formula (XXII):

[0230] [Chem.33]

[0231] 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, and

[0232] - at least one repeating unit X1.Y1 obtained from the polycondensation of at least at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl.

[0233] Whatever the alternative / embodiment considered, the transparent polyamide generally comprises, in addition to the repeating unit derived from the compound of formula (I) (typically in addition to the repeating unit of formula (XXI') or (XXII) defined above), one or more other unit(s), and in particular a unit XI.Y1 as defined above.

[0234] In particular, the invention relates to a transparent polyamide obtained by polycondensation of the compound of formula (I) according to the invention, of at least one cycloaliphatic diamine XI and of at least one dicarboxylic acid Yl.

[0235] Preferably, the transparent polyamide comprises, in addition to the repeating units derived from the compound of formula (I), repeating units chosen from the repeating units of a PA chosen from PA MACM.10, PA PACM.10, PA MACM.12, PA PACM.12, PA MACM.14, PA PACM.14, PA MACM.18, PA PACM.18, MACM.I, MACM.T and a mixture thereof, for example PA MACM.I / MACM.T.

[0236] In a particularly preferred manner, the polyamide comprises, in addition to the repeating units derived from the compound of formula (I), repeating units chosen from the repeating units of a PA chosen from MACM.10, PA MACM.12, and PA MACM.14.

[0237] Preferably, the polyamide comprising the repeating unit derived from the compound of formula (I) and the repeating unit X1.Y1 is amorphous.

[0238] Transparent copolyamide A / X1.Y 1

[0239] In one embodiment, the transparent polyamide is obtained by polycondensation of the compound of formula (I) according to the invention, of at least one cycloaliphatic diamine XI, of at least one dicarboxylic acid Yl and of at least one monomer A chosen from an amino acid and a lactam.

[0240] The embodiments described above for monomer A are applicable.

[0241] The transparent polyamide therefore comprises, in addition to the repeating unit resulting 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 A chosen from a unit obtained from at least one amino acid and a unit obtained from at least one lactam.

[0242] The amino acid is in particular as defined above. Preferably, the amino acid comprises from 9 to 12 carbon atoms. It can thus be chosen from 9-aminononanoic acid (denoted 9), 10-aminodecanoic acid (denoted 10), 11-aminoundecanoic acid (denoted 11) and 12-aminododecanoic acid (denoted 12). Preferably, the repeating unit A is obtained from 11-aminoundecanoic acid (H).

[0243] The lactam is in particular as defined above, is preferably caprolactam (6) or lauryllactam (12).

[0244] Advantageously, the units of type A are units of PA 11 (polyundecanamide), PA 12 (polydodecanamide) or PA 6 (polycaprolactam).

[0245] Preferably, the polyamide comprises, in addition to the repeating unit derived from the compound of formula (I), repeating units chosen from the repeating units of a PA chosen from PA Z / MACM.10, PA Z / MACM.12, PA Z / MACM.14, in which Z represents 11, 12, 10.10 or 10.12.

[0246] More particularly preferably, the repeating unit A is obtained from a single amino acid or a single lactam. However, it is entirely possible to envisage using, to obtain this same unit A, a mixture of two or more aminocarboxylic acids, a mixture of two or more lactams, but also a mixture of one, two or more aminocarboxylic acids with one, two or more lactams.

[0247] Preferably, the polyamide comprises, in addition to the repeating unit derived from the compound of formula (I), repeating units chosen from the repeating units of a PA chosen from PA 11 / MACM.10, PA 11 / PACM.10, PA 11 / MACM.12, PA 11 / PACM.12, PA 11 / MACM.14, PA 11 / PACM.14, PA 11 / MACM.18, PA 11 / PACM.18, PA 12 / MACM.10, PA 12 / PACM.10, PA 12 / MACM.12, PA 12 / PACM.12, PA 12 / MACM.14, PA 12 / PACM.14, PA 12 / MACM.18, PA 12 / PACM.18, le PA 10.10 / MACM.10, le PA 10.10 / PACM.10, le PA 10.10 / MACM.12, the PA 10.10 / PACM.12, the PA 10.10 / MACM.14, the PA 10.10 / PACM.14, the PA 10.10 / MACM.18, the PA 10.10 / PACM.18, the PA 10.12 / MACM.10, the PA 10.12 / PACM.10, the PA 10.12 / MACM.12, the PA 10.12 / PACM.12, the PA 10.12 / MACM.14, the PA 10.12 / MACM.14, the PA 10.12 / MACM.18, the PA 10.12 / PACM.18, the PA 12.10 / MACM.10, the PA 12.10 / PACM.10, the PA 12.10 / MACM.12, the PA 12.10 / PACM.12, the PA 12.10 / MACM.14, the PA 12.10 / PACM.14, the PA 12.10 / MACM.18, the PA 12.10 / PACM.18, the PA 12.12 / MACM.10, the PA 12.12 / PACM.10, the PA 12.12 / MACM.12, the PA 12.12 / PACM.12, the PA 12.12 / MACM.14, the PA 12.12 / PACM.14, the PA 12.12 / MACM.18, the PA 12.12 / PACM.18, le PA 10.14 / PACM.10, le PA 10.14 / MACM.12, the PA 10.14 / PACM.12, the PA 10.14 / MACM.14, the PA 10.14 / PACM.14, the PA 10.14 / MACM.18, the PA 10.14 / PACM.18, the PA 12.14 / MACM.10, the PA 12.14 / PACM.10, the PA 12.14 / PACM.12, the PA 12.14 / PACM.12, the PA 12.14 / MACM.14, the PA 12.14 / PACM.14, the PA 12.14 / MACM.18, the PA 12.14 / PACM.18, the PA PACM.10 / MACM.10, the PA PACM.12 / MACM.12, the PA PACM.14 / MACM.14, PA 11 / PACM.1O / MACM.1O, 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, the PA 11 / BMACM.6, the PA 11 / BMACM.6, the PA 11 / PACM.6, the PA 11 / IPD.6, the PA 12 / BMACM.6, the PA 12 / PACM.6, the PA 12 / IPD.6, the PA 11 / BMACM.1O, the PA 11 / IPD.1O, 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. .

[0248] Preferably, the polyamide comprises, in addition to the repeating unit derived from the compound of formula (I), repeating units chosen from the repeating units of a PA chosen from 11 / BMACM.6, 11 / PACM.6, 11 / IPD.6, 12 / BMACM.6, 12 / PACM.6, 12 / IPD.6, 11 / BMACM.10, 11 / PACM.10, 11 / IPD.10, 12 / BMACM.10, 12 / PACM.10, 12 / IPD.10, 11 / BMACM.14, 11 / PACM.14, 11 / IPD.14, 12 / BMACM.14, 12 / PACM.14, 12 / IPD.14.

[0249] The polyamide comprising the repeating unit derived from the compound of formula (I), the unit A and the unit X1.Y1 may be amorphous or semi-crystalline, and is preferably amorphous.

[0250] The embodiments described below are applicable for any transparent polyamide according to the invention.

[0251] The transparent polyamide according to the invention generally has a transmittance greater than 80%, advantageously greater than 85%, in particular greater than or equal to 90%.

[0252] In one embodiment, the transparent polyamide according to the invention has a Haze value of less than 15%, advantageously less than 10%, preferably less than 5%.

[0253] Preferably, the transparent 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.

[0254] Advantageously, the transparent polyamide is classified V0 in the UL94-vertical test. burning, especially for a test with a 1.6 mm thick transparent polyamide sample.

[0255] The number-average molar mass Mn of the transparent 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 transparent polyamide can therefore advantageously have a high molar mass.

[0256] The weight-average molar mass Mw of the transparent 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.

[0257] The polydispersity index IP of the transparent 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.

[0258] The polydispersity index IP of the transparent polyamide is generally greater than or equal to 1.0, in particular greater than or equal to 2.0.

[0259] The absolute value of the difference between the total acidity and the total basicity of the transparent polyamide is preferably between 0 and 200 peq / g.

[0260] Preferably, the transparent polyamide has an inherent viscosity of between 0.40 and 1.70.

[0261] The transparent polyamide can be amorphous or semi-crystalline.

[0262] The transparent 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.

[0263] Among the reinforcing fibers, mention may be made of carbon or glass fibers, natural fibers or a mixture thereof.

[0264] Among the additives, mention may be made of flame retardants, chain limiting agents, impact modifiers, pigments, dyes, light (UV) and / or heat stabilizers, plasticizers, surfactants, optical brighteners, antioxidants, natural waxes, mold release agents, or mixtures thereof.

[0265] The flame retardants are in particular chosen from DOPO and its derivatives, melamine cyanurate, melamine polyphosphate, red phosphorus, metallic dialkylphosphinates and mixtures thereof.

[0266] To the extent that the transparent polyamides according to the invention are self-flame retardant, they can be free of flame retardant agent (used as an additive).

[0267] 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 allows reaction with the amide, amine or transparent polyamide carboxylic acid.

[0268] 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 transparent polyamide may comprise an impact modifier, in particular of an elastomeric nature and preferably functionalized by maleic anhydride.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] The mass proportion of the fillers is in particular from 0.5 to 50.0% relative to the weight of the transparent polyamide.

[0273] The mass proportion of the reinforcing fibers is in particular 5 to 75% relative to the weight of the transparent polyamide.

[0274] The mass proportion of the additives is in particular 0.05 to 3.00% relative to the weight of the transparent polyamide.

[0275] The cumulative mass proportion of the fillers, reinforcing fibers, and additives is in particular 0.1 to 80% relative to the weight of the transparent polyamide.

[0276] According to a seventh object, the invention relates to the use of the transparent polyamide defined above as a flame-retardant additive in thermoplastic polymer matrices, in particular polyamide, polyolefin, polyester, PMMA or mixtures thereof.

[0277] According to an eighth object, the invention relates to a method for preparing an article comprising a step of extruding, molding or overmolding the transparent polyamide defined above, whereby an article is obtained.

[0278] 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 transparent 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 good impact resistance and good endurance to mechanical, chemical, UV and thermal aggression. These sporting articles include 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. Mention may also be made, in general, of 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.Non-limiting examples include car components such as headlight guards, rearview mirrors, small parts for off-road vehicles, tanks, in particular, for mopeds, motorcycles, scooters, subject to mechanical and chemical attack, screws, cosmetic items subject to mechanical and chemical attack, lipsticks, pressure gauges, aesthetic protection elements such as gas bottles. Mention may also be made of objects or parts of objects for electronics requiring compliance with dimensions, for example parts for mobile phones, computers, tablets, etc.

[0279] According to a ninth object, the invention relates to the article comprising the transparent polyamide as defined above, or capable of being obtained by this process.

Claims

Claims

1. 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 R” * "COOR1

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):

7. A process for preparing a compound according to any one of claims 1 to 6, comprising the reaction: - of a compound A of formula (Xla) or (Xlb): [Chem. 40] R^OOG'^^NHg (Xla) wherein R1 and n are as defined in claim 1, [Chem.41] (Xlb) wherein 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): (Xi I) 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): [Chem. 44]

8.

9.

10.

11. (XIII) wherein R2 and R3 are as defined in claim 1 and R6 represents H or OH. A method according to claim 7, wherein compound A has the formula (Xla) or (Xlb), wherein n represents 5 or 10. The method of claim 7, wherein compound A is laurolactam. A method according to any one of claims 7 to 9, wherein compound B is selected from benzaldehyde, vanillin and ethylvanillin. 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'): H (XH!)

12.

13.

14.

15. wherein L, R4 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. Transparent polyamide obtained by polycondensation of a compound according to

16.

17.

18. any one of claims 1 to 6. Transparent polyamide according to claim 15, comprising at least one repeating unit X1.Y1 obtained from the polycondensation of at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl. Transparent polyamide according to claim 16, 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. Transparent polyamide according to claim 16 or 17, obtained by polycondensation of a compound according to claim 5 with at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl, said transparent polyamide comprising: - a repeating pattern of formula (XXII):

19. wherein m, n, L, R2, R3 and R4 are as defined in claim 1 and R5 is as defined in claim 5, and - at least one repeating unit X1.Y1 obtained from the polycondensation of at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl. Transparent polyamide according to any one of claims 15 to 17, obtained by polycondensation: - 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, and, - when L2 is not a divalent cycloaliphatic group, with at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl, said transparent polyamide comprising a repeating unit of formula (XXI'):

20.

21.

22.

23.

24.

25. in which: - m, n, L, R2, R3 and R4 are as defined in claim 1, and - L2 is a divalent aliphatic group comprising from 4 to 36 carbon atoms, it being understood that, when L2 is not a divalent cycloaliphatic group, then the transparent polyamide further comprises at least one repeating unit X1.Y1 obtained from the polycondensation of at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl. Transparent polyamide according to any one of claims 15 to 19, having a mass proportion of atomic phosphorus of at least 0.1%. Transparent 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. Use of a transparent 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. Process for the preparation of a transparent polyamide according to any one of claims 15 to 21 comprising the polycondensation of a compound of formula (I) as defined in claim 1, optionally with at least one cycloaliphatic diamine XI and at least one dicarboxylic acid Yl. An article comprising a transparent polyamide according to any one of claims 15 to 21. Process for preparing an article comprising a step of extruding, molding or overmolding the transparent polyamide according to one of any of claims 15 to 21, whereby an article is obtained.