FR2989375A1 - NOVEL BRANCHED AND UNSATURATED COMPOUNDS FOR THE MANUFACTURE OF RETICULABLE POLYMERS - Google Patents

Abstract

The present invention relates to novel branched and unsaturated difunctional compounds obtained from fatty acids. It also relates to a process for their preparation and their uses, especially as monomers in the synthesis of polymers. In particular, the invention relates to amine, acid, ester, nitrile, azide and alcohol functional compounds, especially derived from renewable resources, particularly useful in the synthesis of polymers. The subject of the invention is also polymers obtained from these novel compounds, in particular polyamides, and their use for the manufacture of industrial objects or of everyday life.

Description

NOVEL BRANCHED AND UNSATURATED COMPOUNDS FOR THE MANUFACTURE OF RETICULABLE POLYMERS.

Field of the Invention: The present invention relates to novel branched and unsaturated di-functional compounds obtained from fatty acids. It also relates to a process for their preparation and their uses, especially as monomers in the synthesis of polymers. In particular, the invention relates to amine, acid, ester, nitrile, azide and alcohol functional compounds, especially derived from renewable resources, particularly useful in the synthesis of polymers. The subject of the invention is also polymers obtained from these novel compounds, in particular polyamides, and their use for the manufacture of industrial objects or of everyday life.

The polymers are macromolecules obtained from a repetition of identical (homopolymer) or different (copolymer) units that can lead to elastomers, thermoplastics, thermoplastic elastomers or thermosets. They are used in the composition of many industrial and everyday objects such as plastics, electrical or electronic equipment or automobiles. State of the art: The polyamides are currently obtained by polyaddition of a lactam or by polycondensation of at least one amino acid or at least one diamine with at least one dicarboxylic acid or at least one carboxylic acid derivative or by using nylon salts. The diamines and amino acids used in these polymers are either linear or cyclo-aliphatic or aromatic. They therefore lead to the formation of linear aliphatic or aromatic polyamides having melting temperatures of the order of 200-300 ° C or non-crystalline polyamides but whose softening point remains high. A high melting or softening temperature has certain disadvantages. Indeed, polymers having high melting or softening temperatures can not, for example, be used in certain transformation processes such as fluidized bed application, electrostatic spraying. They can not also be used to cover heat-sensitive substrates such as wood or plastics. It is known to reduce the glass transition temperature of a polyamide by using a plasticizer.

The use of a plasticizer has the following disadvantages. The plasticizer is an additive not chemically bound to the polymer chains. It therefore tends to migrate plastics in which it has been incorporated into other plastic or other materials placed in close contact with the polyamide. Moreover, the plasticizer can be volatile and therefore contributes to the pollution of the environment. This has a direct and negative impact on health. One possibility of limiting the use of plasticizers is to reduce the glass transition temperature of a polyamide either by varying the composition of the polyamide (use of 2, 3, 4 ... different monomers) or by grafting alkyl chains. or aryl on the monomer. Among the existing graft monomers that can play this role, there are N-alkylated or N-arylated diamines and C-alkylated lactams, derived from petroleum, and therefore non-renewable raw materials. The alkyl or aryl chains used are either short linear chains comprising 1 to 4 carbon atoms or cyclic chains such as methylphenyl, cyclohexyl, cyclohexylmethyl and methoxyethyl. There is also N-heptyl-11-aminoundecanoic acid, which is obtained from 11-aminoundecanoic acid and heptanal, both derived from castor oil and therefore from renewable resources. However, the number of chemical groups which can be grafted on the amine function or in the alpha, beta, gamma or delta position of the carboxylic function of the monomers is quite limited. Furthermore, it is known to reduce the melting temperature of a polyamide by decreasing the molar mass of the polymer. However a decrease in the molar mass also causes a loss of the mechanical properties of the polyamides. The crosslinking makes it possible to compensate for the loss of properties resulting from the decrease in the melting temperature. Thermally crosslinkable polyamides are known as described in US2011 / 0288258 and JP 2003/327634. However, the thermal crosslinking has the disadvantage of using chemical additives that are responsible for emissions of organic compounds (VOC). Photochemically crosslinking is an increasingly developed alternative to thermal crosslinking. In fact, photochemical crosslinking makes it possible to overcome the use of solvents, thus reducing pollutant emissions and preserving the environment. Photochemically crosslinkable polyamides are generally functionalized polyamides. The functionalization (or grafting) processes consist in introducing a functional compound into the polymer during its polymerization. However, the copolymerization of these functional compounds is often difficult to control and leads to non-homogeneous distributions.

There is therefore a need to obtain branched and unsaturated polymers, especially branched and unsaturated polyamides, having both good mechanical properties and a lowered melting temperature. There is also a need to obtain polymers that can easily be crosslinked photochemically. An object of the present invention is to provide monomers and polymers at least partially overcoming the aforementioned drawbacks. A first objective of the present invention is to obtain new unsaturated and branched monomers making it possible to modify the properties of the polymer in which they are incorporated and allowing the photochemically cross-linking of the polymer. This objective is achieved through the design and synthesis of unsaturated and branched diamines, amino acids, amino esters, diols, diazotides and dinitriles having an alkyl chain located at a or R of the amine, alcohol, acid, azide or nitrile function. The compounds according to the invention have a wide variety of hydrocarbon chain lengths which advantageously makes it possible to modulate the chemical and mechanical properties of the polymers in which they are used. The presence of unsaturations in the compounds according to the invention offers the possibility of establishing cross-linking bonds between chains, again making it possible to modulate the mechanical properties of the polymers in which they are present and making it possible to dispense with a process. functionalization difficult to master. This objective is achieved through the design and synthesis of unsaturated and branched diamines, amino acids or amino esters having an alkyl chain located at a or R of the amine function which is of primary class or at a or R of the acid function. The compounds according to the invention are therefore more reactive than the N-alkylated diamines of the prior art which have a secondary amine function. Furthermore, the compounds according to the invention have a wide variety of hydrocarbon chain lengths.

A second objective of the present invention is to develop a novel process for synthesizing these unsaturated and branched compounds which is simple, comprises a limited number of reaction steps, or is adaptable to raw materials of renewable origins and be industrializable. This objective is achieved by using as starting material an unsaturated carboxylic acid, especially a naturally occurring fatty acid, comprising either a hydroxyl function or an epoxy ring.

Another object of the present invention is to develop polymers, especially polyamides, whose mechanical, crystalline and thermal properties can be adjustable. This objective is achieved by using the unsaturated and branched compounds according to the invention as monomers. The unsaturated and branched compounds according to the invention have unsaturated and branched alkyl chains of variable length. This diversity of chemical structures can therefore make it possible to lower the melting temperature of the polymers, in particular polyamides, thus favoring the use of less energy-intensive methods of implementation, or even of widening the range of mechanical properties (flexibility ) and therefore of application domains by varying the length of the branched chain or by acting on the crosslinking of the polymer. Document FR-1230155 describes a mixture of branched and saturated C18 diamines and its use as an epoxy resin hardener. However, this process uses as raw material an amine whose origin is unknown and does not allow access to a wide variety of compounds. US Pat. No. 2,309,509 describes the preparation of several branched and saturated diamines from ketoacids of fatty acids. Several documents mention branched and saturated amino acids obtained from ketoacids of fatty acids (US-2,312,967, US-2,283,683, GB-634,172 and US-2,524,046) as well as their use for the synthesis of polyamides. However, none of the processes described in these documents has been developed industrially.

Articles titled "Unsaturated PA X, 20 from Renewable Resources via Metathesis and Catalytic Amidation" by Mutlu H and al Macromol. Chem. Phys., 210, 1019 (2009), "Linear Unsaturated Polyamides: Nylons 6 u18 and 18 u18" by Bennett C et al, Macromol. Chem. Phys., 205, 2438 (2004) and "Unsaturated Polyamides from Bio-Based Z-Octadec-9-Enedioic Acid" from Pardal F et al, Macromol. Chem. Phys., 209, 64 (2008) describe the synthesis of an unsaturated polyamide obtained from a vegetable oil. The article entitled "A new UV-curable powder coating based on a, unsaturated copolyamide 6/11/12" by Marion N'Negue Minsta et al, Eur. Polym. J., 45, 2043 (2009) discloses an α, β-unsaturated copolyamide (6/11/12) which can be crosslinked photochemically. However, none of these articles describes an unsaturated and branched polyamide, nor its manufacturing process nor its photochemical transformation. The method of the invention provides access to numerous compounds, many of which have never been described in the prior art, including diamine, amino acid, aminoester, dialcohol, diazide and dinitrile compounds, and provides access to a varied range compounds of various functionalities. Thus, it gives access to a wide variety of crosslinking monomers and compounds that can be used in the synthesis of polymers and thus allows the production of polymers having properties, in particular mechanical, crystalline and thermal properties that are varied and variable. SUMMARY OF THE INVENTION A first subject of the invention relates to compounds of formula (I) represented below: Y (CH 2) x R 1 -CH 2 -X (I) in which: R 1 represents a hydrocarbon group comprising a number n is an integer of carbon atoms, R2 represents a hydrocarbon group comprising an integer number p of carbon atoms, at least one of R1 and R2 is unsaturated, x = 0 or x = 1, 3 <n <10 , 6 <p <13, Y is selected from the group consisting of NH 2, N 3, OH, O-SO 2 -CH 3, CN, X is selected from the group consisting of CH 2 -NH 2, CH 2 -CH 2 -NH 2, CH 2 -OH , CH2-CN, CH2-N3, CH2-O-SO2-CH3 and COOR3 with R3 is H or C1-C12 alkyl, and when Y is NH2 then x = 0 or x = 1 and X is selected from the group formed by CH 2 -NH 2, CH 2 -CH 2 -NH 2, COOR 3 with R 3 represents H or C 1 -C 12 alkyl, when Y is N 3, then x = 0 and X is selected from the group consisting of CH 2 -N 3, CH 2-CN, COOR3 with R3 represents H or C1-C12 alkyl, when Y is O-SO2-CH3 then x = 0 and X is selected from l the group formed by CH 2 -O-SO 2 -CH 3, CH 2 -CN, COOR 3 with R 3 represents H or C 1 -C 12 alkyl; and when Y is CN then x = 0 and X is selected from the group consisting of CH2-CN, CH2-N3, when Y is OH then x = 0 and X is CH2-OH. According to an embodiment of the invention, in the compounds of formula (I): Y = OH, x = 0 and X = CH 2 -OH, or - Y = NH 2, x = 0 or x = 1 and X is selected from the group consisting of CH2-N112, CH2-CH2-NH2 and COOH, or - Y = CN, x = 0 and X = CH2-CN, - Y = N3, x = 0 and X = CH2-N3 . In one variant of the invention, in the compounds of formula (I), R1 and R2 are linear. In one variant of the invention, in the compounds of formula (I), 16 <n + p <18. In one variant of the invention, in the compounds of formulas (I), (R 1 / R 2) are chosen from : - (CH3- (CH2) 5- / -CH2-CH = CH- (CH2) 7-); - (CH3- (CH2) 4- CH-CH CH (CH2) 7-); - (CH3- (CH2) 2, - / -CH2-CH = CH-CH2-CH = CH- (CH2) 7-); - (CH3-CH2-CH = CH- (CH2) 2- / CH2-CH = CH- (CH2) 7-); - (cm (rH (rH / -) - '- (CH3- (CH2) 4 CH-CHCH-CH / - (CH2) 7-); - (CH3- (CH2) 5- / -CH2-CH = CH- (CH2) 9-); - (CH3-CH2-CH = CH- (CH2) 2- / -CH2-CH = CH- (CH2) 9-); - (rH rH (rH) crrr / (ru ) - - (cm (crcr) / (cu) - - (CH2 = CH- (CH2) 2-CH = CH-CC-CC- / - (CH2) 6-); - (CH3- ( CH2) 4-CH = CH-CH2- / - (CH2) 8-); - (CH3- (CH2) 4-CH = CH-CH2-CH2- / - (CH2) 7-); - (ru (ru ) / (ru) ru (ru) l- - (CH3- (CH2) 5 -CH2-CH = CH- (CH2) 7-);. (ru (ru) / (ru) ru (ru) l- Another object of the invention relates to a process for preparing a compound of formula (Ia) comprising at least one reduction step of at least one compound of formula (Ib) according to the following scheme: ## STR2 ## wherein R1 represents a hydrocarbon group comprising an integer n number of carbon atoms, R2 represents a hydrocarbon group comprising an integer number p of carbon atoms, at least one of R1 and R2 is unsaturated, x = 0 or x = 1, 3 <n <10, 6 <p <13, X is selected from the group consisting of CH 2 -NH 2, CH 2 -CH 2 -NH 2 and COOR 3 with R 3 is H or C 1 -C 12 alkyl, and Y 'is selected from the group consisting of N 3 or CN, X 'is selected from the group consisting of CH2-N3, CH2-CN, COOR3 with R3 is H or C1-C12 alkyl, and when x = 0 then Y' = N3, when x = 1 then Y '= CN when X = COOR3 then X '= COOR3, when X = CH2-CH2-NH2, then X' = CH2-CN, when X = CH2-NH2, then X '= CH2-N3. According to one embodiment, the method further comprises at least one step of preparing at least one compound of formula (Ib) from at least one compound (Ic) according to the following scheme: Y "Y ' ## STR2 ## wherein X 'is selected from the group consisting of CH 2 -N 3, COOR 3 and CH 2-CN, Y' is selected from the group consisting of N3, CN, X "is selected from the group consisting of CH2-0-SO2-CH3, CH2-CN, COOR3 Y" is selected from the group consisting of -O-SO2-CH3, OH , CN; and when Y '= N3 and X' = CH2-N3, then Y "= -O-SO2-CH3 and X" = CH2-O-SO2-CH3, when Y '= N3 and X' = CH2-CN then Y "= -O-SO2-CH3 and X" = CH2-O-SO2-CH3 or X "= CH2-CN, when Y '= N3 and X' = COOR3 then Y" = -O-SO2-CH3 or Y "= OH and X" = COOR3, when Y '= CN and X' = CH2-N3, then Y "= CN and X" = CH2-O-SO2-CH3, when Y '= CN and X' = CH 2-CN then Y "= -O-SO 2 -CH 3 and X" = CH 2 -O-SO 2 -CH 3 According to one embodiment, the process for preparing a compound of formula (Id) comprises at least one step for reducing an ester or carboxylic acid functional group according to the following scheme: ## STR2 ## in which: R 1 represents a hydrocarbon group comprising an integer n number of carbon atoms, R2 represents a hydrocarbon group comprising an integer number p of carbon atoms, at least one of R1 and R2 is unsaturated, x = 0 or x = 1 , 3 <n <10, 6 <p <13, R3 represents H or a C1-C12 alkyl group. Another subject of the invention relates to a polymer prepared from at least one monomer chosen from the compounds of formula (I) as described above and in which: Y = OH, x = 0 and X = CH 2 -OH , or - Y = NH2, x = 0 or x = 1 and X is selected from the group consisting of CH2-N112, CH2-CH2-NH2 and COOH, or - Y = CN, x = 0 and X = CH2-CN Y = N3, X = 0 and X = CH2-N3. According to one embodiment of the invention, the invention relates to a polymer resulting from the condensation of: at least one monomer of formula (I) with x = 0 or x = 1, Y = NH 2 and X = COOH, - at least one monomer of formula (I) with x = 0 or x = 1, Y = NH2 and X = CH2-NH2 or X = CH2-CH2-N1-12 and at least one diacid monomer, of at least one monomer of formula (I) with x = 0 or x = 1, Y = NH 2 and X = CH 2 -NH 2 or X = CH 2 -CH 2 -NH 2 and at least one diisocyanate monomer, at least one monomer of formula (I) with x = 0, Y = OH and X = CH 2 -OH and at least one diacid monomer, at least one monomer of formula (I) with x = 0, Y = OH and X = CH 2 -OH and at least one diisocyanate monomer, at least one monomer of formula (I) with x = 0, Y = CN and X = CH 2 CN and at least one diamine monomer, at least one monomer of formula (I) with x = 0, Y = CN and X = CH 2 CN and at least one diol monomer, at least one monomer of formula (I) with x = 0, Y = N3 and X = CH2-N3 with at least one dialyne monomer. According to another embodiment, the invention relates to a crosslinked polymer obtained by photochemical treatment, in particular by ultraviolet treatment of at least one polymer described above. According to another embodiment, the invention relates to a photocurable composition comprising at least one polymer as described above and at least one initiator. According to another embodiment, the invention relates to a resin composition comprising at least one polymer and at least one crosslinking agent chosen from the compounds of formula (I) as described above and in which: Y = OH, x = 0 and X = CH2-OH, or - Y = NH2, x = 0 or x = 1 and X is selected from the group consisting of CH2-N112, CH2-CH2-NH2 and COOH, or - Y = CN, x = 0 and X = CH2-CN, Y = N3, x = 0 and X = CH2-N3.

Detailed description. Compounds of the invention: A first object of the invention is compounds of formula (I) represented below: Y (CH 2) x R 1 -CH-R2-X (I) in which: R 1 represents a grouping hydrocarbon compound comprising an integer n number of carbon atoms, R2 represents a hydrocarbon group comprising an integer number p of carbon atoms, at least one of R1 and R2 is unsaturated, x = 0 or x = 1, 3 <n <10, 6 <p <13, Y is selected from the group consisting of NH 2, N 3, OH, O-SO 2 -CH 3, CN, X is selected from the group consisting of CH 2 -NH 2, CH 2 -CH 2 -NH 2 , CH2-OH, CH2-CN, CH2-1.13, CH2-0-SO2-CH3 and COOR3 with R3 is H or C1-C12 alkyl, and when Y is NH2 then x = 0 or x = 1 and X is selected from the group consisting of CH2-NH2, CH2-CH2-NH2, COOR3 with R3 is H or C1-C12 alkyl, when Y is N3 then x = 0 and X is selected from the group consisting of 1 \ 13, CH2-CN, COOR3 with R3 represents H or C1-C12 alkyl, when Y is O-SO2-CH3 then x = 0 and X is chosen from the group consisting of CH2 -O-SO2-CH3, CH2-CN, COOR3 with R3 is H or C1-C12alkyl; and when Y is CN then x = 0 and X is selected from the group consisting of CH2-CN, CH2-N3, when Y is OH then x = 0 and X is CH2-OH. By hydrocarbon group is meant in the sense of the present invention a linear or branched alkyl, alkenyl or alkynyl group.

Among the compounds of formula (I), the compounds corresponding to formula (Ia) are among the preferred ones: NH 2 (I-12) x R 1 -CH-R 2 X (la) with R 1 represents a hydrocarbon group comprising a number n an integer of carbon atoms, R2 represents a hydrocarbon group comprising an integer number p of carbon atoms, at least one of R1 and R2 is unsaturated, x = 0 or x = 1, 3 <n <10, Wherein X is selected from the group consisting of CH 2 -NH 2, CH 2 -CH 2 -NH 2 and COOR 3 with R 3 being H or C 1 -C 12 alkyl. According to this variant, when X represents COOR3, preferentially R3 = H.

Among the compounds of formula (I), the compounds corresponding to formula (Ib) are among the preferred ones: Y 'R 1 -CH-R 2 X' (1b) with R 1 represents a hydrocarbon group comprising an integer n number of carbon, R2 represents a hydrocarbon group comprising an integer number p of carbon atoms, at least one of R1 and R2 is unsaturated, 3 <n <10, 6 <p <13, Y 'is chosen from the group formed N3 or CN, X 'is selected from the group consisting of CH2-N3, CH2-CN, COOR3 with R3 is H or C1-C12alkyl. According to this variant, preferably Y 'represents N3.

The compounds corresponding to the formula (Tc) below are of particular interest because they are intermediates for the synthesis of the preferred compounds (I): Y "R 1 -CH-R 2 X" with R 1 represents a hydrocarbon group comprising a number n carbon atom, R2 represents a hydrocarbon group comprising an integer number of carbon atoms, at least one of R1 and R2 is unsaturated, 3 <n <10, 6 <p <13, X "is selected from the group consisting of -CH2-O-SO2-CH3, -CH2-CN; COOR3 Y "is selected from the group consisting of CH2-O-SO2-CH3, OH, CN; when Y "= O-SO2-CH3, then X" = CH2-O-SO2-CH3 or X "= -CH2-CN or X" = COOR3, when Y "= OH, then X" = COOR3, when Y " = CN, then X "= CH2-O-SO2-CH3. Among the compounds of formula (I), formula (Id) is one of the preferred compounds: ## STR5 ## R 1 represents a hydrocarbon group comprising an integer n number of carbon atoms. carbon, R2 represents a hydrocarbon group comprising an integer number p of carbon atoms, at least one of R1 and R2 is unsaturated, 3 <n <10, 6 <p <13, in the formulas explained above , the variables R1, R2, R3, x have, unless otherwise indicated, the same meaning as in formula (I). The preferred compounds of formula (I) are those which satisfy: Y = OH, x = 0 and X = CH 2 -OH, or Y = NH 2, x = 0 or x = 1 and X is chosen from the group formed by CH 2 NH2, CH2-CH2-NH2 and COOR3 with R3 representing H, or - Y = CN, x = 0 and X = CH2-CN, - Y = N3, X = O and X = CH2-N3. Indeed, these compounds make it possible to prepare polymers, either by autocondensation or by condensation with another monomer, as will be explained below. According to a preferred embodiment, the compounds (I), in particular each of its variants (Ia), (Ib), (Ic) and (Id) satisfy one or more of the characteristics below, taken separately or in combination. - R3 represents H or a C1-C6 alkyl. Preferably, R3 represents H or a C1-C3 alkyl and even more preferably R3 represents a group chosen from H, CH3 or CH2-CH3. - 3 <n <10, preferably n = 3, 5, 6, 8, 9 or 10. - 6 <p <13, preferably p = 6, 7, 8, 10, 11, 12, 13. - 16 <n + p <18, preferably (n, p) represents: (6,10), (5,11), (3,13), (9,7), (6,12), (10) , 6), (8, 8), (5,13), or (6,12), - R1 and / or R2 are linear. In one embodiment, the R1 chain is saturated. Preferably, according to this variant, R1 is chosen from the group formed by CH3- (CH2) 2-, CH3- (CH2) 4-, CH3- (CH2) 5-. In another embodiment, the chain R1 comprises at least one unsaturation. In a preferred variant, the chain R 1 comprises at least one carbon-carbon double bond or a carbon-carbon triple bond or optionally a mixture of double and triple bonds when the chain R 1 comprises several unsaturations. Preferably, according to this variant, the chain R1 is chosen from the group formed by CH3-CH2-CH = CH- (CH2) 2-, CH3- (CH2) 4 -CH = CH- (CH2) 2-, CH3- ( CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2, CH 2 CH (CH 2) 4-CC-CC-, CH 3 - (CH 2) 5-CC-CC-, CH 2 = CH- (CH 2) 2-CH = CH-CC- CC-, CH3- (CH2) 4-CH = CH-CH2-; CH3- (CH2) 4-CH = CH-CH2-CH2-.

In one embodiment, the chain R2 is saturated. According to this embodiment, preferably, the chain R2 is chosen from the group formed by - (CH2) 6-, - (CH2) 7-, - (CH2) 8- In another embodiment, the chain R2 comprises at least one unsaturation. Preferably, the unsaturation is located at the alpha, beta or gamma position of the carbon carrying the functions - (CH 2) n - Y and R 1 with R 1, R 2 and x as defined above. Preferably, the unsaturation is a carbon-carbon double bond. According to this variant, even more preferably, the chain R 2 is chosen from the group formed by -CH 2 -CH =CH- (CH 2) 7; CH-CH CH-CH (CH 2) 7-; -CH2-CH = CH-CH2-CH = CH- (CH2) 7-; -CH2-CH = CH- (CH2) 7-, -CH2-CH-CH- (CH2) 9-; - (CH2) 2.-CH-CH- (CH2) 7-; - (CH2) 2-CH-CH- (CH2) 9-- In another variant of the invention, the preferred specific combinations (R1 / R2) are the following: - (CH3- (CH2) 5- -CH2- CH = CH- (CH2) 7-); - (CH3- (CH2) 4- CH-CH CH (CH2) 7-); - (CH3- (CH2) 2- / -CH2-CH = CH-CH2-CH = CH- (CH2) 7-); - (CH3-CH2-CH = CH- (CH2) 2- CH2-CH = CH- (CH2) 7-); - (CH3- (CH2) 4-CH = CH- (CH2) 2- - (CH2) 7-); - (CH3- (CH2) 4 CH-CH CH-CH / - (CH2) 7-); - (CH3- (CH2) 5- CH2-CH = CH- (CH2) 9-); - (CH3-CH2-CH = CH- (CH2) 2- / -CH2-CH = CH- (CH2) 9-); - (cF-1) C- (CH 1), 1H- (CH 3 - (CH 2) 5 -C = CC = C- / - (CH 2) 6-); - (CH 2 = CH- (CH 2) 2, -CH = CH-CC-CC- / - (CH2) 6-); - (CH3- (CH2) 4-CH = CH-CH2- / - (CH2) 8-); - (CH3- (CH2) 4-CH = CH-CH2-CH2- / - (CH2) 7-); - (ru (- CH - / - (CH - rH (rH -) - - (CH3- (CH2) 5- CH2) CH = CH- (CH 2) 7-); (r - (CH - (CH 2) 5 -CH 2 -CH = CH- (CH 2) 9- According to a variant of the invention which will be explained below, the compounds (I) can be obtained in the form of mixtures (Ii) and (Iii): ## STR2 ## C1-12) x R'i CC-R12 XH2H (Iii) in which either R'1 is R1 and CH2-R '2 is R2 or CH2-R'1 is R1 and R'2 is R2. variant relates to all of the preferred formulas (I), (Ia), (Ib), (Te), (Id) which have been described above, and mixtures (Ii) and (Iii) are obtained in substantially equimolar amounts of Ii) and (Iii) The compounds of the invention have the advantage over the compounds of the prior art of having at least one branching and at least one unsaturation. Indeed, the compounds of the invention (I) have a difunctional main chain represented by Y- (CH 2) x -CH-R2-X and a side chain represented by R 1 (or branching) and at least one unsaturation is in the main chain R2 and / or in the side chain R1. The compounds of the invention advantageously comprise a sidechain of variable and variable length (from 3 to 10 carbon atoms). Moreover, in the case where Y = NH 2, the compounds of the invention comprise alkyl chains located in alpha or beta of the Y = NH 2 function, these compounds are therefore amines of primary class, and therefore are advantageously more reactive. that the secondary amine function present in the N-substituted diamines of the prior art. The diversity of the chemical structures of the compounds according to the invention advantageously allows the development of a wide range of products, especially in the polymer field and more particularly in the polyamide field. Indeed, the compounds of formula (A) can serve as monomers for the synthesis of polymers. The presence of at least one unsaturation in the main chain and / or in the side chain affords the possibility of cross-linking between polymer chains thus making it possible to modulate the mechanical properties of the polymers in which the compounds of formula A are present. In addition, the presence of branching of variable length in the compounds of formula (A) advantageously makes it possible to modify the crystallinity of the polymers consisting of these compounds and, in particular, to modify their thermal properties. Thus, for example, branched polyamides have melting temperatures which can be much lower than their linear equivalents of the prior art. This makes it possible to envisage methods for using these branched polyamides at low temperature, which is not currently possible because of the generally high melting temperatures of the polyamides present on the market which limit their application to media which are sensitive to heat. high temperatures (plastics, wood ...). The processes for the preparation of the compounds of the invention The subject of the invention is also a process for the preparation of the compounds of formula (I) which is set out below in its different variants. In all the schemes set out below, unless otherwise indicated, the variables R1, R2, x, X, Y have the same definition as in formula (I). When one or more of these variables has a more limited meaning it is then indicated in connection with the scheme concerned. Preparation of compounds of formula (I) with Y = NH 2: According to the invention, when Y = NH 2, the compounds (I) are represented by formula (Ia). According to this variant, the process of the invention is characterized in that it comprises at least one step of reducing a compound of formula (Ib) according to scheme 1 below: Y 'NH 2 (CH 2) x R 1 ## STR2 ## Scheme X is selected from the group consisting of CH 2 -NH 2, CH 2 -CH 2 -NH 2 and COOR 3 with R 3 being H or C 1 -C 4 alkyl. C12, and Y 'is selected from the group consisting of N3 or CN, X' is selected from the group formed CH2-N3, CH2-CN, COOR3 with R3 is H or C1-C12 alkyl, and when x = Then Y '= N3, when x = 1 then Y' = CN, when X = COOR3 then X '= COOR3, when X = CH2-CH2-NH2 then X' = CH2-CN, when X = CH2-NH2 then X '= CH2-N3. Indeed, by reducing the nitrile and azide functions of the compounds (Ib), amine functions are obtained. This step is carried out according to means well known to those skilled in the art. For example, treatment with LiAlH 4 in anhydrous diethyl ether can be used at room temperature and with stirring.

The compounds of formula (Ib) can be obtained by different synthetic routes. Preparation of compounds of formula (I) with Y = N 3: In a variant of the process, the compound of formula (Ib) is obtained directly by conversion of the alcohol function of a fatty acid of formula (Ie) to an azide function according to Scheme 2 below: ## STR2 ## wherein X 'represents a group selected from CH2N3 and COOR3, and R3 represents H or C 1 -C 12 alkyl, X "'is a group selected from OH and COOR 3, and R 3 is H or C 1 -C 12 alkyl.

This step is carried out according to means well known to those skilled in the art. In particular, treatment with a diphenylphosphoryl azide in the presence of 1,8-diazabicyclo [5.4.0] undec-7-ene can be used. According to another variant, when Y represents N3 in the formula (I), the compound (Ib) can be obtained by a process comprising at least one step of converting a mesyl to azide by means well known to the human being. in particular, by NaN3 treatment according to Scheme 3 below: SO, C1-1, O (Ic) (Ib) Scheme 3 with X 'is chosen from the group formed by COOR3 or CH2-CN, when X' = CH2-N3 then X "= CH2-0-802-CH3, when X '= CH2-CN then X" = CH2-CN, when X' = COOR3 then X "= COOR3.

This step is carried out according to means well known to those skilled in the art. In particular, it is possible to use a treatment with NaN3 while stirring with heating of the reaction medium. Preparation of compounds of formula (I) with Y = CN: When Y represents CN in formula (I), compound (I) is obtained by a process comprising at least one step of converting mesyl to nitrile by means which are well known to those skilled in the art, in particular by treatment with KCN according to Scheme 4 below: ## STR2 ## in which R 1 - CH - R 2 - X - R 1 - CH - R 2 - (IC) (Ib) this scheme: - when X 'represents COOR3, X "represents COOR3, - when X' represents CH2-CN, X" represents CH2-CN or CH2-OSO2CH3, - when X 'represents N3, X "represents N3.

Preparation of compounds of formula (Ic) with Y "= O-SO 2 -CH 3: In a preferred embodiment, the compound (Tc) comprising a group Y" = OSO 2 CH 3 can be obtained from the corresponding alcohol (Id) by means well known to those skilled in the art, in particular by treatment with a mesyl halide, in particular with mesyl chloride, according to scheme 5 below: ## STR1 ## Wherein: X "represents a group selected from COOR3 and CH2-0-SO2-CH3, when X" = COOR3 then X "'= COOR3 and -" R1-CR2- X "H (Id) (Ic) when X "= CH 2 -O-SO 2 -CH 3 then X" '= CH 2 -OH.

Preparation of compounds of formula (I) with X = CH 2 OH and Y = OH: In a preferred embodiment, the process further comprises at least one step of preparing at least one compound of formula (I) with X = CH 2 OH and Y = OH from at least one compound (Ie) by reduction of at least one carboxylic ester or carboxylic acid functional group COOR 3 according to the following scheme: ## STR2 ## R 1 - CH 2 R 2 --COOR 3 ## STR2 ## Preparation of compounds of formula (Ie) The compound (Ie) can be a fatty acid or an ester of such an acid. In the case of an ester, it can be obtained from the corresponding acid by means well known to those skilled in the art. According to one variant, it is also possible to use as starting material an epoxidized fatty acid, such as C18: 1 vernal acid (9Z, 12.13-0) or C18: 1 coronary acid (12Z, 9.10-0). ), alchornic acid C20: 1 (11Z, 14.15-0). These amino acids have the particularity of having an epoxy ring which can be opened to give a mixture of two hydroxylated fatty acids according to Scheme 7 below which illustrates the particular case of vernolic acid.

According to this scheme, the epoxide group is reduced, for example by treatment with a hydride such as sodium tetrahydroborate to yield two alcohols which differ only in the position of the hydroxyl function. All fatty acids naturally carrying an epoxide function are likely to lead to such mixtures. The invention therefore relates to mixtures of compounds (Ii) and (Iii) corresponding to formula (I), in which X, Y, x have the same meaning as in formula (I), ie R'1 represents R1 and CH2-R'2 represents R2 or CH2-R '1 represents R1 and R'2 represents R2 and the R'i-epoxy-R'2-COOH molecule is a naturally epoxidized fatty acid included in the list which has been given here -above. In these mixtures, the compounds (Ii) and (Iii) are substantially present in equivalent molar amounts. YY C1-12) x C1-12) x R'1912-191-1: Z'FX R'1 CC-R'-X (Ii) H H2 2 (Iii) Starting product of the processes: The starting material of the synthesis of the compounds of formula (Ia) and intermediate products (Ib), (Tc), (Id), (Ie), therefore of all the compounds of formula (I) is an unsaturated fatty acid or an ester unsaturated fatty acid comprising either a hydroxyl function or an epoxy group. Subsequently, the term "fatty acid" defines a fatty acid either in its carboxylic acid form, either in its salt form or in its ester form. The fatty acid may be monounsaturated or polyunsaturated, cis or trans configuration. The unsaturation may be a carbon-carbon double bond or a carbon-carbon triple bond. When a polyunsaturated fatty acid is used, the unsaturations may be one or more carbon-carbon double bonds or one or more carbon-carbon triple bonds or a mixture of carbon-carbon double bonds or triple bonds. The variable position of the hydroxyl function or of the epoxy group on the hydrocarbon chain of the fatty acid makes it possible to obtain compounds of formula (I), the length of the branch of which varies. All the unsaturated fatty acids comprising either a hydroxyl function or an epoxy group are suitable except those in which the hydroxyl function is located at the end of the hydrocarbon chain opposite the end bearing the acid or ester function, on the last carbon atom of the hydrocarbon chain; the epoxy group is located at the end of the hydrocarbon chain opposite the end bearing the acid or ester function, on the last carbon atom and the penultimate carbon atom of the hydrocarbon chain Among the monounsaturated fatty acids that can be used as starting material, mention may be made of: vernal acid C18: 1 (9Z, 12,13-0), ricinoleic acid C18: 1 (9Z, 12-OH), C18: 1 strophantus acid (12Z, 9-OH), lesquerolic acid C20: 1 (11Z, 14-OH), coronary acid C18: 1 (12Z, 9.10-0), alchornic acid C20: 1 (11Z, 14.15 -0). These are all cis-configuration fatty acids. Among the polyunsaturated fatty acids that can be used as starting products, mention may be made of: C 18: 2 coriolic acid (9Z, 11E, 13-OH), C 18: 2 avianoleate acid (9Z, 12Z, 15-OH), C18: 2 (9Z, 15Z, 12-OH) densipolic acid, C18: 2 13-dimorphecolic acid (10E, 12E, 9-OH), C18: 2 α-dimorphecolic acid (10E, 12Z, 9) -OH), C20: 2 auricolic acid (11Z, 17Z, 14-OH), C18: 1 isanolic acid (17,8-OH). According to one variant, it is also possible to use as starting products an epoxidized fatty acid, such as vernic acid C18: 1 (9Z, 12.13 -0), coronary acid C18: 1 (12Z, 9.10-0). ), alchornic acid C20: 1 (11Z, 14.15-0). These fatty acids have the particularity of having an epoxy ring which can be opened to give a mixture of two hydroxylated fatty acids.

The fatty acids derived from renewable raw materials and preferably used as starting material are chosen from the group formed by: vernic acid C18: 1 (9Z, 12,13-0), ricinoleic acid C18: 1 w-9 (9Z, 12-OH), C18: 1 strophantus acid (12Z, 9-OH), lesquerolic acid C20: 1 (11Z, 14-OH), C18: 1 coronary acid (12Z, 9, 10-0), alchornic acid C20: 1 (11Z, 14,15-0), coriolic acid C18: 2 (9Z, 11E, 13-OH), avenoleate C18: 2 (9Z, 12Z , 15-OH), densipolic acid C18: 2 (9Z, 15Z, 12-OH), 13-dimorphecolic acid C18: 2 (10E, 12E, 9-OH), α-dimorphecolic acid C18: 2 (10E, 12Z, 9-OH), C20: 2 auricolic acid (11Z, 17Z, 14-OH), C18: 1 isanolic acid (17, 8-OH). The invention also relates to a process for obtaining a compound of formula (I) as defined above which uses as starting material at least one fatty acid appearing in the lists given above. The monounsaturated or polyunsaturated fatty acids bearing either a hydroxyl function or an epoxy group are available from the suppliers, in particular from the following suppliers: TCI Fine Chemicals, Aldrich, AAA Chemicals, 3B Scientific Corporation, 1K Scientific Co ... Advantageously, the process synthesis of the invention can therefore be implemented from fatty acids that can be obtained and are available from natural raw materials of plant origin or animal origin, including algae, so from renewable raw materials. Such raw materials allowing the extraction of fatty acids are available in particular from the following companies: Olvea, Novance, Chempri Oleochemicals, Chempri Oleochemicals ...

Processes for their production are described in: Bokeno [Isano] oil. I. The Fat Acids of the Oil and Their Separation, Kaufmann H.P., Herminghaus H., Fette und Seifen, 53, 537 (1951); Geranium sanguineum (Geraniaceae) seed oil: A new source of petroselinic and vernolic acid, Tsevegsuren N., Aitzetmuller K., Vosmann K., Lipids, 39 (6), 571 (2004); and in WO 2011/143753.

The synthesis method according to the invention has the advantage of being simple to implement because it uses a small number of transformation steps. It also makes it possible to obtain sufficient yields, in particular for an industrial implementation. Moreover, the process according to the invention makes use of the use of raw materials of renewable natural origins, that is to say of raw materials of non-fossil origin, in particular such as oil, coal and gas. For the purposes of the present invention, the term "raw materials of renewable natural origin" or "renewable raw materials" means a renewable raw material which is a natural animal or plant resource whose stock can be reconstituted over a period of time. short on the human scale. In particular, this stock must be renewed as quickly as it is consumed. Thus monounsaturated or polyunsaturated fatty acids of natural origin are derived from vegetable oils extracted from various plants such as sunflower, rapeseed, castor oil, lesquerella, vernonia, ougokea, dimorphoteca, strophantus, olive, soybean, palm, coriander, celery, dill, carrot, fennel, meadowfoam (Limnanthes Alba), avocado, sea buckthorn, safflower and camelina. They can also come from the animal world land or sea, and in the latter case, both in the form of fish, mammals and algae. These are usually fats derived from ruminants, fish such as cod, or marine mammals such as whales or dolphins. Renewable raw materials contain 14 carbon 14C, unlike materials from fossil materials. Carbon-containing materials derived from living organisms, whether animal or plant, consist of a mixture of 3 isotopes: 12C (representing approximately 98.892%), 13C (representing approximately 1.108%) and 14C (present in trace amounts). : 1.2.1040%). In a living organism, the 14C / 12C ratio is kept constant by metabolism because carbon is continuously exchanged with the external environment. The proportion of 14C being constant in the atmosphere, it is the same in the organism, as long as it is alive, since it absorbs this 14C in the same way as the ambient 12C. The average ratio of 14C / 12C in a living organism is equal to 1.2.10-12. 12C is stable, that is, the number of 12C atoms in a given sample is constant over time. 14C, on the other hand, is radioactive and the number of atoms of 14C in a sample decreases over time (t) according to the law: n = no exp (-at), in which: - no is the number of 14C to the origin (on the death of the creature, animal or plant), - n is the number of 14C atoms remaining at the end of time t, - a represents the decay constant (or radioactive constant); a is related to the half-life. The half-life is the time after which any number of radioactive nuclei or unstable particles of a given species are halved by disintegration. The half-life of carbon 14 is 5730 years. Given the half-life of carbon 14, the carbon content 14 is substantially constant from the extraction of renewable raw materials, to the production of compounds, in particular monomers according to the invention and even up to end of their use. Therefore, the presence of carbon 14 in a material, whatever the quantity, gives an indication of the origin of the molecules constituting it, namely that they are bio-sourced, that is, say that they come from renewable raw materials and not fossil materials. This mass quantity of bio-sourced organic carbon, ie derived from renewable raw materials relative to the total mass of carbon, can be measured by determination of the carbon content 14 according to one of the methods described in the ASTM D6866-06 standard. (Standard Test Methods for Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis). This standard ASTM D6866-06 includes three methods of measuring organic carbon from renewable raw materials (biobased carbon in English). Consequently, the presence of carbon 14 in a material, whatever the quantity, gives an indication of the origin of the molecules constituting it, namely that a certain fraction comes from renewable raw materials and not from materials. fossils. The measurements carried out by the methods described in the ASTM D6866-06 standard, in particular by mass spectrometry or by liquid scintillation spectrometry, make it possible to distinguish monomers or starting reactants derived from renewable materials from monomers or reagents derived from fossil materials. . These measurements can be used as a test to identify the origin of the compounds. The polymers obtained from the compounds of the invention: The invention also relates to the use of the novel branched compounds of formula (I) as described above for the synthesis of polymers, in particular for the synthesis of polyamides, polyureas, polyurethanes, polyesters. It also relates to the use of preferred variants of these novel branched compounds which have been described in detail above.

The invention relates in particular to at least one polymer prepared from at least one monomer selected from the compounds of formula (A), which are a subfamily of compounds (I), Y (CH2) x R1-CH - R 2 -X (A) in which: R 1 represents a hydrocarbon group comprising an integer n number of carbon atoms, R 2 represents a hydrocarbon group comprising an integer number p of carbon atoms, at least one of R 1 and R2 is unsaturated, x = 0 or x = 1, 3 <n <10, 6 <p <13, Y is selected from the group consisting of NH2, N3, OH, CN, X is selected from the group consisting of CH2- NH2, CH2-CH2-NH2, CH2-OH, CH2-CN, CH2-N3, and COOR3 with R3 is H, and Y = OH, x = 0 and X = CH2-OH, or Y = NH2, x = 0 or x = 1 and X is selected from the group consisting of CH2-NH2, CH2-CH2-NH2 and COOH, where Y = CN, x = 0 and X = CH2-CN, or Y = N3, X = 0 and X = CH2-N3. The invention relates in particular to polymers prepared from monomers of formula (A) as described above but also to their preferred variants of the monomers of formula (A) which have been described in detail above and especially preferred variants in which one or more of the characteristics below, taken separately or in combination is verified: - R3 represents H or a C1-C6 alkyl. Preferably, R3 represents H or a C1-C3 alkyl and even more preferably R3 represents a group chosen from H, CH3 or CH2-CH3. - 3 <n <10, preferably n = 3, 5, 6, 8, 9 or 10. - 6 <p <13, preferably p = 6, 7, 8, 10, 11, 12, 13. - 16 <n + p <18, preferably (n, p) represents: (6,10), (5,11), (3,13), (9,7), (6,12), (10) , 6), (8, 8), (5,13), or (6,12), - R1 and / or R2 are linear. R1 is selected from the group consisting of CH3- (CH2) 2-, CH3- (CH2) 4-, CH3- (CH2) 5-, CH3-CH2-CH = CH- (CH2) 2-, CH3- ( CH2) 4-CH = CH- (CH2) 2-, CH3- (CH2) 4 CH-CH CH-CH, CH3-CH2-CH = CH = CH2-CH2-, CH2 = CH- (CH2) 4-CC -CC-, CH3- (CH2) 5-CC-CC-, CH2 = CH- (CH2) 2-CH = CH-CC- CE13- (CH2) 4-CH = CH-CH2-; CH3- (CH2) 4-CH = CHCH 2-CH2-. R2 is selected from the group consisting of - (CH2) 6-, - (CH2) 7-, - (CH2) 8-, -CH2-CH = CH- (CH2) 7; CH-CH CH-CH (CH 2) 7-; -CH2-CH = CH-CH2-CH = CH- (CH2) 7-; -CH2-CH = CH- (CH2) 7-, -CH2-CH = CH- (CH2) 9-; - (CH2) z-CH = CH- (CH2) 7-; - (CH2) 2-CH = CH- (CH2) 9-. The invention also relates to the use of at least one branched compound of formula (A) as described above with Y = NH 2, x = 0 or x = 1, X = COOH for the synthesis of pseudoproteins by incorporating one or more of these amino acids into a natural or synthetic protein sequence, using any technique known to those skilled in the art. The new branched diamines and the new branched amino acids of formula (A) which have been described above can be used for the synthesis of polymers, in particular the synthesis of polyamides. The subject of the invention is also any polymer or copolymer of polyamide type obtained by polycondensation of at least one diacid and at least one monomer of formula (A) with x = 0 or x = 1, Y = NH 2 and X = CH 2 -NH 2 or X = CH 2 -CH 2 -NH 2 such as those described above. The subject of the invention is also any polymer or copolymer of polyamide type obtained by polycondensation of at least one monomer of formula (A) with x = 0 or x = 1, Y = NH 2 and X = COOH such as those which have been described above. The new branched diamines of formula (A) which have been described above can be used for the synthesis of polymers, in particular the synthesis of polyureas. The subject of the invention is also any polymer or copolymer of polyurea type obtained by polycondensation of at least one diisocyanate and of at least one monomer of formula (A) with x = 0 or x = 1, Y = NH 2 and X = CH2-NH2 or X = CH2-CH2 -NFI2 The invention also relates to any polymer or copolymer of polyamide type obtained by polycondensation of at least one diamine and at least one monomer of formula (A) with x = 0 , Y = CN and X = CH2-CN. The invention also relates to any polymer or copolymer of polyamide type obtained by polycondensation of at least one diol and at least one monomer of formula (A) with x = 0, Y = CN and X = CH2-CN. The novel branched diols of formula (A) which have been described above can be used for the synthesis of polymers, in particular the synthesis of polyurethanes, polyesters and polyamides. Reference can be made to Synthesis of polyamides from p-Xylylene glycol and dinitriles, Lakouraj M.M., Mokhtary M., J. Polym. Res., 16 (6), 681 (2009) and Synthesis of poly (ether amide) s from p-xylylene glycol and bis (ether nitrile) s, Lakouraj M.M., Mokhtary M., Polym. Int., 58, 1167 (2009) which describe the synthesis of polymers of this type. The subject of the invention is also any polymer or copolymer of polyurethane type obtained by polycondensation of at least one diisocyanate and at least one monomer of formula (A) with x = 0, Y = OH and X = CH 2 -OH.

The invention also relates to any polymer or copolymer of polyester type obtained by polycondensation of at least one diacid and at least one monomer of formula (A) with x = 0, Y = OH and X = CH 2 -OH. The branched diazotides of formula (A) can be used in combination with dialyne monomers to synthesize polymers by so-called "click chemistry" reactions. Reference can be made to "Click Chemistry in Polymer and Materials Science" W.H.Binder and R. Sachsenhofer, Macromol. Rapid Commun., 28, 15-54 which describes the synthesis of polymers by this method. Among the known and commercially available dialkyl monomers, there may be mentioned in particular: 1,4-diethynylbenzene (available from Aldrich Fluka). The subject of the invention is also a copolymer resulting from the reaction between at least one monomer of formula (A) as defined above with Y = N 3, x = 0 and X = CH 2 -N 3 and at least one dialyne monomer.

The monomers (A) with Y = N3, x = 0 and X = CH2-N3 can also be used as crosslinking agents in polymers such as polymers bearing alkyne, alkene, nitrile or vinyl functional groups. The subject of the invention is also a resin composition comprising at least one polymer or a copolymer and comprising at least one compound (A) with Y = N 3, x = 0 and X = CH 2 -N 3 as crosslinking agent. The diamines of formula (A) with x = 0 or x = 1, Y = NH 2 and X = CH 2 -NH 2 or X = CH 2 -CH 2 -NH 2 may also be used as crosslinking agents in polymers such as polyepoxide polymers, polyamines or polyols. The subject of the invention is also a resin composition comprising at least one polymer or copolymer and comprising at least one diamine of formula (A) with x = 0 or x = 1, Y = NH 2 and X = CH 2 -NH 2 or X = CH2-CH2-NH2 as crosslinking agent.

The subject of the invention is also resin preparation kits comprising on the one hand at least one composition based on a polymer or a copolymer, and on the other hand at least one compound (A) capable of crosslinking the polymer or the copolymer, the polymer composition and the compound (A) being in a package adapted to prevent the crosslinking reaction between the polymer and the crosslinking agent from occurring without the intervention of an operator. Such a kit makes it possible to prepare a hardenable resin, the first and second compositions being mixed just before use. Advantageously, the invention relates to polymers prepared from monomers of which at least 20% by weight are obtained from materials of renewable origin according to ASTM D6866-06. Even better, these polymers are prepared from monomers of which at least 30% by weight are obtained from materials of renewable origin according to ASTM D686606, preferably at least 40%, and still more preferably at least 50%.

The branched monomers of formula (A) according to the present invention have the advantage of giving access to a wide variety of polymers with flexible thermal and mechanical properties. The branched monomers of formula (A) have branches of variable lengths. These branches make it possible to modulate the thermal properties of the polymers in which they are incorporated, in particular for polyamides. Thus, for example, the branched polyamides have melting temperatures which can be much lower than their linear equivalents. This makes it possible to envisage methods for using these polyamides at low temperature, which is not currently possible because of the generally high melting temperatures of the polyamides present on the market. The branched monomers of formula (A) according to the invention still advantageously make it possible to vary the mechanical properties, in particular of polyamides, by acting as internal plasticizer, making it possible, for example, to improve the flexibility of the materials. Thus, the polymers according to the present invention have the advantage of having a limited plasticizer content relative to the polymers of the prior art since the branched monomer of formula (A) acts as a chain spacer because of the presence of branches chemically bonded to the polymer chains, that is to say that the branched monomer of formula (A) acting as internal plasticizer. The migration of the plasticizer during the aging of the polymer, leading, for example, to an alteration of the properties of the polymer or to a contamination of the surfaces in contact is therefore advantageously very limited in the polymers of the invention.

These branched monomers of formula (A) constitute an alternative to diamine and amino acid derivatives derived from fossil resources. They also allow the use of vegetable oils in the field of polymers, especially plastic materials.

The polymers according to the invention comprise at least one unsaturation. The presence of at least one unsaturation in the branched monomer of formula (A) also advantageously makes it possible to obtain polymers of modular structures. In fact, this unsaturation constitutes a privileged site for the insertion of chemical groups thus making it possible to modify the chemical and / or mechanical resistance of the polymers obtained, in particular polyamides. Advantageously, this unsaturation also constitutes a privileged site for the establishment of chemical bonds between chains (crosslinking), thus making it possible to improve the chemical and / or mechanical resistance of the polymers obtained, in particular polyamides. The crosslinking of the polymers according to the present invention is carried out by means well known to those skilled in the art. In particular, the crosslinking can be carried out by a photochemical treatment, such as an ultraviolet treatment, or by heating in the presence of unsaturated crosslinking agents such as styrene, or of crosslinking agents containing at least two thiol or azide functions.

Thus, another subject of the invention is a crosslinked polymer obtained by a suitable treatment, in particular a photochemical treatment, in particular an ultraviolet treatment, of at least one polymer as defined above. Preferably, the crosslinked polymer is obtained by ultraviolet treatment of at least one polyamide or copolyamide comprising at least one monomer of formula (A) as defined above and at least one radical initiator. The polymers of the invention may also, within a composition, be mixed with other materials such as other polymers, or one or more additives chosen from fillers, fibers, dyes, stabilizers, impact modifiers, surfactants, pigments, brighteners, antioxidants, natural waxes and mixtures thereof. Another subject of the invention is a photocurable composition, in particular by photochemical treatment, in particular by ultraviolet radiation, comprising a polymer according to the invention as defined above and at least one initiator.

Preferably, the photo-crosslinkable composition comprises at least one polyamide or a copolyamide according to the invention and at least one initiator. For the purposes of the present invention, the term "initiator" is intended to mean a photosensitive chemical molecule which reacts by creating one or more free radicals. The initiators can be radical photoinitiators. Many initiators are known to those skilled in the art, including: acetophenone derivatives, acylphosphine oxides, benzophenone and its derivatives, thioxanthone and its derivatives.

The subject of the invention is also kits for the preparation of a photocrosslinked resin comprising on the one hand at least one radical initiator and on the other hand at least one composition based on a polymer or a copolymer according to the invention, such as a polyamide or copolyamide, in a packaging adapted to prevent initiation of the photocrosslinking reaction of the polymer to occur without the intervention of an operator. Such a kit makes it possible to prepare a resin based on a crosslinked polymer, the initiator and the polymer being mixed just before use. Such packaging may consist of a container having two or three internal compartments for the separate storage of each of the components. There may be provided means for contacting the contents of the different compartments so as to initiate crosslinking in the container. It is also possible to provide a kit consisting of two or three separate vials associated in the same package and each comprising the appropriate amounts of each product for the preparation of the crosslinked polymer, so as to avoid weighing operations and / or dosage. In a variant of the invention, the photocurable composition according to the invention is solid, in particular is in the form of a powder used to cover a support. Advantageously, the solid photocurable composition comprises at least one polyamide or copolyamide according to the invention. This photocurable composition has the advantage, because of the presence of branched monomers in the polyamide or copolyamide, to have a lower processing temperature than the powder-based polymer-based compositions of the prior art. The photocurable composition according to the invention therefore advantageously makes it possible to cover heat sensitive substrates, such as wood and its derivatives (plywood, particle board, fiber, etc.), plastic or cardboard. The photocurable composition may also be used to cover metal or mineral substrates such as concrete, steel, reinforced concrete or cellular concrete, for which it is desired to avoid losing certain qualities of the support when applying a coating .

Thus, the subject of the invention is also a polymer film obtained by photochemical or thermal treatment of at least one polymer according to the invention. The subject of the invention is also a polymer film obtained by photochemical treatment, in particular by ultraviolet treatment, of a photocrosslinkable composition according to the invention. Obtaining the film from a polymer or photocurable composition according to the invention is carried out by means well known to those skilled in the art. The following documents describing the synthesis of these films can be consulted: Optimization of wettability and adhesion of a UV curable powder coating on polypropylene substrates, Wouters M., Muixi PC, by Ruiter B., Contact Angle, Wettability and Adhesion Vol 5, 207-227 (2008) - Basics and Applications of Photopolymerization Reactions, Fouassier JP, Allonas X. Ed., 1, 269-284 (2010); UV-curable powder coatings for heat-sensitive substrates, Schwarb R., Knoblauch M., Cox J., Coatings Tech., 7 (7), 44-49 (2010). The polymers of the invention, when they are not crosslinked, can be extruded, coextruded, injected, blown, molded, overmolded, calendered or thermoformed. It can be made of such objects as for example tubes, films, plates, rods, bottles, containers, items of electrical and electronic equipment such as telephone, computer, multimedia systems etc ... The invention therefore also relates to a support covered with a film according to the invention or coated with the ultra-violet photocurable composition according to the invention, the support being chosen from plastics, wood and its derivatives, a mineral carrier, a metal alloy, or mixtures thereof. Figures: Figure 1: Scheme 9: Example of synthesis of 1-hexyl-dodec-3-ene-1,12-diamine (10). Figure 2: Scheme 10: Example of synthesis of 1-hexyl-tridec-3-ene-1,13-diamine (22). 3: Scheme 11: Synthesis Example of methyl 12-amino-12-hexyl-dodec-9-enoate (16) and 12-amino-12-hexyl-dodec-9-enoic acid (16 ') . Experimental part Schemes 9 to 11 describe examples of syntheses of compounds of the invention made from methyl ricinoleate (1) or ricinoleic acid (1 ').

Procedures: - Purification of methyl ricinoleate (compound 1) Methyl ricinoleate (TCI Europe,> 75%) is purified by double distillation under vacuum.

A.S. Bailey, V.G. Kendall, P. B. Lumb, J. C. Smith, C. H. Walker; J. Chem. Soc., 1957, 3027-3032 (Beilstein IV, 1026, 1207). Purification of Ricinoleic Acid (Compound 1) Ricinoleic acid is obtained by hydrolysis of methyl ricinoleate. General procedure for the reduction with LiAlH 4 (synthesis of compounds 2, 10 and 22) In a two-necked flask equipped with a magnetic stirrer and a refrigerant, 9.6 mmol of 1, 1 'and 4 in 50 ml of anhydrous diethyl ether are added to either 45 ml of a solution of LiAlH 4 (1.1 g, 28.8 mmol) in anhydrous diethyl ether for the reduction of the compounds 1, 1 ', or to 75 ml of a solution of LiAlH 4 ( 1.8 g, 48.4 mmol) in anhydrous diethyl ether for the reduction of compounds 4. After stirring for 6 h at room temperature, the lithioaluminate complex is hydrolysed. The mixture is then washed with saturated NaCl solution. The products 2, 10 and 22 are obtained after drying over MgSO 4 and evaporation of solvent. (Yield 80-85% for compounds 2, 10 and 22). General procedure for the reaction with mesyl chloride (synthesis of compounds 3, 14 and 14 ') In a two-necked flask equipped with magnetic stirring and a condenser, compounds 2, 1 and 1' (22, 7 mmol in hydroxyl functions) are solubilized in 50 ml of anhydrous diethyl ether. 6.0 mL of Net3 (45.5 mmol) followed by 3.9 mL (50.0 mmol) of mesyl chloride are then added. After stirring for 1 hour at room temperature, the organic medium is washed with water. The products 3, 14 and 14 'are obtained after drying over MgSO 4 and evaporation of solvent (yield 90%). General procedure for the nucleophilic substitution reaction of the mesylate groups with sodium azide (synthesis of compounds 4, 15, 15 'and 21) In a two-necked flask equipped with a magnetic stirrer and a condenser, the compounds 3, 14, 14 'and 20 (61 mmol in mesylate functions) are solubilized in 140 mL of DMF. Then, 97.5 mmol of NaN3 are added. After 24h stirring at 75 ° C, the organic medium is washed with 50 mL of water. The products 4, 15, 15 'and 21 are obtained after extraction in diethyl ether (6 × 50 ml), drying over MgSO 4 and evaporation of solvent (yield 70-90%). - Procedure for obtaining the azide function from the alcohol function in a single step (synthesis of compounds 15, 15 ') In a two-necked flask provided with a magnetic stirrer and a refrigerant, the compounds 1 1 '(25.6 mmol) are solubilized in 40 mL of DMF.

Then, diphenylphosphoryl azide (51.2 mmol) and 1,8-diazabicyclo [5.4.0] undec-7-ene (56.3 mmol) are added. After stirring for 16 hours at 100 ° C., the organic medium is washed with 30 ml of water. The products 15, 15 'are obtained after drying over MgSO 4, evaporation of solvent and purification on a chromatographic column (cyclohexane / ethyl acetate = 9/1). (Yield: 60%) - Procedure for chemical hydrogenation (synthesis of products 16, 16 ') In a two-necked flask equipped with a magnetic stirrer and a condenser, compounds 15, 15' (14, 8 mmol) and hydrazine (74.0 mmol) in ethanol / water (60 mL / 9 mL, respectively). After 4 hours of stirring under reflux, the catalyst is removed by filtration and the solvent evaporated to give the products 16, 16 '(yield: 80%). Procedure for the nucleophilic substitution reaction of mesylate groups with cyanide ions (synthesis of product 20) In a two-necked flask equipped with a magnetic stirrer and a condenser, compound 3 (10.3 mmol in functions mesylate) are solubilized in 96 mL of THF / DMSO (60/40). 41.2 mmol of KCN are then added. After stirring for 28 hours at 40 ° C., the organic medium is washed with 40 ml of water. The product is obtained after extraction into diethyl ether (6 × 50 mL), drying over MgSO 4 and evaporation of solvent (yield: 89%). Of course, the present invention is not limited to the examples and to the embodiment described and shown, but it is capable of numerous variants accessible to those skilled in the art.

Claims (13)

REVENDICATIONS1. Compounds of formula (I) represented below: Y (.2)), R1 -CH-R2 -X (I) in which: R1 represents a hydrocarbon group comprising an integer n number of carbon atoms, R2 represents a hydrocarbon group comprising an integer number p of carbon atoms, at least one of R1 and R2 is unsaturated, x = 0 or x = 1, 3 <n <10, 6 <p <13, Y is selected from the group formed by NH 2, N 3, OH, O-50 2 -CH 3, CN, X is chosen from the group formed by CH 2 -NH 2, CH 2 -CH 2 -NH 2, CH 2 -OH, CH 2 -N, CH 2 -N 3, CH 2 0-502-CH3 and COOR3 with R3 represents H or C1-C12 alkyl, and when Y is NH2 then x = 0 or x = 1 and X is selected from the group consisting of CH2-NH2, CH2-CH2-NH2 , COOR3 with R3 represents H or C1-C12 alkyl, when Y is N3 then x = 0 and X is selected from the group consisting of CH2-N3, CH2-CN, COOR3 with R3 is H or C1-C4alkyl; C12, when Y is O-502-CH3 then x = 0 and X is selected from the group consisting of CH2-0-502-CH3, CH2-CN, COOR3 with R3 being e H or a C1-C12 alkyl; and when Y is CN then x = 0 and X is selected from the group consisting of CH2-CN, CH2-N3, when Y is OH then x = 0 and X is CH2-OH. 2. A compound according to claim 1 wherein: Y = OH, x = 0 and X = CH 2 -OH, or - Y = NH 2, x = 0 or x = 1 and X is selected from the group consisting of CH 2 -NH 2, CH 2 -CH 2 -NH 2 and COOH, where Y = CN, x = 0 and X = CH 2 CN, Y = N 3, X = O and X = CH 2 -N 3. 3. A compound according to any one of claims 1 or 2 wherein: R1 and R2 are linear. 4. A compound according to any one of claims 1 to 3 wherein 16 <n + p <18. 5. A compound according to any one of claims 1 to 4 wherein (R1 / R2) are selected from: - (CH3- (CH2) 5- CH2-CH = CH- (CH2) 7-); - (CH3- (CH2) 4- CH-CH CH (CH2) 7-); - (CH3- (CH2) 2- / -CH2-CH = CH-CH2-CH = CH- (CH2) 7-); - (CH3-CH2-CH = CH- (CH2) 2- CH2-CH = CH- (CH2) 7-); - (CH3- (CH2) 4-CH = CH- (CE12) 2- - (CH2) 7-); - (CH3- (CH2) 4 CH-CH CH-CH / - (CH2) 7-); - (CH3- (CH2) 5- CH2-CH = CH- (CH2) 9-); - (CH3-CH2-CH = CH- (CH2) 2- / -CH2-CH = CH- (CH2) 9-); . (ru (cH 1 crcr / (CH 1+, 1 - 2 -, 4 --- --- = / - / I - (CH 3 - (CH 2) 5 -C = CC = C- / - (CH) 2) 6-); - (CH2 = CH- (CH2) 2, -CH = CH-CC-CC- / - (CH2) 6-); - (CH3- (CE12) 4-CH = CH-CH2- / - (CH2) 8-); - (CH3- (CH2) 4-CH = CH-CH2-CH2- / - (CH2) 7-); - (rH (CH 1 / (CH 1 ru ul- (CH)) ## STR5 ## wherein R 2 (CH 2) n -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 2) 4- (2) 2, -., "= '" - - (CH 3 - (CH 2) 5 -CH 2 -CH = CH- (CH 2) 94 6. A process for preparing a compound of formula (Ia) comprising at least one step of reducing at least one compound of formula (Ib) according to the following scheme: NH 2 Y '(f 1 -12), R 1 -OH- Wherein R1 represents a hydrocarbon group comprising an integer n number of carbon atoms, R2 represents a hydrocarbon group comprising an integer number p of carbon atoms, and R1 represents a hydrocarbon group comprising an integer n number of carbon atoms; at least one of R1 and R2 is unsaturated, x = 0 or x = 1, 3 <n <10, 6 <p <13, X is selected from the group consisting of CH2-NH2, CH2-CH2- NH2 and COOR3 with R3 represents H or C1-C12 alkyl, and Y 'is selected from the group consisting of N3 or CN, X' is selected from the group consisting of CH2-N3, CH2-CN, COOR3 with R3 represents H or a C1-C12 alkyl, and when x = 0 then Y '= 1 \ 13, when x = 1 then Y' = CN, when X = COOR3 then X '= COOR3, when X = CH2-CH2-NH2 then X '= CH2-CN, when X = CH2-NH2, then X' = CH2-N3. 7. The method of claim 6 further comprising at least one step of preparing at least one compound of formula (lb) from at least one compound (Ic) according to the following scheme: Y "Y 'II R1- R1-CH-R2-X "a-R1-CH-R2-X '(Ic) (Ib) with X' is selected from the group consisting of CH2-N3, COOR3 and CH2-CN, Y 'is selected from the group consisting of N3, CN, X "is selected from the group consisting of CH2-O-SO2-CE13, CH2-CN, COOR3 Y- is selected from the group consisting of -O-SO2-CH3, OH, CN ; and when Y '= 1 \ 13 and X' = CH2-1 \ 13 then Y "= -O-SO2-CH3 and X" = CH2-O-SO2-CH3, when Y '= N3 and X' = CH2 -CN then Y "= -O-SO2-CH3 and X" = CH2-O-SO2-CH3 or X "= CH2-CN, - when Y '= N3 and X' = COOR3 then Y" = -O-SO2 -CH3 or Y "= -OH and X" = COOR3, - when Y '= CN and X' = CH2-N3 then Y "= CN and X" = CH2-0-SO2-CH3, - when Y '= CN and X '= CH2-CN, then Y "= -O-SO2-CH3 and X" = CH2-O-SO2-CH3 8. Process for the preparation of a compound of formula (Id) comprising at least one reduction step of an ester or carboxylic acid functional group according to the following scheme: ## STR2 ## Wherein R 1 represents a hydrocarbon group comprising an integer n number of carbon atoms, R 2 represents a hydrocarbon group comprising an integer number p of carbon atoms, and at least one of R1 and R2 is unsaturated, x = 0 or x = 1, 3 <n <10, 6 <p <13, R3 represents H or a C1-C12 alkyl group. 9. Polymer prepared from at least one monomer chosen from the compounds of formula (I) according to any one of claims 2 to 5. 10. Polymer according to claim 9 resulting from the condensation of: at least one monomer of formula (I) with x = 0 or x = 1, Y = NH 2 and X = COOH, - at least one monomer of formula (I) with x = 0 or x = 1, Y = NH2 and X = CH2-NH2 or X = CH2-CH2-NH2 and at least one diacid monomer, - at least one monomer of formula (I) with x = 0 or x = 1, Y = NH2 and X = CH2-NH2 or X = CH2-CH2-NH2 and at least one diisocyanate monomer, - at least one monomer of formula (I) with x = 0, Y = OH and X = CH 2 -OH and at least one diacid monomer; at least one monomer of formula (I) with x = 0, Y = OH and X = CH 2 -OH and at least one diisocyanate monomer, of at least one monomer of formula (I) with x = 0, Y = CN and X = CH 2 CN and of at least one diamine monomer, of at least one monomer of formula (I) with x = 0 , Y = CN and X = CH2-CN and at least one diol monomer, at least one monomer of formula (I) with x = 0, Y = N3 and X = CH2-N3 with at least one dialyne monomer . 11. Crosslinked polymer obtained by photochemical treatment, in particular by ultraviolet treatment of at least one polymer defined according to claim 10. 12. Photocurable composition comprising at least one polymer according to claim 9 or 10 and at least one initiator. 13. Resin composition comprising at least one polymer and at least one crosslinking agent chosen from the compounds according to any one of claims according to any one of claims 2 to 5.