Flame-retardant low-viscosity polyamide composition and use thereof for preparing a composite

Abstract

The invention relates to a polyamide composition comprising: a polyamide or a mixture of polyamides, said polyamide or, as appropriate, mixture of polyamides having an inherent viscosity of at most 0.8; and at least one compound of formula (1). The invention also relates to the use of same for preparing a composite.

Description

[0001] Flame-retardant low-viscosity polyamide composition and its use for composite preparation

[0002] Field of invention

[0003] The present invention relates to a flame-retardant low-viscosity polyamide composition and its use, in particular for the preparation of composites.

[0004] Technical background

[0005] Composites, and more specifically composites comprising reinforcing fibers impregnated with a polymer matrix, are used in many technical fields, particularly in aeronautics, aerospace, wind, automotive, railway and marine applications. These applications mainly require composites with high mechanical performance, particularly at high operating temperatures.

[0006] Polyamides are interesting in the manufacture of such composites, particularly due to their lightness and recyclability. However, they have a high viscosity, even in the molten state, which makes the impregnation of fibrous substrates, for the preparation of composites, complicated and causes impregnation defects likely to cause mechanical deficiencies.

[0007] Low viscosity polyamide compositions have been developed for the impregnation of these fibrous substrates, said impregnated fibrous substrates are then used, during this use the low viscosity polyamide composition will polymerize and consequently increase in viscosity to provide a matrix having in particular good mechanical properties.

[0008] A similar viscosity increase process also exists for polyamide compositions intended, for example, for the manufacture of parts by rotational molding and for the coating of metal supports with powders.

[0009] Polyamide compositions, particularly those intended for the preparation of these composites, may have limitations in their use due to inadequate fire resistance, particularly in the field of transport, electronic or electrical applications or those intended for use in public places. This is why the flame retardancy of polymer compositions has always been an important area of ​​research. In addition, polyamides are difficult to flame retard since, when melted, they release gases that fuel the flames.

[0010] Flame retardant compositions containing halogenated or antimony-based compounds have long been used. However, their eco- and genotoxic potential has severely restricted the applications in which they can be used.

[0011] As a replacement, it is known to use compounds of metal salts of phosphorus compounds such as aluminum phosphinates, metal oxides of a transition metal from Group VB, VIB, VI IB or VI II B of the periodic system, organic compounds such as melamine polyphosphates or melamine cyanurates as indicated in EP3700976. These compounds, not totally compatible with polymer matrices, do not however allow good fire resistance to be obtained unless significant contents are used which then have a negative impact on the properties of the matrix, in particular the mechanical properties (in particular due to the agglomeration and / or precipitation of the compounds of metal salts of phosphorus compounds in the matrix in an uncontrolled manner). As an example, we can cite the flame retardant fillers marketed under the name Exolit® by the company Clariant.These flame retardant fillers are immiscible in polyamide resins, which degrades the mechanical properties of the resin.

[0012] DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and DOPO derivatives, notably obtained by reaction with itaconic acid (ITA), are also known for flame retarding polymer matrices. However, the use of these compounds will limit the maximum achievable molar mass of the polyamide chains and will therefore prevent the rise in viscosity of the polyamide composition, thus limiting the properties, notably mechanical, of the composite obtained.

[0013] There is therefore an interest in providing polyamide compositions having good flame retardant properties while allowing a rise in viscosity, for example during its processing. There is therefore an interest in providing a flame retardant polyamide composition for which the flame retardant does not prevent the rise in viscosity of said polyamide composition. There is also an interest in providing such a composition which has good mechanical properties or limits the reduction in mechanical properties compared to the composition not comprising said compound.

[0014] The objective is thus to provide a composition that provides a compromise between good fire resistance properties, in particular a low self-extinguishing time, and an increase in viscosity of the composition. Another objective is to provide such a composition that also has good mechanical properties, in particular in terms of ductility and elongation at break.

[0015] Yet another objective is to provide such a composition having at least one of the following additional properties:

[0016] Good dispersion of the flame retardant compound in the composition;

[0017] Solubility of the flame retardant compound in the composition;

[0018] Absence of toxicity of the flame retardant compound. Summary of the invention

[0019] The present invention relates to a polyamide composition comprising:

[0020] - A polyamide or a mixture of polyamides in which the polyamide, or where appropriate, the mixture of polyamides, has an inherent viscosity of not more than 0.8; and

[0021] - A compound of formula (1): in which: p represents 0 or 1;

[0022] R 1 and R 2 , identical or different, represent:

[0023] - H ;

[0024] - a linear or branched alkyl group comprising from 1 to 10 carbon atoms;

[0025] - a group of formula (2) n represents an integer chosen from 0, 1, 2, 3 or 4

[0026] R 5 , identical or different, represents:

[0027] - an alkyl group, linear or branched, comprising from 1 to 30 carbon atoms;

[0028] - a cycloalkyl group, comprising from 3 to 30 carbon atoms;

[0029] - an alkoxy group, the alkyl part of which, linear or branched, comprises from 1 to 30 carbon atoms;

[0030] - an -O-cycloalkyl group in which the cycloalkyl comprises from 3 to 30 carbon atoms; - an aryl group comprising from 6 to 30 carbon atoms;

[0031] - an aryloxy group, the aryl part of which comprises from 6 to 30 carbon atoms;

[0032] - an -Alk-aryl group with Alk representing a linear or branched alkyl comprising from 1 to 30 carbon atoms and aryl comprising 6 to 30 carbon atoms;

[0033] R 6 , identical or different, represents a bond or a group -(CF )™- where m is an integer between 1 and 5; at least one of R 1 or R 2 represents a group of formula (2), when R 1 and R 2 both represent a group of formula (2) these groups may be the same or different; or R 1 and R 2form a cycle of formula (3) with

[0034] R 7 represents a group of formula (4) n represents 0, 1, 2, 3, or 4

[0035] R 5 represents an alkyl group, linear or branched, comprising 1 to 30 carbon atoms, optionally substituted;

[0036] R 8 represents a hydrogen atom, a group of formula (4) or an alkyl group comprising from 1 to 10 carbon atoms;

[0037] R 9 and R 10 , identical or different, represent H, an alkyl group comprising from 1 to 10 carbon atoms or R 9 and R 10 form a bridge comprising one or two CH2 groups;

[0038] R represents: a linear or branched alkylene group comprising from 4 to 36 carbon atoms, optionally the alkylene is interrupted by at least one heteroatom and / or is optionally substituted; a cycloalkylene group comprising from 4 to 10 carbon atoms; an alkylene-cycloalkylene-alkylene group, the linear or branched alkylene comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, optionally substituted, the cycloalkylene comprising from 4 to 10 carbon atoms; a cycloalkylene-alkylene-cycloalkylene group, the linear or branched alkylene comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, optionally substituted, the cycloalkylene comprising from 4 to 10 carbon atoms; an arylene group comprising from 6 to 30 carbon atoms;an alkylene-arylene-alkylene group in which the alkylenes, identical or different, are linear or branched alkylenes comprising from 1 to 10 carbon atoms and the arylene comprises from 6 to 30 carbon atoms; an alkylene-arylene group in which the alkylenes, identical or different, are linear or branched alkylenes comprising from 1 to 10 carbon atoms and the arylene comprises from 6 to 30 carbon atoms;

[0039] A represents:

[0040] - a hydrogen atom;

[0041] - a group of formula (5) with r representing 0 or 1;

[0042] R 3 or R 4 , identical or different, represent:

[0043] - H ;

[0044] - a linear or branched alkyl group comprising from 1 to 10 carbon atoms;

[0045] - a group of formula (2') n represents an integer chosen from 0, 1, 2, 3 or 4

[0046] R5 , identical or different, represents:

[0047] - an alkyl group, linear or branched, comprising from 1 to 30 carbon atoms;

[0048] - a cycloalkyl group, comprising from 3 to 30 carbon atoms;

[0049] - an alkoxy group, the alkyl part of which, linear or branched, comprises from 1 to 30 carbon atoms;

[0050] - an -O-cycloalkyl group in which the cycloalkyl comprises from 3 to 30 carbon atoms;

[0051] - an aryl group comprising from 6 to 30 carbon atoms;

[0052] - an aryloxy group, the aryl part of which comprises from 6 to 30 carbon atoms;

[0053] - an -Alk-aryl group with Alk representing a linear or branched alkyl comprising from 1 to 30 carbon atoms and aryl comprising 6 to 30 carbon atoms;

[0054] R 6, identical or different, represents a bond or a group -(CF )™- where m is an integer between 1 and 5, preferably 1; at least one of R 3 or R 4 represents a group of formula (2'), when R 3 and R 4 both represent a group of formula (2') these groups may be the same or different; or R 3 and R 4 form a cycle of formula (3') with

[0055] R 7 represents a group of formula (4')

[0056] R 5 represents a hydrogen atom or an alkyl group comprising from 1 to 10 carbon atoms;

[0057] R 8 represents a hydrogen atom, a group of formula (4') or an alkyl group comprising from 1 to 10 carbon atoms;

[0058] R 9 and R 10 , identical or different, represent H, an alkyl group comprising from 1 to 10 carbon atoms or R 9and R 10 form a bridge comprising one or two CH2 groups.

[0059] Preferably, the compound of formula (1) is a compound of formula (Ia)

[0060] Preferably, in this compound (la):

[0061] - R represents a linear or branched alkylene group comprising from 6 to 18 carbon atoms;

[0062] - R 1 and R 3 , identical, represent a group of formula (2): n equal to 0

[0063] R 6 represents a bond or a CH2 group, n represents 0;

[0064] - R 2 and R 4represent H. Preferably, the composition comprises, relative to the total weight of the composition, from 50 to 99%, preferably from 60 to 99%, preferably from 70 to 99%, preferably from 80 to 99%, preferably from 85 to 95%, by weight of the polyamide or the polyamide mixture and from 1 to 40%, preferably from 4 to 30%, preferably from 5 to 20%, by weight of at least one compound of formula (1).

[0065] The composition may comprise from 0.01 to 40%, preferably from 0.01 to 20% by weight, preferably from 0.01 to 10% by weight, more preferably from 0.01 to 5%, by weight of additive relative to the total weight of the composition.

[0066] Preferably, the polyamide of the composition is chosen from: aliphatic polyamides chosen from polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 66 (PA-66), polyamide 46 (PA-46), polyamide 610 (PA-610), polyamide 612 (PA-612), polyamide 1010 (PA-1010), polyamide 1012 (PA-1012), polyamide 11 / 1010 and polyamide 12 / 1010, or a mixture thereof or a copolyamide thereof, and polyetheramide or polyetheresteramide (PEBA) copolymers (or copolymer with polyamide blocks and polyether blocks); preferably chosen from polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 66 (PA-66), polyamide 46 (PA-46), polyamide 610 (PA-610), polyamide 612 (PA-612), polyamide 1010 (PA-1010), polyamide 1012 (PA-1012), polyamide 11 / 1010 and polyamide 12 / 1010, or a mixture thereof;semi-aromatic polyamides, optionally modified by urea units, chosen from a PA MXD6 and a PA MXD10 or a semi-aromatic polyamide of formula A / XT in which A is chosen from a unit obtained from at least one amino acid, a unit obtained from at least one lactam and at least one unit corresponding to the formula (Ca diamine). (Cb diacid), with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the unit (Ca diamine) being chosen from aliphatic, linear or branched diamines, cycloaliphatic diamines and alkylaromatic diamines and the unit (Cb diacid) being chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids and aromatic diacids;XT denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid, with x representing the number of carbon atoms of the Cx diamine, x being between 6 and 36, advantageously between 9 and 18, in particular a polyamide of formula A / 6T, A / 9T, A / 10T or A / 11T, A being as defined above, in particular a polyamide PA 6 / 6T, a PA 66 / 6T, a PA 6I / 6T, a PA MPMDT / 6T, a PA PA11 / 10T, a PA 11 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, a PA 11 / BACT, PA BACT / 10T / 6T, a PA 11 / BACT / 10T; T corresponds to terephthalic acid, MXD corresponds to m-xylylenediamine, MPMD corresponds to methylpentamethylenediamine and BAC corresponds to 1,3-bis(aminomethyl)cyclohexane alone or in a mixture with 1,4-bis(aminomethyl)cyclohexane; polyetheramide or polyetheresteramide copolymers (PEBA) (or copolymer with polyamide blocks and polyether blocks).;

[0067] The present invention also relates to a composite comprising fibers impregnated with the composition according to the invention.

[0068] The present invention also relates to the use of a composition according to the invention for the preparation of a composite comprising fibers.

[0069] The present invention also relates to a composite obtained by impregnation of fibers with the composition according to the invention.

[0070] Detailed description

[0071] The invention is now described in more detail and in a non-limiting manner in the following description.

[0072] Unless otherwise stated, all percentages are by mass.

[0073] In this text, the quantities indicated for a given species may apply to this species according to all its definitions (as mentioned in this text), including the more restricted definitions.

[0074] In the context of the present invention, the term “viscosity increase” means the fact, for a starting composition comprising, preferably predominantly, at least one polyamide or where appropriate a mixture of polyamides, and having a determined inherent viscosity, of seeing its inherent viscosity increase in particular by heating to a temperature higher than the glass transition temperature (Tg) of said composition, preferably at a temperature higher than the glass transition temperature (Tg) of the starting polyamide composition by at least 10°C, preferably at least 20°C, preferably at least 100°C, even more preferably between 120 and 340°C.The increase in viscosity reflects the polymerization of the starting polyamide composition by reaction, for example by polycondensation on itself or by polyaddition with a chain extender, to result in a final product having an inherent viscosity at least 10% higher than the inherent viscosity of the starting polyamide or polyamide mixture in the absence of the compound (1).

[0075] Tg is determined by differential scanning calorimetry (DSC) according to ISO 11357-2:2013.

[0076] It is thus necessary to distinguish between the starting polyamide composition having a low inherent viscosity and the final polyamide composition (after processing) which has an inherent viscosity at least 10%, preferably at least 25%, higher than that of the starting polyamide composition in the absence of compound (1).

[0077] Polyamide composition

[0078] The invention relates firstly to a polyamide composition comprising:

[0079] - a polyamide or a mixture of polyamides, said polyamide, or where appropriate said mixture of polyamides, having an inherent viscosity of at most 0.8;

[0080] - at least one compound of formula (1) in which: p represents 0 or 1;

[0081] R 1 and R 2 , identical or different, represent:

[0082] - H ;

[0083] - a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms;

[0084] - a group of formula (2) n represents an integer chosen from 0, 1, 2, 3 or 4 R 5 , identical or different, represents:

[0085] - a linear or branched alkyl group comprising from 1 to 30 carbon atoms, preferably from 1 to 15 carbon atoms, for example from 1 to 10 carbon atoms, the alkyl being optionally substituted;

[0086] - a cycloalkyl group, comprising from 3 to 30 carbon atoms, preferably 5 to 10 carbon atoms;

[0087] - an alkoxy group, the alkyl part of which, linear or branched, comprises from 1 to 30 carbon atoms, preferably from 1 to 15 carbon atoms, for example from 1 to 10 carbon atoms;

[0088] - an -O-cycloalkyl group in which the cycloalkyl comprises from 3 to 30 carbon atoms, preferably from 5 to 10 carbon atoms;

[0089] - an aryl group comprising from 6 to 30 carbon atoms, preferably from 6 to 10 carbon atoms;

[0090] - an aryloxy group, the aryl part of which comprises from 6 to 30 carbon atoms, preferably from 6 to 10 carbon atoms;

[0091] - an -Alk-aryl group with Alk representing a linear or branched alkyl comprising from 1 to 30 carbon atoms, preferably from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms, and the aryl comprising 6 to 30 carbon atoms, preferably 6 to 10 carbon atoms;

[0092] R 6 represents a bond or a group -(CF )™- in which m is an integer between 1 and 5, preferably 1; at least one of R 1 or R 2 represents a group of formula (2) and when R 1 and R 2 both represent a group of formula (2) these groups may be the same or different; or R 1 and R 2 form a cycle of formula (3) with

[0093] R 7 represents a group of formula (4) n represents 0, 1, 2, 3, or 4

[0094] R 5represents a linear or branched alkyl group comprising 1 to 30 carbon atoms, preferably 1 to 15 carbon atoms, for example 1 to 10 carbon atoms, the alkyl being optionally substituted;

[0095] R 8 represents a hydrogen atom, a group of formula (4), or an alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms;

[0096] R 9 and R 10 , identical or different, represent H, an alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms or

[0097] R 9 and R 10 form a bridge comprising one or two CH2 groups;

[0098] R represents: a linear or branched alkylene group comprising from 4 to 36 carbon atoms, preferably from 6 to 18 carbon atoms, optionally the alkylene is interrupted by at least one heteroatom and / or is optionally substituted; a cycloalkylene group comprising from 4 to 10 carbon atoms; an alkylene-cycloalkylene-alkylene group, the linear or branched alkylene comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, optionally substituted, the cycloalkylene comprising from 4 to 10 carbon atoms; a cycloalkylene-alkylene-cycloalkylene group, the linear or branched alkylene comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, optionally substituted, the cycloalkylene comprising from 4 to 10 carbon atoms; an arylene group comprising from 6 to 30 carbon atoms, preferably from 6 to 10 carbon atoms;an alkylene-arylene-alkylene group in which the alkylenes, identical or different, are linear or branched alkylenes comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms and the arylene comprises from 6 to 30 carbon atoms, preferably from 6 to 10 carbon atoms; an alkylene-arylene group in which the alkylenes, identical or different, are linear or branched alkylenes comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms and the arylene comprises from 6 to 30 carbon atoms, preferably from 6 to 10 carbon atoms;

[0099] A represents:

[0100] - a hydrogen atom;

[0101] - a group of formula (5) with r representing 0 or 1;

[0102] R 3 or R 4 , identical or different, represent:

[0103] - H ;

[0104] - a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms;

[0105] - a group of formula (2') n represents an integer chosen from 0, 1, 2, 3 or 4

[0106] R 5 , identical or different, represents:

[0107] - a linear or branched alkyl group comprising from 1 to 30 carbon atoms, preferably from 1 to 15 carbon atoms, for example from 1 to 10 carbon atoms;

[0108] - a cycloalkyl group, comprising from 3 to 30 carbon atoms, preferably from 5 to 10 carbon atoms;

[0109] - an alkoxy group, the alkyl part of which, linear or branched, comprises from 1 to 30 carbon atoms, preferably from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms; - an -O-cycloalkyl group, the cycloalkyl of which comprises from 3 to 30 carbon atoms, preferably from 5 to 10 carbon atoms;

[0110] - an aryl group comprising from 6 to 30 carbon atoms, preferably from 6 to 10 carbon atoms;

[0111] - an aryloxy group, the aryl part of which comprises from 6 to 30 carbon atoms, preferably from 6 to 10 carbon atoms;

[0112] - an -Alk-aryl group with Alk representing a linear or branched alkyl comprising from 1 to 30 carbon atoms, preferably from 1 to 15 carbon atoms, for example from 1 to 10 carbon atoms, and the aryl comprising 6 to 30 carbon atoms, preferably from 6 to 10 carbon atoms;

[0113] R 6 , identical or different, represents a bond or a group -(CF )™- where m is an integer between 1 and 5, preferably 1; at least one of R 3 or R 4 represents a group of formula (2') and when R 3 and R 4 both represent a group of formula (2') these groups may be the same or different; or R 3 and R4 form a cycle of formula (3') with

[0114] R 7 represents a group of formula (4')

[0115] R 5 represents a hydrogen atom or an alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms;

[0116] R 8 represents a hydrogen atom, a group of formula (4'), or an alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms R 9 and R 10 , identical or different, represent H, an alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms or R 9 and R 10 form a bridge comprising one or two CH2 groups.

[0117] In the context of the present invention, the inherent viscosity of the polyamide, or where appropriate of the mixture of polyamides, is measured after dissolution of said polyamide or said mixture of polyamides. The inherent viscosity is determined in m-cresol according to ISO 307:2007.

[0118] Preferably, the compound of formula (1) is a compound of formula (!') in which R 1 , R 2 , R 3 , R 4 , R and p are as defined in formula (1) above and at least one of R 1 and R 2 and at least one of R 3 and R 4 represents a group of formula (2) which may be the same or different.

[0119] Preferably, in the compounds of formula (1'): p represents 0 or 1;

[0120] R 1 and R 2 , identical or different, represent:

[0121] - a group of formula (2) n is 0

[0122] R 6 represents a bond or a group -(CH?)™- in which m is an integer between 1 and 5, preferably 1;

[0123] - H ;

[0124] - a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms; at least one of R 1 or R 2 represents a group of formula (2) and when R 1 and R 2 both represent a group of formula (2) these groups may be the same or different; or R 1 and R 2 form a cycle of formula (3) with

[0125] R 7 represents a group of formula (4) n is 0

[0126] R 8 represents a hydrogen atom or an alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms;

[0127] R 9 and R 10, identical or different, represent H, an alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms or

[0128] R 9 and R 10 form a bridge comprising one or two CH2 groups;

[0129] R represents: a linear or branched alkylene group comprising from 4 to 36 carbon atoms, preferably from 6 to 18 carbon atoms, optionally the alkylene is interrupted by at least one heteroatom and / or is optionally substituted; an alkylene-arylene-alkylene group in which the alkylenes, identical or different, are linear or branched alkylenes comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms and the arylene comprises from 6 to 30 carbon atoms, preferably from 6 to 10 carbon atoms;

[0130] R 3 or R 4 , identical or different, represent: a group of formula (2); - H;

[0131] - a linear or branched alkylene group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms; at least one of R 3 or R 4 represents a group of formula (2) and when R 3 and R 4 both represent a group of formula (2) these groups may be the same or different; or R 3 and R 4 form a cycle of formula (4).

[0132] Preferably, in the compounds of formula (1'): p represents 0 or 1;

[0133] R 1 and R 2 , identical or different, represent:

[0134] - a group of formula (2) n is 0

[0135] R 6 represents a bond or a group -(CF )™- in which m is an integer between 1 and 5, preferably 1;

[0136] - H; at least one of R 1 or R 2 represents a group of formula (2) and when R 1 and R 2both represent a group of formula (2) these groups may be the same or different; or

[0137] R 1 and R 2 form a cycle of formula (3) with

[0138] R 7 represents a group of formula (4) n is 0

[0139] R 8 represents a hydrogen atom, an alkyl group comprising from 1 to 5 carbon atoms;

[0140] R 9 and R 10 , identical or different, represent H, an alkyl group comprising from 1 to 5 carbon atoms; or

[0141] R 9 and R 10 form a bridge comprising a CH2 group;

[0142] R represents: a linear or branched alkylene group comprising from 4 to 36 carbon atoms, preferably from 6 to 18 carbon atoms, optionally the alkylene is interrupted by at least one heteroatom and / or is optionally substituted;

[0143] R3 or R 4 , identical or different, represent: a group of formula (2);

[0144] - H; at least one of R 3 or R 4 represents a group of formula (2) and when R 3 and R 4 both represent a group of formula (2) these groups may be the same or different; or R 3 and R 4 form a cycle of formula (4).

[0145] Preferably, the compound of the invention is a compound of formula (Ia) in which R 1 , R 2 , R 3 , R 4 and R are as defined in formula (1) above and at least one of R 1 and R 2 and at least one of R 3 and R 4 represents a group of formula (2) which may be the same or different.

[0146] Preferably, in compounds of formula (Ia): R 1 and R 2, identical or different, represent:

[0147] - a group of formula (2) n is 0

[0148] R 6 represents a bond or a group -(CH?)™- in which m is an integer between 1 and 5, preferably 1;

[0149] - H ;

[0150] - a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms; at least one of R 1 or R 2 represents a group of formula (2) and when R 1 and R 2 both represent a group of formula (2) these groups may be the same or different; or

[0151] R 1 and R 2 form a cycle of formula (3) with

[0152] R 7 represents a group of formula (4) n is 0

[0153] R 8represents a hydrogen atom or an alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms; R 9 and R 10 , identical or different, represent H, an alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms or

[0154] R 9 and R 10 form a bridge comprising one or two CH2 groups;

[0155] R represents: a linear or branched alkylene group comprising from 4 to 36 carbon atoms, preferably from 6 to 18 carbon atoms, optionally the alkylene is interrupted by at least one heteroatom and / or is optionally substituted; an alkylene-arylene-alkylene group in which the alkylenes, identical or different, are linear or branched alkylenes comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms and the arylene comprises from 6 to 30 carbon atoms, preferably from 6 to 10 carbon atoms;

[0156] R 3 or R 4 , identical or different, represent: a group of formula (2);

[0157] - H ;

[0158] - a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms; at least one of R 3 or R 4 represents a group of formula (2) and when R 3 and R 4 both represent a group of formula (2) these groups may be the same or different; or R 3 and R 4 form a cycle of formula (4).

[0159] Preferably, in compounds of formula (Ia):

[0160] R 1 and R 2 , identical or different, represent:

[0161] - a group of formula (2) n is 0

[0162] R 6 represents a bond or a group -(CH?)™- in which m is an integer between 1 and 5, preferably 1;

[0163] - H; at least one of R 1 or R 2 represents a group of formula (2) and when R 1 and R 2 both represent a group of formula (2) these groups may be the same or different; or R 1 and R 2 form a cycle of formula (3) with

[0164] R 7 represents a group of formula (4) n is 0

[0165] R 8 represents a hydrogen atom, an alkyl group comprising from 1 to 5 carbon atoms;

[0166] R 9 and R 10 , identical or different, represent H, an alkyl group comprising from 1 to 5 carbon atoms; or

[0167] R 9 and R 10 form a bridge comprising a CH2 group;

[0168] R represents: a linear or branched alkylene group comprising from 4 to 36 carbon atoms, preferably from 6 to 18 carbon atoms, optionally the alkylene is interrupted by at least one heteroatom and / or is optionally substituted;

[0169] R 3 or R 4 , identical or different, represent: a group of formula (2);

[0170] - H; at least one of R 3 or R 4 represents a group of formula (2) and when R 3 and R 4 both represent a group of formula (2) these groups may be the same or different; or R 3 and R 4 form a cycle of formula (4). Preferably, in compounds of formula (Ia):

[0171] R 1 and R 3 , identical or different, preferably identical, represent a group of formula (2) n is 0

[0172] R 6represents a bond or a -(CH2)- group;

[0173] R represents: a linear or branched alkylene group, comprising from 6 to 18 carbon atoms;

[0174] R 2 and Represent H.

[0175] Preferably, the compound of formula (1) according to the invention is compound (lb):

[0176] Preferably, the composition according to the present invention comprises: Mainly a polyamide, or a mixture of polyamides, said polyamide, or where appropriate said mixture of polyamides, having an inherent viscosity of at most 0.8;

[0177] At least one compound of formula (1) according to the invention.

[0178] In the context of the present invention, the term "predominantly" means a content of at least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight, preferably at least 90% by weight, preferably between 50 and 99% by weight, relative to the total weight of the composition.

[0179] Polyamide or polyamide blend can also be called polyamide matrix.

[0180] Particularly advantageously, the inventors have shown that the compounds of formula (1) according to the invention do not prevent the viscosity of the composition from increasing during its use, in particular after heating to a temperature higher than the glass transition temperature (Tg) of the polyamide or polyamide blend, preferably higher by at least 10°C, preferably higher by at least 20°C, preferably higher by at least 100°C, even more preferably between 120 and 340°C, and that advantageously, the inherent viscosity of the final matrix (after viscosity increase) is at least 10%, preferably at least 60%, even more preferably at least 120% higher compared to the starting composition in the absence of compound (1).

[0181] Advantageously, the compounds of formula (1), while providing good fire resistance and not preventing the rise in viscosity of the composition during its implementation, have little or no impact on the mechanical properties of the polyamide matrix compared to a composition not comprising said compound.

[0182] The composition according to the invention may be in the form of powder or granules.

[0183] Preferably, the polyamide or, where appropriate, said polyamide mixture of the composition according to the invention has an inherent viscosity of between 0.30 and 0.80.

[0184] Preferably, the final composition, after implementation and therefore increased viscosity, has an inherent viscosity of at least 0.90, preferably at least 1.00, more preferably at least 1.10.

[0185] The at least one polyamide according to the invention is chosen from aliphatic, cycloaliphatic polyamides or semi-aromatic PAs (also called polyphthalamides (PPA)).

[0186] The nomenclature used to define polyamides is described in ISO 1874-1:2011 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", particularly on page 3 (tables 1 and 2) and is well known to those skilled in the art. Preferably

[0187] - said aliphatic polyamide is chosen from polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 66 (PA-66), polyamide 46 (PA-46), polyamide 610 (PA-610), polyamide 612 (PA-612), polyamide 1010 (PA-1010), polyamide 1012 (PA-1012), polyamide 11 / 1010 and polyamide 12 / 1010, or a mixture thereof or a copolyamide thereof, and polyetheramide or polyetheresteramide copolymers (PEBA) (or copolymer with polyamide blocks and polyether blocks); preferably selected from polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 66 (PA-66), polyamide 46 (PA-46), polyamide 610 (PA-610), polyamide 612 (PA-612), polyamide 1010 (PA-1010), polyamide 1012 (PA-1012), polyamide 11 / 1010 and polyamide 12 / 1010, or a mixture thereof, and

[0188] - said semi-aromatic polyamide is a semi-aromatic polyamide, optionally modified by urea units, in particular a PA MXD6, a PA MXD10, a PA PXD6, a PA PXD10, a PA 9T, or a PA 10T or a semi-aromatic polyamide of formula X / YAr, as described in EP1505099, in particular a semi-aromatic polyamide of formula A / XT in which A is chosen from a unit obtained from at least one amino acid, a unit obtained from at least one lactam and at least one unit corresponding to the formula (Ca diamine).(Cb diacid), with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the unit (Ca diamine) being chosen from aliphatic, linear or branched diamines, cycloaliphatic diamines and alkylaromatic diamines and the unit (Cb diacid) being chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids and aromatic diacids; X.T denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid, with x representing the number of carbon atoms of the Cx diamine, x being between 6 and 36, advantageously between 9 and 18, in particular a polyamide of formula A / 6T, A / 9T, A / 10T or A / 11T, A being as defined above, in particular a polyamide PA 6 / 6T, a PA 66 / 6T, a PA 6I / 6T, a PA MPMDT / 6T, a PA 11 / 6T, a PA PA11 / 10T, a PA 11 / 6T / 10T, a PA 6T / 8T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, a PA 11 / BACT, PA BACT / 10T / 6T, a PA 11 / BACT / 10T; T corresponds to terephthalic acid, MXD corresponds to m-xylylenediamine, PXD corresponds to p-xylylenediamine, MPMD corresponds to methylpentamethylenediamine and BAC corresponds to 1,3-bis(aminomethyl)cyclohexane alone or in a mixture with 1,4-bis(aminomethyl)cyclohexane. Terephthalic acid can be in a mixture with 1,4-cyclohexanedicarboxylic acid (CHDA).

[0189] Preferably:

[0190] - said aliphatic polyamide is chosen from polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 66 (PA-66), polyamide 46 (PA-46), polyamide 610 (PA-610), polyamide 612 (PA-612), polyamide 1010 (PA-1010), polyamide 1012 (PA-1012), polyamide 11 / 1010 and polyamide 12 / 1010, or a mixture thereof or a copolyamide thereof, and polyetheramide or polyetheresteramide (PEBA) copolymers (or copolymer with polyamide blocks and polyether blocks); preferably chosen from polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 66 (PA-66), polyamide 46 (PA-46), polyamide 610 (PA-610), polyamide 612 (PA-612), polyamide 1010 (PA-1010), polyamide 1012 (PA-1012), polyamide 11 / 1010 and polyamide 12 / 1010, or a mixture thereof, and said semi-aromatic polyamide is a semi-aromatic polyamide, optionally modified with urea units, in particular a PA MXD6 and a PA MXD10 or a semi-aromatic polyamide of formula X / YAr,as described in EP1505099, in particular a semi-aromatic polyamide of formula A / XT in which A is chosen from a unit obtained from at least one amino acid, a unit obtained from at least one lactam and at least one unit corresponding to the formula (Ca diamine). (Cb diacid), with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the unit (Ca diamine) being chosen from linear or branched aliphatic diamines, cycloaliphatic diamines and alkylaromatic diamines and the unit (Cb diacid) being chosen from linear or branched aliphatic diacids, cycloaliphatic diacids and aromatic diacids;,

[0191] XT denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid, with x representing the number of carbon atoms of the Cx diamine, x being between 6 and 36, advantageously between 9 and 18, in particular a polyamide of formula A / 6T, A / 9T, A / 10T or A / 11T, A being as defined above, in particular a polyamide PA 6 / 6T, a PA 66 / 6T, a PA 6I / 6T, a PA MPMDT / 6T, a PA PA11 / 10T, a PA 11 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, a PA 11 / BACT, PA BACT / 10T / 6T, a PA 11 / BACT / 10T.

[0192] T corresponds to terephthalic acid, MXD corresponds to m-xylylenediamine, MPMD corresponds to methylpentamethylenediamine and BAC corresponds to 1,3-bis(aminomethyl)cyclohexane. Preferably, said polyamide is a semi-aromatic polyamide selected from a PA MPMDT / 6T, a PA PA11 / 10T, a PA 11 / BACT, a PA 11 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, PA BACT / 10T / 6T, a PA 11 / BACT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T, a PA 11 / MXDT / 10T.

[0193] Preferably, said polyamide is an aliphatic polyamide PAU or PA12, preferably PAU.

[0194] Preferably said polyamide is a semi-aromatic polyamide PA 11 / BACT / 10T, PA 11 / 10T, PA 11 / 6T / 10T, PA MXD10, PA 9T.

[0195] According to one variant, the polyamide is a polyetheramide or polyetheresteramide (PEBA) copolymer (or copolymer with polyamide blocks and polyether blocks). The polyamide blocks of these copolymers may be chosen from blocks of polyamide 6, polyamide 11, polyamide 6.10, polyamide 6.12, polyamide 10.10, polyamide 10.12, polyamide 10.14, polyamide 12, and combinations thereof. The polyether blocks of these copolymers may be chosen from polyether blocks comprising terminal amine functions; such polyethers comprising terminal amine functions are, for example, known under the trade name Jeffamine®.

[0196] Advantageously, the at least one polyamide according to the invention has a glass transition temperature Tg greater than or equal to 40°C, preferably greater than or equal to 80°C, preferably greater than or equal to 100°C, in particular greater than or equal to 120°C, in particular greater than or equal to 140°C.

[0197] The composition according to the invention may comprise at least one chain extender. The chain extenders may be any type of chain extender known to those skilled in the art, such as, for example, those cited in patent applications EP3325537 and EP3131741. Preferably, the composition according to the invention does not comprise a chain extender.

[0198] The composition according to the invention may comprise additives, such as for example one or more flame retardant agents other than a compound of formula (1), one or more flame retardant synergists, one or more metal oxides, a catalyst, one or more antioxidants, one or more thermal stabilizers, one or more UV stabilizers, one or more light stabilizers, one or more lubricants, one or more fillers, one or more plasticizers, one or more nucleating agents, one or more colorants, one or more electrically conductive agents, one or more thermally conductive agents, or a mixture thereof. The composition according to the invention may comprise from 0.01 to 40% by weight, preferably from 0.01 to 20% by weight, preferably from 0.01 to 10% by weight, more preferably from 0.01 to 5% by weight, of additives relative to the total weight of the composition.Preferably, the composition according to the invention comprises from 50 to 99%, preferably from 60 to 99%, preferably from 70 to 99%, preferably from 80 to 99%, even more preferably from 85 to 95% by weight of the polyamide or where appropriate of the mixture of polyamides and from 1 to 40%, preferably from 4 to 30%, even more preferably 5 to 20%, by weight of compound of formula (1) relative to the total weight of the composition.

[0199] Process for the preparation of compounds of formula (1)

[0200] Compounds of formula (1) can be obtained by:

[0201] 1) reaction between a DOPO compound (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) or one of its derivatives and a dicarboxylic acid comprising double or triple unsaturation or the corresponding anhydride;

[0202] 2) then reaction of the compound obtained in step 1) with a diamine of formula NH2-RD with D representing H or NH2, R being as defined above.

[0203] DOPO derivatives are compounds of formula (5) with R 5 and n being as defined above.

[0204] The dicarboxylic acids are preferably compounds of formula (6) or the corresponding anhydrides:

[0205] C(O)(OH)-BC(O)(OH) (6) with B is

[0206] - a linear alkylene group comprising from 2 to 3 carbon atoms and a double or triple bond, and which may be substituted by an alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms; or

[0207] - a group of formula (7) in which represents a double or triple bond R 8 , R 9 and R 10 being as defined above.

[0208] Use of the compositions according to the invention

[0209] The composition according to the invention can be used in the coating of fibers or the manufacture of composites comprising fibers, in molding processes such as rotational molding, in part coating processes which can in particular use powders.

[0210] The present invention also relates to a composite comprising fibers, for example continuous fibers, impregnated with the composition of the invention.

[0211] The present invention also relates to a composite obtained by impregnation of fibers, for example continuous fibers, with the composition of the invention and polymerization of said composition.

[0212] The invention will be explained in more detail in the following examples.

[0213] Examples

[0214] Example 1: Preparation of the compound of formula (lb)

[0215] 2.0 equivalents of DDP (6H-dibenz[c,e][l,2]oxaphosphorin-6-ylmethyl)-p-oxide-butanedioic acid) and 1.0 equivalent of 1,10-diaminodecane are introduced into a reactor equipped with mechanical stirring. The reactor is then heated to 220°C under nitrogen scavenging and kept stirring for 2 hours under nitrogen scavenging. The water vapor formed during the reaction is condensed outside the reaction medium to promote the reaction. At the end of the reaction, the reaction medium is drained hot from the reactor and cooled to room temperature. The resulting compound lb is finally ground into powder form. Example 2: Flame-retardant polymer composition

[0216] The following compositions are prepared on an Xplore MC 15 HT twin-screw micro-extruder at 100 rpm. The compositions are introduced via dry blends. The melt temperature setpoint is 230 °C for the PAU examples, and 290 °C for the PPA examples. After a certain mixing time at these temperatures, the blends are then injected on an Xplore IM12 micro-injector to produce ISO527-1BA specimens.

[0217] PAU polyamide is a PAU prepolymer, with an inherent viscosity in initial solution of 0.5 dL / g.

[0218] The PPA (polyphthalamide) is Rilsan® MATRIX RNM0540, which is a polyphthalamide of composition 11 / BACT / 10T with an inherent viscosity in initial solution of 0.5 dL / g

[0219] Aflammit® PMN200 is a flame retardant synergist

[0220] Lunastab® DDP is a flame retardant (CAS 63562-33-4)

[0221] Table 1

[0222] Unless otherwise stated, percentages are expressed by weight relative to the total weight of the composition. Presentation of the evaluation tests

[0223] Fire tests are carried out on ISO-527-1 BA specimens, conditioned for 48 hours at 23°C and 50% relative humidity before testing. The specimens are fixed vertically with a clamp. A flame of 50 W power and height 20 mm is then positioned for 10 s at 10 mm from the bottom of the specimen. As soon as no flame is visible on the sample, a 2 ème application of the same flame is carried out on the rest of the test piece under the same conditions. The self-extinction time "tl" corresponds to the time in seconds between the end of the l ère application of the flame and the disappearance of the flame on the sample. The self-extinction time “t2” corresponds to the time in seconds between the end of the 2 èmeapplication of the flame and the disappearance of the flame on the sample. Each composition is evaluated on 5 test pieces. The “maximum self-extinction time” corresponds to the maximum self-extinction time observed on these 5 test pieces (the greatest self-extinction time measured, between the maximum “tl” measured and the maximum “t2” measured). The “sum of self-extinction times” corresponds to the sum of the self-extinction times for these 5 test pieces (i.e. the sum of the 5 “tl” measured and the 5 “t2” measured). The lower these 2 values, the higher the fire resistance.

[0224] The inherent viscosity in solution is measured on dumbbells. The viscosity increase is measured by comparing the inherent viscosity measured on the dumbbell to the inherent viscosity of the polyamide or polyamide blend before heating. The inherent viscosity is determined in m-cresol according to ISO 307:2007.

[0225] Example 3: Results

[0226] The resulting compositions were analyzed to determine their fire resistance and inherent viscosity after heating in the extruder. The results are shown in Tables 2 and 3 below.

[0227] Table 2

[0228] Table 3

[0229] REV = Viscosity increase

[0230] Examples 1-5 according to the invention illustrate formulations comprising mainly a polyamide in accordance with the invention (PAU prepolymer, which is a polyamide 11 with an inherent viscosity in solution of 0.5 dL / g) and a compound of formula (1) in accordance with the invention (compound of formula (lb)), in contents ranging from 6.0 to 16.7% by weight).

[0231] The formulations of Examples 1 to 5 exhibit improved flame retardant properties compared to a comparative formulation C1 lacking compound of formula (1) in accordance with the invention.

[0232] The results in Table 2 thus illustrate the fire resistance properties which are conferred by the compound of formula (1) to the formulations of the invention.

[0233] The maximum self-extinction time as well as the sum of the self-extinction times are in fact significantly lower for the formulations of examples 1 to 5 (“maximum self-extinction time” = 12 s maximum and “sum of the self-extinction times” between 2 and 27 s), compared to those measured for formulation Cl (“maximum self-extinction time” = 65 s and “sum of the self-extinction times” > 200 s).

[0234] It is further noted that these fire resistance properties are observed even at low contents of compound of formula (1) according to the invention (from 6.0% by weight according to the formulation of example 1) and are all the more marked as the quantity of compound of formula (1) is important in the formulation.

[0235] The results in Table 3 illustrate, for their part, that the presence of a compound of formula (1) in polyamide formulations according to the invention does not impact the increase in viscosity of said polyamides (estimated via the relative REV%, at different passage time conditions) during the production of the mixture in the extruder.

[0236] The relative REV% of the formulations of examples 1 to 5 are in fact equivalent to the relative REV% of the comparative formulation Cl, under the same mixing conditions (transition time of 15 min and material temperature of 230°C).

[0237] The results in Table 3 also show that the increase in viscosity can be observed, more generally, for formulations of the invention, whatever the experimental conditions (in particular with other passage times such as for example passage times of 30 min (formulation of example 1) or 42 min (formulation of example 4)).

[0238] Conversely, a comparative formulation C2 containing a flame retardant compound of the prior art (Luna-stab® DDP) prevents the rise in viscosity of a polyamide formulation containing it (relative REV% equivalent to 0).

[0239] The same performances are observed for the formulations of Examples 6 to 8, mainly comprising another type of polyamide in accordance with the invention (prepolymer of Rilsan® MATRIX RNM0540, which is a polyphthalamide of composition 11 / 1,3-BACT / 10T and inherent viscosity in solution of 0.5 dL / g), and a compound of formula (1) in accordance with the invention (compound of formula (1b)), in contents ranging from 8.3 to 11.3% by weight). The formulations of Examples 6 to 8 have improved fire resistance properties compared to a comparative formulation C3 devoid of compound of formula (1) in accordance with the invention.

[0240] The maximum self-extinction time as well as the sum of the self-extinction times are in fact significantly lower for the formulations of examples 6 to 8 (“maximum self-extinction time” = 11 s at most and “sum of the self-extinction times” between 17 and 66 s), compared to those measured for formulation C3 (“maximum self-extinction time” = 62 s and “sum of the self-extinction times” > 200 s).

[0241] The results in Table 3 illustrate, for their part, that the presence of a compound of formula (1) in polyamide formulations according to the invention does not prevent the increase in viscosity of said polyamides (estimated via the relative REV%, at a given passage time) during the production of the mixture in the extruder.

[0242] We observe significant relative REV% for the formulations of examples 6 to 8 in comparison with that of the comparative formulation C3, for identical passage times and temperatures (15 min and 290°C respectively).

[0243] The relative REV% of the formulations of examples 6 to 8 are in fact equivalent to the relative REV% of the comparative formulation C3, under the same mixing conditions (transition time of 15 min and material temperature of 290°C).

[0244] The data relating to the formulation of example 7 illustrate more particularly the interest of adding a flame retardant synergist agent in addition to the compound of formula (1), in particular to improve the fire resistance performance without negatively impacting the viscosity increase performance.

[0245] The compounds of formula (1), while providing good fire resistance and not preventing the rise in viscosity of the composition during its implementation, finally have little or no impact on the mechanical properties of the polyamide matrix compared to a composition not comprising said compound.

Claims

Claims 1. Polyamide composition comprising: A polyamide or a mixture of polyamides in which the polyamide, or where appropriate, the mixture of polyamides, has an inherent viscosity of not more than 0.8, the inherent viscosity being determined in m-cresol according to ISO 307:2007; and A compound of formula (1): in which: • p represents 0 or 1; • R 1 and R 2 , identical or different, represent: - H ; - a linear or branched alkyl group comprising from 1 to 10 carbon atoms; - a group of formula (2) n represents an integer chosen from 0, 1, 2, 3 or 4 R 5 , identical or different, represents: - an alkyl group, linear or branched, comprising from 1 to 30 carbon atoms; - a cycloalkyl group, comprising from 3 to 30 carbon atoms; - an alkoxy group, the alkyl part of which, linear or branched, comprises from 1 to 30 carbon atoms; - an -O-cycloalkyl group in which the cycloalkyl comprises from 3 to 30 carbon atoms; - an aryl group comprising from 6 to 30 carbon atoms; - an aryloxy group, the aryl part of which comprises from 6 to 30 carbon atoms; - an -Alk-aryl group with Alk representing a linear or branched alkyl comprising from 1 to 30 carbon atoms and aryl comprising 6 to 30 carbon atoms; R 6 , identical or different, represents a bond or a group -(CF )™- where m is an integer between 1 and 5; at least one of R 1 or R 2 represents a group of formula (2), when R 1 and R 2 both represent a group of formula (2) these groups may be the same or different; • or R 1 and R 2 form a cycle of formula (3) with R 7 represents a group of formula (4) n represents 0, 1, 2, 3, or 4 R 5 represents an alkyl group, linear or branched, comprising 1 to 30 carbon atoms, optionally substituted; R 8 represents a hydrogen atom, a group of formula (4) or an alkyl group comprising from 1 to 10 carbon atoms; R 9 and R 10 , identical or different, represent H, an alkyl group comprising from 1 to 10 carbon atoms or R 9 and R 10 form a bridge comprising one or two CH2 groups; • R represents: an alkylene group, linear or branched, comprising from 4 to 36 carbon atoms, optionally the alkylene is interrupted by at least one heteroatom and / or is optionally substituted; a cycloalkylene group comprising from 4 to 10 carbon atoms; an alkylene-cycloalkylene-alkylene group, the linear or branched alkylene comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, optionally substituted, the cycloalkylene comprising from 4 to 10 carbon atoms; a cycloalkylene-alkylene-cycloalkylene group, the linear or branched alkylene comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, optionally substituted, the cycloalkylene comprising from 4 to 10 carbon atoms; an arylene group comprising from 6 to 30 carbon atoms;an alkylene-arylene-alkylene group in which the alkylenes, identical or different, are linear or branched alkylenes comprising from 1 to 10 carbon atoms and the arylene comprises from 6 to 30 carbon atoms; an alkylene-arylene group in which the alkylenes, identical or different, are linear or branched alkylenes comprising from 1 to 10 carbon atoms and the arylene comprises from 6 to 30 carbon atoms; • A represents: a hydrogen atom; a group of formula (5) with r representing 0 or 1; R 3 or R 4 , identical or different, represent: - H ; - a linear or branched alkyl group comprising from 1 to 10 carbon atoms; - a group of formula (2') n represents an integer chosen from 0, 1, 2, 3 or 4 R 5 , identical or different, represents: - an alkyl group, linear or branched, comprising from 1 to 30 carbon atoms; - a cycloalkyl group, comprising from 3 to 30 carbon atoms; - an alkoxy group, the alkyl part of which, linear or branched, comprises from 1 to 30 carbon atoms; - an -O-cycloalkyl group in which the cycloalkyl comprises from 3 to 30 carbon atoms; - an aryl group comprising from 6 to 30 carbon atoms; - an aryloxy group, the aryl part of which comprises from 6 to 30 carbon atoms; - an -Alk-aryl group with Alk representing a linear or branched alkyl comprising from 1 to 30 carbon atoms and aryl comprising 6 to 30 carbon atoms; R 6 , identical or different, represents a bond or a group -(CF )™- where m is an integer between 1 and 5, preferably 1; at least one of R 3 or R 4 represents a group of formula (2'), when R 3 and R 4both represent a group of formula (2') these groups can be the same or different; • or R 3 and R 4 form a cycle of formula (3') with R 7 represents a group of formula (4') R 5 represents a hydrogen atom or an alkyl group comprising from 1 to 10 carbon atoms; R 8 represents a hydrogen atom, a group of formula (4') or an alkyl group comprising from 1 to 10 carbon atoms; R 9 and R 10 , identical or different, represent H, an alkyl group comprising from 1 to 10 carbon atoms or R 9 and R 10 form a bridge comprising one or two CH2 groups.

2. Composition according to claim 1, in which the compound of formula (1) is a compound of formula (Ia) in which R 1 , R 2 , R 3 , R4 and R are as defined in claim 1.

3. Composition according to claim 1, in which: • R represents a linear or branched alkylene group comprising from 6 to 18 carbon atoms; • R 1 and R 3 , identical, represent a group of formula (2): n equal to 0 R 6 represents a bond or a CH2 group, n represents 0; R 2 and R 4 represent H.

4. Composition according to any one of claims 1 to 3 comprising, relative to the total weight of the composition, from 50 to 99%, preferably from 60 to 99%, preferably from 70 to 99%, preferably from 80 to 99%, preferably from 85 to 95%, by weight of the polyamide or the polyamide mixture and from 1 to 40%, preferably from 4 to 30%, preferably from 5 to 20%, by weight of at least one compound of formula (1).

5. Composition according to any one of claims 1 to 4 comprising from 0.01 to 40%, preferably from 0.01 to 20% by weight, preferably from 0.01 to 10% by weight, more preferably from 0.01 to 5%, by weight of additive relative to the total weight of the composition.

6. Composition according to any one of claims 1 to 5 in which the polyamide is chosen from: - aliphatic polyamides chosen from polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 66 (PA-66), polyamide 46 (PA-46), polyamide 610 (PA-610), polyamide 612 (PA-612), polyamide 1010 (PA-1010), polyamide 1012 (PA-1012), polyamide 11 / 1010 and polyamide 12 / 1010, or a mixture thereof or a copolyamide thereof, and polyetheramide or polyetheresteramide (PEBA) copolymers (or copolymer with polyamide blocks and polyether blocks); preferably chosen from polyamide 6 (PA-6), polyamide 11 (PA-11), polyamide 12 (PA-12), polyamide 66 (PA-66), polyamide 46 (PA-46), polyamide 610 (PA-610), polyamide 612 (PA-612), polyamide 1010 (PA-1010), polyamide 1012 (PA-1012), polyamide 11 / 1010 and polyamide 12 / 1010, or a mixture thereof; - semi-aromatic polyamides, optionally modified by urea units, chosen from a PA MXD6 and a PA MXD10 or a semi-aromatic polyamide of formula A / XT in which A is chosen from a unit obtained from at least one amino acid, a unit obtained from at least one lactam and at least one unit corresponding to the formula (Ca diamine). (Cb diacid), with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the unit (Ca diamine) being chosen from aliphatic, linear or branched diamines, cycloaliphatic diamines and alkylaromatic diamines and the unit (Cb diacid) being chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids and aromatic diacids; X.T denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid, with x representing the number of carbon atoms in the Cx diamine, x. being between 6 and 36, advantageously between 9 and 18, in particular a polyamide of formula A / 6T, A / 9T, A / 10T or A / 11T, A being as defined above, in particular a polyamide PA 6 / 6T, a PA 66 / 6T, a PA 6I / 6T, a PA MPMDT / 6T, a PA PA11 / 10T, a PA 11 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, a PA BACT / 10T, a PA BACT / 6T, a PA 11 / BACT, PA BACT / 10T / 6T, a PA 11 / BACT / 10T; T corresponds to terephthalic acid, MXD corresponds to m-xylylenediamine, MPMD corresponds to methylpentamethylenediamine and BAC corresponds to 1,3-bis(aminomethyl)cyclohexane alone or in mixture with 1,4-bis(aminomethyl)cyclohexane; - polyetheramide or polyetheresteramide copolymers (PEBA) (or copolymer with polyamide blocks and polyether blocks).

7. Composite comprising fibers impregnated with the composition according to any one of claims 1 to 6.

8. Use of a composition according to any one of claims 1 to 6 for the preparation of a composite comprising fibers.

9. Composite obtained by impregnation of fibers with the composition according to any one of claims 1 to 6 and polymerization of said composition.

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