WO2014012829A1

WO2014012829A1 - Novel polyamide, preparation process therefor and uses thereof

Info

Publication number: WO2014012829A1
Application number: PCT/EP2013/064581
Authority: WO
Inventors: Stéphane JEOL; Floryan Decampo; Leon ZHU
Original assignee: Rhodia Operations; Rhodia China Co.
Priority date: 2012-07-20
Filing date: 2013-07-10
Publication date: 2014-01-23
Also published as: US9938377B2; US20150175745A1; IN2015DN00356A; JP2015522689A; JP6328629B2; US9670319B2; EP2875063A1; NO2875063T3; WO2014012240A1; US20170226286A1; EP2875063B1

Abstract

The present invention relates to a novel polyamide synthesized from biobased monomers. The novel polyamide comprises the repeating unit of formula (I) below: Formula (I), in which R represents a covalent bond or a divalent hydrocarbon-based chosen from saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics and alkylaromatics. The present invention also relates to the process for preparing the said polyamide, to its uses, and to articles and compositions comprising the polyamide.

Description

NOVEL POLY AMU EREFOR AND USES

THEREOF [0001 ] The present invention relates to a novel po!yamide, to a process for preparing it and to its uses. The invention more particularly relates to a polyamide synthesized from biobased monomers.

[0002] The term "biobased" means that the material in question is derived from renewable resources. A renewable resource is a natural - animal or plant - resource whose stock can be reconstituted over a short period ^' uman timescale. It is in particular necessary for this stock ^* able to be renewed as quickly as it is consumed. [0003] Unlike materials derived from fossil materials, renewable starting materials contain a large proportion of ¹⁴C. This characteristic may especially be determined via one of the methods described in standard ASTM D6866, especially according to the mass spectrometry method or the liquid scintillation spectrometry method. [0004] These renewable resources are generally produced from cultivated or non- cultivated vegetable matter such as trees, plants such as sugarcane, corn, cassava, wheat, rapeseed, sunflower, palm, castor-oil plant or the like, or from animal matter such as fats (tallow, etc.). [0005] Polymers synthesized from biobased monomers are of major interest nowadays since they make it possible to reduce the en ironmental footprint. There are a large number of combinations of biobased monomers or of combinations of monomers that are biobased and derived from fossil resources, which may be used to generate polymers that are then termed biobased. Some of these biobased polymers may be used to replace polymers derived from fossil resources. This is the case, for example, for polyamide PA 6.10, synthesized from hexamethylenediamine (fossil resoui ¹ - d fr . -based sebacic acid derived from castor oil, which can replace irived from fossil resources) especially in motor vehicle applications. [0006] Among the biobased monomers, there is great interest in 2,5- furandicarbox lic acid, obtained, for example, from hydroxymethy!furfural (HMF), which is itself obtained, for example, from sugars, such as glucose. [0007] 2,5-Furandicarboxy!ic acid is especially used in direct replacement for terephthalic acid, derived from fossil resources, and in combination with diols such as ethylene glycol, 1 ,3-propanediol or 1 ,4-butanediol, to synthesize semi-crystalline polyesters that have excellent properties_., whether for wrapping or textile applications, Thus, polyethylene furanoate (PEF) may be used instead of polyethylene terephthalate (PET) for the production of bottles.

[0008] industrially, polyesters of the ^c - are mainly synthesized via a direct estenfication route between terephthalic acid and diols.

[0009] However, modifications of these industrial units prove to be necessary in order to synthesize high-quality PEFs, since, in the course of this reaction, the 2,5- furandicarboxyiic acid degrades into furan, which is a toxic, carcinogenic and flammable molecule.

[0010] ft is therefore more judicious to perform the synthesis of PEFs according to another industrial route for the manufacture of PETs from dimethyl terephthalates. When applied to PEFs, this "clester" route is the reaction between dimethyl 2,5- furanoate and an excess of diol, the excess of diol being removed by distillation under vacuum to make the polyester chains grow.

(001 1 ] Semi-crystalline polyamides such as PA v ^: ··^' . and PA 46 or polyphthaiamides PA (51766, PA 6T/MT and P.A 6T/6I, ^' 0T are ^" f tare technical polymers that are widely used in applications such as motor vehicles, textiles or in the electrical and electronics (E&E) sector. They constitute the vast majority of the polyamides sold worldwide. Amorphous polyamides are, for their part, more marginal since the amorphous nature often limits the application performances and the working temperature range, 10012] Polyamides have also been synthesized from 2,5-furandtcarboxylic acid especially for the purpose of replacing terephthalic acid with a bioba' tnomer in contrast with polyesters derived from 2,5-furandicarboxylic acid, it appears, from a recent study by Ulrich Fehrenbacher published in Chemie ingenieur Technik Po!yrnere) 2009, 81 , 1 1 1829-1835, that the polyamides made from the methyl dtester derivative of 2.5-furandicarboxyitc acid and from bsobased commercial diamines (e.g_. 1 , 10-diamtnodecane) or derived from fossil resources (e.g. hexamethy!enediamine or 1 , 12-diaminododecane) are amorphous. [0018] This characteristic represents a curb on the development of polyamides from 2,5-furandicarboxyttc acid, since they cannot replace the semi-crystalline polyamides derived from fossil resources. [0014] Furthermore, as for polyesters, the use of 2,5-furandicarboxylic acid for po!yamide manufacture should be avoided since it generates furan, which is toxic

[0015] Another curb on the development of these polyamides is t ;e to a

^"diester aminolysis^" process, i.e. a process that consists in reacting a diamine with a diester Specifically, such a process has two major drawbacks in contrast with the case of the polyesters synthesized via the "diester" route. The first drawback is the appearance of side reactions that have an impact on the thermal properties (for example the crystallization) of the polyamides. The second drawback is that it is necessary to work with a stoichiometric amount of diamine and of diester in order to obtain polyamides of high molar masses. However, it is difficult to control this stoichiometric amount of diamine and of diester from an industrial point of view,

[0016] T ere is thus still a need to propose novel polyamides, which are preferably semi-crystalline, derived from biobased molecules, which can replace the polyamides derived from fossil resources,

[0017] Furthermore, there is also a need to find a synthetic roi these biobased polyarnides that is simple, clean s reducible and that advantageously uses the industrial equipment already in place for standard polyamides such as polyamide 66, furthermore, the manufacturing process for synthesizing these polyamides should advantageously make it possible to achieve high molar masses.

[0018] In this context, it has been discovered, entirety surprisingly, that diacids or derivatives which contain a tetrahydrofuran ring make it possible, especially in combination with diamines, to synthesize novel polyamides that have particularly advantageous properties in the usual applications of polyarnides. These diacids or derivatives, which are advantageously biobased, rnay be obtained especially from biobased 2.5-furandicarboxylic acid [0019] One subject of the invention is thus a novel po!yamide comprising the repeating unit of formula I below;

in which

presents a covaient bond or a divalent hydrocarbon-based group chosen from saturated or unsaturated aiiphatics. saturated or unsaturated cycioaliphatics, aromatics, arylaliphatics and alkylaromattcs.

[0020] A subject of the invention is also a process for prepari polyamide of ention, which comprises a polycondensation reaction betwee

at least one dicarboxylic acid or at least one carboxyfc acid diester or at least one dinitrMe or at feast one acyf dichloride of respective formulae IV, IV, IV" and IV" below

when ^'- - d R₂₎ which are identical or different art ^{' "} - .<yls;

and - at least one diamine of formula V below;

with R as defined above. {0021 J Furtherrr jject of the invention is the use of the polyamide of the invention for preparing articles by moulding, injection moulding, injection/blow-moulding, extruston/blow-moulding , extrusion or spinning. The present invention is thus also directed towards articles obtained from the polyamide according to the invention, the said articles being able to take the form of moulded or extruded pieces, yarns, fibres, filaments or films,

[0022] The articles thus obtained have applications in numerous fields such as technical plastics (motor vehicle, E&E, consumer goods, etc.), industrial yarns, the textile industry, packaging, etc.

{0023] The present invention also relates to compositions comprising at least the polyamide of the invention and options forcing fillers and/or various additives.

[0024] The novel polyamide according to the invention comprises a repeating unit of formula I as described above in which R represents a covalent bond or a divalent hydrocarbon-based group chosen from saturated or unsaturated aliphatics. saturated or unsaturated cycloaliphatics, aromatics, arylaliphattes and aiky!aromatics.

[0025] The term "saturated aliphatic group" means, for example, linear or branched alkyl groups having from 1 to 36 carbon atoms. Preferably, a linear alkyl group having from 4 to 14 carbon atoms will be chosen. [0026] The term "unsaturated aliphatic group" means, for example, that the invention does not exclude the presence of an unsaturatton on the aliphatic hydrocarbon-based chain, such as one or more double bonds that may or may not be conjugated, or alternatively a triple bond, [0027] The hydrocarbon-based chain of trie above aliphatic groups may optionally be interrupted with a heteroatom (for example oxygen, nitrogen, phosphorus or sulphur) or a functional group (for example carbonyl) or may bear one or more substituents (for example hydroxy! or sulphone) provided that they do not interfere under the reaction conditions or with regard to trie intended application.

[0028] As prefe arnpies for the aliphatic grou . mention may be made of the following groups: -(CH₂)₄-. -(C z -<CH₂)₆-. -(CH_z)-CH(CH₃)-{CHi)₃-, -{CH₂)₁₀- and

~<CH₂) i 2-. 8

10029] In formula {t » » _'- also represent a cycloa!ipha!ic (or car ocycHc) group, which is preferably monocyclic or bicyclic. The number of carbon atoms in each ring may range from 4 to 8 carbon atoms, but it is preferably equal to 4, 5 or 6 carbon atoms. The carbocycle may be saturated or may comprise 1 or 2 unsaturations in the ring, preferably 1 to 2 double bonds.

[00301 As preferred examples of carbocyclic and monocyclic groups for A mention may be made of the 1 ,4-cyc!ohexyl or 1 ,3-cyclohexyl group, preferably the trans stereoisomer or else the 4,4'-methytenebis{cycIohexyl) group.

[0031 ] In other advantageous embodiments of the invention, R may also represent an aromatic divalent hydrocarbon-based group comprising, advantageously, at least 5 carbon atoms in its aromatic ring, which may be interrupted with a heteroatom such as a nitrogen atom. Preferably, the divalent aromatic hydrocarbon-based group comprises from 6 to 18 carbon atoms, such as a 1 ,4-benzene, .3-benzene or phthalene group. It may also be a divalent alkylaromatic hydrocarbon-based group such as 1 ,4-phenylene-2.5~dimethyl. or a divalent arylaliphatic hydrocarbon-based group such as the group -{CH₂)_n-Ph-(CH2)n- with n and n^* being integers advantageously between 1 and 4 and the positions of the -<CH2)rv groups are 1.3 and 14. As preferred examples for the aromatic groups R, a 1 ,4-benzene, 1 ,3-benzene or -(CH₂)-Ph-(CH₂)- group in positions 13 and 14 will be chosen..

[0032] According to one particular embodiment of the invention R is a divalent hydrocarbon-based group that is biobased in the sense of the present invention (standard ASTM D6866). 0033] According to one preferred embodiment of the invention, the poiyamide of the invention has a true numbef-average molar mass Mn of between 500 and 50 000 g/mol, preferably between 2000 and 30 000 g mo! and even more preferentially between 5000 and 25 000 g/mol

[00341 The true number-average molar masses are determined by various known methods such as ge! permeation chromatography. The term "true number-average molar masses" should be understood as meaning that they are not measurements as polystyrene equivalents. [0035] According to a first advantageous embodiment, the polyamicle according to the invention predominantly comprises the repeating unit of formula I, This repeating unit of formula 1 is advantageously derived from the polycondensation reaction between a dicarboxylic acid monomer of formula IV as defined above a " ^!

of formula V; H₂N-R~NH₂ (V) with R as defined above. As explained previously, the dicarboxylic acid may also be substituted with a corresponding methyl, ethyl, propyl or butyl diester (formula IV) or alternatively with a corresponding dinitriie (formula IV"), or alternatively an acyi chloride (formula IV"). [0036] The term "predominantly" means that the polyamide may be a homopolyamide consisting entirely of the repeating unit of formula I, but also that it may be a copolymer comprising other repeating, units different from the unit of formula I, these repeating units possibly being derived from comonomers such as other dicarboxylic acids, other diamines, amino acids and/or lactams. These comonomers may represent up to 50 mol%, preferably up to 30 mof% and even more preferentially up to 15 mol% of the total amount of monomers introduced for the preparation of the polyamide of the invention.

[0037] According to a second advantageous embodiment, the polyamide according to the invention comprises to a minor extent the repeating unit of formula I

This repeating unit of formula I is advantageously derived from the polycondensation reaction betweer * ^■••- artraxylic acid monomer of formula IV as defined above and a diamine monomer of formula V: H₂N-R-NH₂ (V) with R as defined above, As explained previously, the dicarboxylic acid may also be substituted with a corresponding methyl, ethyl, propyl or butyl diester (formula IV^") or alternatively with a corresponding dinitriie (formula IV"), or alternatively an acyl chloride (formula IV").

[0038] The term "to a minor extent" means that the polyamide is a copolymer comprising other repeating units different from the unit of formula I . these repeating units possibly being derived from monomers such as other dicarboxylic acids, other diamines, amino acids and/or lactams These other monomers may in that case represent up to 95 mol%, preferably up to 70 moi%, of the total amount of monomers introduced for the preparation of the polyamide of the invention. In other words, the precursor monomers, of the repeating unit <>^f formula i may in that case represent up to 5 mo!%. preferably up to 30 moi%. of the total amount of monomers introduced for the preparation of the polyamide of the invention. The copoiymer in question may be, for example, ^{' ' " "} . PA6T/6TF/66, PA66/t ^{r '} V and

PA610/6TF, in the proportions described above. [0039] Copolymer of the present invention may be chosen in group consisting of: r- ' . , r ^■ 1 . - - 76TF/6 " ^' 3/6TF, : MT^{" '} r ' ^r-T : :5TF. [0040] The dicarboxylic acid monomers of formula IV, diester monomers of formula IV, diniirile monomers of formula IV" and acyl dichloride monomers of formula IV" may be the cis or trans stereoisomers or a mixture thereof. Preferably, the trans stereoisomer will be chosen, For the cis stereoisomer, the chiral carbons in posit:

and 5 may , z Ό > - i ^J . a meso mixture. For the trans stereoisomer, the chiral carbons in positions 2 and 5 may b .^N n r-^{1 T}< \ or the racemic mixture.

[0041 J The diacids of formula IV, which are advantageously biobased. may be synthesized, for example, by catalytic hydrogenation. for example with Raney nickel, from 2,5-furandicarboxylic acid (FDCA) or the methyl diester of that acid, followed by a hydrolysis.

[0042] The diesters of formula IV", which advantageously are biobased, m synthesized, for example, by esterification of THFDCA (diacid of formula IV) with a monoalcohol such as methanol, ethanol, propanol or butanol or by esterification of FDCA with a monoalcohol such as methanol, ethanol, propanoi or butanol, followed by catalytic hydrogenation, for example with Raney nickel.

[0043] The dinttrites of formula IV", which advantageously are biobased, may be synthesized, for example, by nttrilation of THFDCA (diacid of formula IV) with ammonia.

{0044} The acyl dichlorides of formula IV'T which advantageously are biobased, may be obtained, for example, from the reaction ^'DC A (diacid of formula IV) with thionyl chloride, Ϊ0045] The processes for obtaining these various monomers are conventional processes which are known to a person skilled in the art,

(00461 These monomers are particularly advantageous because they are able to confer a semi-crystalline character on the polyamides of the invention.

{0047] The diamine monomers of formula V are advantageously chosen from; hexamethyienediamtne; 1 ,4-diamtnobutane. 1 ,5-diaminopentane; 2onethyH ,5- diaminopentane; 2-methylhexamethylenediamine; 3-methy!hexamethylenediamine; 2.5-dimethylhexamethylenediamine; 2,2 -dimethylpentamethylenediam!ne^' 1 - diaminoheptane, 1 ,8-diaminooctane; 1.9-diaminononanediamine; 2~methyl-1 ,8- ocianediamine, 5-methylnonanediamine, 1 , 10-dtaminodecane; 1.1 1 -diammoundecane; 1. 2-diaminododecane; 2,2,4- and 2,4,4-trimethylhexamethylenediamine; 2,2,7,7- tetramethyiociamethyienediamine; meta-xyiylenediamine; para-xylyienediamine; isophoronediamme; 4.4^'-diaminodiphenylmethane; 4.4'~methy!enebis-

(cyclohexylamine); 1 ,3-bis(aminomethyl) cyclohexane; C2-C 16 aliphatic diamines that may be substituted with one or mor ill- y) groups, the C38 diamines originating from fatty acid dimers known under the nat troine; 2,5-bis(aminomethyt)furan and 2.5- bis(aminomethyl)ietrahydrofuran; para-phenylenediamine; meta-pheny!enediamine; and the ethoxylated diamines known under the name Jeffamine or Elastamtne (polyetherdiamine comprising ethers of ethylene glycol and/or of propyie · - col and/or of tetramethylene glycol),

[0048] The majority of these monomers are commercially available and may be biobased. These monomers are particularly advantageous because they are able to confer a semi-crystalline character on the polyamides of the invention.

[0049] The diamine monomers of formula V may be chosen from 2_t5-bis(aminomethyl)furan and 2,5-bis(aminomethyl)tetrahydrofuran. In the particular embodiment in which the diamine monome of formula V is

2.5- bis(am!nomethyl)tetrahydrofuran, the compound in question may be the cis or trans stereoisomer or a mixture thereof.

[0050] These advantageously biobased diamines ma synthesized, for example for 2.5~bis(aminomethyl)furan, by nitriiation of randicarboxylic acid fotlowed by a selective hydrogenation, and a hydrogenatton of the furan ring of 2,5~bis(amino ethyl)furan to prepare 2,5-bis(aminomethyi)tetrahydrofurar».

[0051 } Dicarboxylic acid comonomers that may be used according to the invention, may be, for example, oxalic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1 ,12-dodecanedtoic acid; 1.3- or ,4-cycSohexanedicarboxylic acid: 1 ,3- or 1 ,4-phenylenediacetic acid: 1 ,3- or 1 ,4-cyc!ohexanediacetic acid; isophthaiic acid; 5-hydroxyisopnthaiic acid; terephthalic acid; 4,4'-benzophenoriedicarboxyfic acid;

2.6- naphtha!enedicarboxylic acid, arid 5-t-butylisophthalic acid, alkali metal salts (Li, Na or K) of sulpho-5-isophthafic aesd, and the C36 fatty acid dimers known under the name

Pnpoi.

(0052J These comonomers are commercially available and may be biobased [0053] The diamine comonom_'-' ' fere v * worriers of formula V) may be chosen, for example, from: hexamethylenedtamine; 1 ,4-diaminobutane; 1 ,5-diaminopentane; 2-methyt-1 ,5-diaminopentane; 2-methylhexamethyienediamine: 3-methylhexamethylenediamine; 2,5-dimethylhexamethylenediamine; 2,2- dimethylpentamethylenediamine; 1 ,7-diaminoheptane, 1 ,8-diaroittooctane;

diaminononanediamino; 2-methyl-1 ,8-octanediamine, 5-methylnonanediamine, 1 , 10- diaminodecane; 1 .1 1 -diammoundecane; 1 ,12-diaminododecane; 2,2,4- and trimethylhexamethylenediamine; 2,2,7,7-tetramethyloctamethylenediamine; meta- xylylenediamine; para-xylylenediam^'me; isophoronediamine; 4, 4' -diamine- diphenylmethane; 4,4^,-methy!enebis(cyclohexylamini ohatic diamines that may be substituted with one or more alkyl groups, ' 3 diamines originating from fatty acid dimers known under the name Priamine; 2,5-bis(aminomethyl)furan and 2,5- bis((aminomethyl)tetrahydrofuran; para-pheny!enediamine; meta-pheny!enediamine; and the ethoxylated diamines known under the name Jeffamme or Elastamtne (polyetherdiamine comprising ethers of ethylene glycol and/or of propylene glycol and/or of tetramethylene glycol),

[0054] These comonomers are commercially available and may be biobasecl.

[0055] The lactam or amino acid comonomers may be chosen, for example, from capro!actam, 6-aminohexanoic acid; 5-aminopentanoic acid. 7-aminoheptanoic acid, 9-arn»nonor»anoic acid, 1 1 -aminoundecanoic acid and dodecanoiactam. [0056] These comonomers are commercially available and may be biobased,

[0057] Several processes for manufacturing the polyamide according to the invention may be envisaged, as described previously. These processes may be continuous or batch processes,

10058} A first process proposed by the present invention is a process for preparing the polyamide according to trie invention, which comprises /condensation reaction between^'

o at least one dicarboxylic acid of formula IV below: o at least one diamine of formula V below:

H₂N-R-NH₂ (V)

with R as defined above.

[0059] According to one preferred embodiment of the invention, at least i mine of formula V is biobased according to standard ASTM D6866

10060] According to one preferred embodiment of the invention, dicarboxylic acid of formula IV is biobased according to standard ASTM D6866. [0061 ] This first process is similar in its conditions to the standard process for preparing polyamide of the type obtair m dicarboxylic acids and diamines, in particular the process for manufacturing polyamide 66 from adipic acid and hexamethy!enediamine or the process for manufacturing the polyamide MXD6 by direct amidation starting with molten adipic acid and meta-xylylenediamine. The processes for manufacturing polyamide 66 and XD6 are known to those skilled in the art The process for manufacturing polyamide of the type obtained from dicarboxylic acids and diamines generally uses as starting mated? t obtained by mixing, in stoichiometric amount generally in a solvent such as water, of .< Jwcid with a diamine. Thus, in the manufacture of poly{hexamethyleneadipamide), adipic acid is mixed with hexamethylenedtamine generally in water to obtain hexamethylenediammonium adipate, which is more commonly known as Nyion salt or "N Salt".

[0062] Thus, in the manufacture of the polyamide according to the invention, the dicarboxylic acid of formula IV is mixed with the diamine of formula V. generally in water to obtain a salt of the two monomers. As explained above, these monomers may comprise up to 50 mol%, preferably up to 30 mol% and even more preferentially up to )l% of other comonomers as described previously.

[0083] The salt solution is optionally concentrated by partial or total evaporation of the water.

[0064] The polyamide is obtained by heating at high temperati d high pressure of an aqueous solution of the monomers (for example a salt solution as described above^'), or of a liquid comprising the monomers, to evaporate the water and/or the liquid while at the same time avoiding the formation of a solid phase.

{0065] The polymerization medium may also comprise additives such as antifoams. chain limiters (monofunctiona! molecules capable of reacting with the acid and/or amine functions), branching agents (i.e. molecules bearing at least three functional groups chosen from carboxyfic acid and amine groups), catalysts, stabilizers

(with respect to UV, heat or light), matting agents (for instance Ti0_2l etc.), lubricants and pigments.

[0066] The poiycondensation reaction is generally performed at a pressure of about 0.5-3.5 MPa (0.5-2.5 MPa) and at a temperature of about 180-320X (215-300°C), The poiycondensation is generally continued in the melt at atmospheric or reduced pressure so as to achieve the desired degree of progress.

10067] The poiycondensation product is a molten polymer or prepolymer. At this stage, the reaction medium may comprise a vapour phase consisting essentially of vapour of the elimination product, in particular water, which may have been formed and/or vaporized.

[0068] This product may be subjected to steps for separating out the vapour phase and for finishing in order to achieve the desired degree of poiycondensation. The separation of the vapour phase m; erformed for example, in a device of cyclone type for a continuous process Such devices are known

[0069} The finishing consists in maintaining the poiycondensation product in molten form, at a pressure in the region of atmospheric pressure or at a reduced pressi a time that is sufficient to achieve the desired degree of progress. Such an operation is known to those skilled in the art. The temperature of the finishing step is advantageously greater than or equal to 200°C and in all cases greater than the solidification temperature of the polymer, The residence time in the finishing device is preferably greater than or equal to 5 minutes.

{0070] In the case of processes that are more suited to the polymerization of the polyamide MXD6, the two monomers are introduced into the reactor without proceeding via a salification phase; this is then referred to as the direct amidation process. The reaction m this case is generally performed at atmospheric pressure.

[0071] The poiycondensation product may also undergo a post-condensation step tn sold or liquid phase. This step is known to those skilled in the art and makes H possible to increase the degree of poiycondensation to a desired value. [0072] The polyamide obtained via the process of the invention in molten form may thus rrnecl directly or may be extruded and granulated, for an optional post- condensation step and/or for subsequent forming afte melting. [0073] ;ond process for preparing the poiyamide according to the invention is a diester aminolysis" process, i.e. at least one diamine of formula V as described previously is reacted with at least one diester of formula IV, preferably a methyl, ethyl, propyl or butyl diester of the carboxylic acid of formula described previously, A similar process applied to different monomers is moreover described in the publication from Ulrich Fehrenbacher in Chemie Ingenieur Technik (Polymt 09, 81 , 11 , 1829- 835 According to one preferred embodiment of the invention, at least one diamine of formula V is biobased according to standard AST D6866 According to one preferred embodiment of the invention, at least one diester of formula IV is biobased according to standard ASTM D6866.

[0074] The present invention also envisages another process for preparing the polyamide according to the invention, the said process comprising the reaction between at least one diamine of formula V as described previously and at least one dinrtrile of formula IV" as described earlier on in the description A similar process applied to different monomers is moreover described in WO2001/079327. According to one preferred embodiment of the invention, at least one diamine of formula V is biobased according to standard ASTM D6866. According to one preferred embodiment of the invention, at least one dinitrile of formula I V is biobased according to standard ASTM D6866.

[0075] Lastly, the present invention also provides another process for preparing the polyamide according to the invention, said process comprising reacting at least one diamine of formula V as described above with at least one acid dichloride of formula IV" as described earlier on above in the description, this reaction generally being carried out in solution or by interfaciai polymerization. This is a synthesis process known to the skilled person and used especially for the synthesis of aromatic polyamides such as Kevlar®.

[0076] The polyamide may be used to make articles by moulding, injection- moulding, injection/blow-mouiding, extrusion/blow-moulding, extrusion or spinning. The articles may thus take the form of mouldings or extrudates, films, yarns, fibres or filaments. [0077| The articles thus obtained have applications in numerous fields such as technical plastics (motor vehicle. E&E, consumer goods), industrial yarns, the textile industry, packaging, etc. {0078] The present invention also relates to compositions comprising at least the poiyamide of the invention, and optionally reinforcing fillers and/or various additives^,

[0079] Such a composition preferentially comprises from 1 % to 80% by weight of the poiyamide according to the invention, relative to the total weight of the composition. This composition may especially comprise other types of polymer, especially such as thermoplastic polymers.

[0080] The composition may also comprise reinforcing or bulking fillers. Reinforcing or bulking fillers are fillers conventionally used for making poiyamide compositions. Mention may be made especially of reinforcing fibrous fillers, such as glass fibres, carbon fibres or organic fibres, non-fibrous fillers such as particulate or lamellar fillers and/or exfoliable or non-exfoliable nanofillers, for instance alumina, carbon black, clays, zirconium phosphate kaolin, calcium carbonate copper, diatomaceous earths, graphite, mica, silica, titanium dioxide, zeolites, talc, wollastonite, polymeric fillers, for instance climethacrylate particles, glass beads or glass powder

[0081] The composition according to the invention may comprise between 5% and 60% by weight of reinforcing or bulking filers and preferentially between 10% and 40% by weight, relative to the total weight of t iposition.

¾ The composition according to the invention comprising the poiyamide as defined previously may comprise at least one impact modifier, i.e a compound that is capable of modifying the impact strength of a poiyamide composition. These impact modifier compounds preferentially comprise functional groups that are reactive with the poiyamide Accordi invention, the term "functional groups that are reactive with the po!yarnide" means groups that are capable of reacting or of interacting chemically with the acid on amine functions of the poiyamide, especially by covatency. ionic or hydrogen interaction or van eier Waals bonding. Such reactive groups ensure good dispersion of the impact modifiers in the poiyamide matrix Good dispersion is generally obtained with impact modifier particles that nave a mean size of between 0, 1 and 2 pm in the matrix. [0083] The corn position according to the invention may also comprise additives usually used for the manufacture of poiyamide compositions. Thus, mention may be made of lubricants, flame retardants. light and/or heat stabilizers, plasticizers, nucleating agents. UV stabilizers, catalysts antioxidants, antistatic agents, dyes, matting agents, moulding additives or other conventional additives.

[0084] These fil < i additives may be added to the modified poiyamide via usual means suited to each filler or additive for instance during the polymerization or mixed in the melt. The poiyamide compositions are generally obtained by mixing the various compounds included in the composition without heat or in the melt The process is performed at more or less high temperature, at more or less high shear depending on the nature of the various compounds. The compounds may be introduced simultaneously or successively. An extrusion device in which the material is heated, and then melted and subjected to a shear force, and conveyed, is generally used.

[0085] It is possible to mix all the compounds in the moll ase in a single operation, for example during an extrusion operation It is possible, for example, to perform a mixing of granules of the polymer materials, to introduce them into the extrusion device in order to melt them and to subject them to a more or less high shea According to particular embodiments, premixirig, optionally in the melt, of some of the compounds may be performed before preparation of the final composition.

{0086] The composition according to the invention, when it is prepared using an extrusion device, is preferably conditioned m the form of granules. The granules are intended to be formed using processes involving melting to obtain articles. The articles are thus constituted by the composition, According to one common embodiment, the modified poiyamide is extruded in the form of rods, for example in a twin-screw extrusion device, which are then chopped into granules. The pieces are then made by melting the granules produced above and feeding the composition in melt form into forming devices, for example injection-moulding devices.

(0087] The composition according to the invention allows the preparation of articles obtained by forming the said composition, for example by extrusion especially extrusion of plates, sheets or films, moulding, especially injection-moulding, rotary moulding, blow- moulding, especially injection/blow-mouiding, or spinning. Articles that may he mentioned include those used in the motor vehicle or electronics and electrical industry, for example. [0088] The articles obtained may especially be mouldings, blow-mouldings or extrudates, yarns, fibres, fiiaments or films,

[0089] The polyamide according to the invention has many advantages. First, tt is advantageously at least partly biobased, which makes it possible to reduce its environmental footprint It also has very advantageous mechanical properties, a high molar mass and, depending on the diamine used, it may be semi-crystalline. The polyamide of the invention may, finally, replar ^j il ^ i.niyamides conventionally used in fields such as technical plastics (motor vehicle, E&E, consumer goods), industrial yarns, the textile industry, packaging, etc

[0090] The process of the invention also has many advantages. In particular, when it is a process of "salt" type it is very easy to control the stoichiometry between the dicarboxylic acid and the diamine. Furthermore, the process does not generate any degradation products such as furan, which is a highly toxic product. In addition, the preparation of the polyamide according to the invention may be performed using industrial equipment usually used in factories for manufacturing polyamides of the type obtained from dicarboxylic acids and diamines, especially polyamide 66 and therefore does not require any additional industrial investment.

[0091 ] Other details or advantages of the invention will emerge more clearly in the light of the examples given belo

EXAMPLES

10092] Melting temperature (Tm, and associated enthalpy >Hm), crystallization temperature (Tc), and glass transition (Tg) are determined by Different!. nning Calorimetry (DSC) using a Perkin Elmer Pyiis 1 , with heating and cooling rate of l OXVmtn, [0093] Thermal stability is evaluated by Theme-Gravimetric Analysis (TGA) under nitrogen using a Perkin Elmer TGA7. by heati 3 sampie from 40°C to 600X at a heating rate of t OX/inm Degradation tempera! "responding to the weight toss of 1 % . 3% and 10% are recorded and respectively named Tdec1 %. Tdec3% and Tdec l 0% [0094] 1 H NiviR analysis of polyamide is achieved using a Bruker AV500 in 1 T 1 , 3.3^.3-Hexafluoro-2-propanoS-d2 or D-^,SO„ if deuterated HFIP is not a good solvent_. [0095] Amine end-groups (AEG) and carboxyllc end-groups (C eventrations (in nirnol/kg) are determined by titration. We calculate the average molecular weight in number Mn_-EG from end-grous concentration by n._EG=2000000/(AEG+CEG). [0096] Viscosity Index (VI, in rriL/g) is measured in formic acid slvent according to ISO307

[0097] Example 1 » aration of - i elyamide from 2,5-furandicarboxylic acid (FDCA) and hexamethyleneiiamine

[0098] A salt of 2,5-furandicarboxylic acid (FDCA) and of hexamethylenediamine is prepared by adding 2 g of FDCA (0.01 28 mol) to 4.59 g of aqueous 32,5% hexamethylenediamine solution (0.0128 mol). Exothermicity is produced during the salification, and the reaction medium is then maintained at 50° C for 2 hours and becomes perfectly clear The salt is recovered and then analysed by thermogravtmetric analysis coupled to an infrared detector: this involves heating the salt at 10°C/min. A substantial evolution of C0₂ and of furan is detected at and above 245 C. i.e. during the melting of the salt 6FDCA which is a sign of degradation of the 2,5-furandicarboxylic acid units, it is therefore not possible to prepare polyamides of high molecular mass via this route

[0099] Examples 2: Preparation of polyamides from THFDCA and diamines

{00100] A salt of hexamethylenediamine and of 2_t 5-tetrah drofurandicar oxylic acid

(monomer noted THFDCA o is prepared by mixing at room temperature the monomers in stoichiometric amount (2 g of TF (0,0125 mol) and of hexamethylenediamine) in ethanof. The reaction medium is heated at 70 ^:'C for 2 hours. After cooling, the dry sail is recovered by filtration and drying. This is the salt named 6TF . fCM A salt of 1 , 10-diaminodecane and of 2,5-tetrahydrofurandicarboxylic acid is prepared by mixing at room temperature the monomers in stoichiometric amount (2 g of TF (0.0125 mol) and 7 .. .. ; · ·^' 1 , 10-dtaminodecane) at 20% in water. The reaction medium is heated at 70°C for 2 hours. After cooling, the dry sait is recovered by filtration and drying. This is the salt named 10TF.

[00102] Each sail is heated above its melting point and the amidation reaction takes piace The polyamides obtained have satisfactory thermal characteristics

[001 03] Examph nthesis of homopolyamides by cluster route [0C Dimethyl 2,5-tetrahydrofuranoate eis/tratis 90/10 (named dmTHFDCA eisrtrans 90/10) is synthesized as follows. In a 3 L flask equipped with a reflux condenser and a thermometer furan-2,5-dicarboxylic acid (FDCA) (200 g, 1 28 mol), H₂S0₄ (98%, 90 ml) were dissolved in 1 ,4 L of methanol. The reaction mixture was stirred under reflux for 22h. After cooling to R.I, the mixture was concentrated in vacuum and the residue was dissolved in 1.5 L of DCM. The obtained solution was washed by water (2*400ml), saturated NaHCO_? solution (2*300ml). and brine (2x300ml), The organic layer was dried and concentrated in vacuum to give 203 g of white solid (86% yield), and the solid was used for next step without further purification.

[00105] In rr reactor the white solid obtained (250 g, 1.36mol), Pd/C (10%,

25 0 g) were suspended in 2.5 I of methane ^" --ction mixture was stir 50° C under an atmosphere of hydrogen at 20 bar. and monitored VIS When the reaction is completed the mixture was filtered through silica gel and the filtrate was concentrated in vacuo and distilled under reduced pressure to give 2: orless oil (85°C /50Pa.

89% yield),

[00106] 2,5-tetrahydrofurandicarboxylic acid els/trans 90/10 (name< DCA) is synthesized as follows In a 50ml round-bottomed flask equipped with a reflux condenser the dmTHFDCA (1g, 5.3 mmol) was dissolved in 1 ml of id 5 ml of water. The mixture was heated at 100°C and monitored by LC-MS, When the reaction is completed the mixture was concentrated under vacuum to give 0,78 g of white solid (92% yield). If necessary the product would be further purified by recrystallization, [00107] We synthesize polyamides starting from dimethyl 2,5-tetrahydrofuranoate cis/trans 90/10 (named dmTHFDCA cis/trans 90/10) and a stoichiometric amount of a diamine, Diamir liuated are: hexamethylene diamine, 1 , 0-diaminodecane, 1 ,4- diaminobutane, meta-xyiylene diamine. isophorone diamine, 1 ,3- bis(aminomethyl)cyclohexane anc dethylenebis(2-methylcyclohexylamine) mixture of isomers all supplied by Sigma-Aldrich.

[00108] The same method is used to synthesize all the different polyamides, Here is described the method used for the synthesis of PA 10TF. [00109] In a glass reactor is introduced 16,002 g of dmTHFDCA cis/trans 90/10 pr ourselves according to the procedure described (purity 98%, 0,083 mot) and

, 10-diaminodecane (purity 98%, ¹ J mot), Nitrogen blanket is then used and the monomers are stirred using a mechanical stirrer. The glass reactor is trnrnersed in a heating bath regulated at 80°C and then heated to final temperature (230X) with heating rate of 5°C/min. Methanol produced during the reaction between the diester and the diamine (beginning of the appearance of boiling in ;tion mixture when bath is at 90^flC) is removed by distillation. When the reactor is at final temperature. pressure in t ^> I'.^SS reactor is decreased to about 60 mbar and maintained under vacuum during 30 minutes. Nitrogen is introduced to come back to atmospheric pressure, stirring is stopped and the glass reactor removed from heating bath to coo! the reaction mixture, A yellowish transparent solid is recovered.

[001 10] 1 H NMR analysis in deuterated HFIP confirms the reaction between THFDCA and 1 ,10-dtaminodecane. Thermal properties analysis shows that the PA 1 QTF_cjs/transgom is an amorphous solid with Tg= i has a very good thermal stability up to more than 280°C. giving-a broad processing window between Tg and Tdec1%.

[0011 1] A similar method is used for the synthesis of polyamides with dmTHFDCA cts/trans 90/10 and various dtamtties. Thermal properties of the homopolyamides are reported in Table 1.

In any case all homopolyamides are all yellowish transparent amorphous solids with Tg up to 162°C, depending on the rigidity of the diamine used. They can compete with other existing commercial amorphous polyamides.

Properties of homopolyamides synthesized using dmTHFDCA cts/trans

(001 13] Example 4: synthesis .· < >TF copoiyamicies using salt route

[0C We use a sample of THFDCA cis/trans 95/5 for the synthesis of PA 66/6TF

95/5, 90/10 and 80/20 mof/mol. Polymerization of theses copolyamides is achieved using a classical PA 66 synthesis process : we prepare an aqueous salt composed with diacids mixtures (adipic acid and THFDCA) and hexamethylene diamine at a concentration of 52 wt. -% in water and 70°C, we concentrate the aqueous salt up to 70 wt-% under atmospheric pressure by removing water by heating, we then heat the reactor under 17,5 bar pressure (distillation of water under pressure), we depressurize to atmospheric pressure when the temperature of the reaction mixture reaches 250 C and we finish the reaction at (ring 30 min at atmospheric pressure The copolyamides are extruded from the reactor under pressure, cooled in a cold water bath to get a strand and then pelletized

[001 15] For PA 66/6TF 95/5 mol/mol, we started the reaction by mixing 142,62 g {0,544 mol) of Nylon 66 salt (stoichiometric salt of adipic acid and hexamethylene diamine), 1 1 ,78g (0,0330 mol) of hexamethylene diamine at 32,5% in water. 4,57 g (0,029 mol) of ΤΗΓ . ¹ - , 30 g of water and 2g of an anti-foaming agent

[001 6] For PA 66/6TF 90/10 mol/mol, we started the reaction by mixing 134,48 g {0,513 mof) of Nylon 66 salt (stoichiometric salt of adipic acid and hexamethylene diamine), 20,50 g (0,057 mol) of hexamethylene diamine at 32,5% in water. 9, 12 g (0,057 mol) of THFDCA. water and 2g of an anti-foaming agent,

[001 17] For PA 66/6TF 80/20 mol/mol. we started the reaction by mixifv ¹ · -, ^« g (0,453 mol) of Nylon 66 salt (stoichiometric salt of adipic acid a i · ^methylene diamii ) of hexamethylene diamine at 32,5% in water, 18, 13 g

(0, 1 13 mol) of THFDCA, 1 C water and 2g of an arrti-foaming agent.

{001 18] Properties of these copolyamides are reported in Table 2.

[001 191 The more THFDCA is included r 6 chains, the tower the Ttn. Hrn and Tc. We generally use comonomers to decrease the crystallization kinetics to get molded part having a better surface aspect or for fiber spinning. As a comparison, '61 80/20 rnol/mol (imsGphfhaiic acid} synthesized using the same method80/2Q rnol/mol has the following thermal properties. Tm=240°C, Tc=193°C and Tg=76°C. PA 66 copolyamides having THFDCA or isophthaiic acid as comonomers in similar content, exhibit similar crystallization kinetics but THFDCA doesn't increase Tg

[00120] We observed in our conditions that the ess/trans ratio of THFDCA changed from 9S/S to 82/ 18 mol/mol after the synthesis of PA 66/6TF 80/20 mol/mol. Table 2. Properties of copolyamides synthesized using THFDCA cis/trans 95/5.

^''Determined at 40°C/min

[00121 ] Pellets of copolyamides are then dried during 16h at 90X under vacuum before being submitted to injection molding to get specimens (bars 90x13x1 ,6 mm³) using a micro-extruder DS MIDI 2000 with barrel temperature at 280X and mould temperature at 7GX,

[00122] Water absorption (i X, saturation) of the copolyamides is analyzed by placing the specimens in water at room temperature and by following the weight of the specimens until no change in weight is observed. W; sorption is determined by calcuiating {mf-mi)/mi, with mi=initial weight of the specimen before the test (dry), mf=final weight when the specimen is saturated with water.

[00123] PA 66/6THF 100/0, 95/5, 90/10 and 80/20 mol mol respectively absorb 8,5wt- %, 9.9 wt.-%. 11wt.-%, 14wt.-% of water It is higher than water absorption obtain with isophthalic acid as a comonomer, These copolymers would be interesting to increase the moisture absorption of textile fiber to bring higher comfort.

{00124] Exai ithesis of polyphthalamide copolyamide using salt route

{001251 We synthesized PA 6T76TF 50/50 mol/mol 3/40 mol/mol using an aqueous salt route We use a sample of THFDCA cis/trans 95/5 for these syntheses

[00126} Polymerization of theses copolyamides is achieved using a classical PA 68 synthesis process with a few modifications : we prepare an aqueous salt composed with diacids mixtures (terephthaiic acid and THFDCA) and diamine at a concentration of 52 wt -% in water and 70X, we close the reactor and we heat t e reactor under 17.5 Oar pressi filiation of water under pressure), we depressurize to atmospheric pressure when the temperature of the reaction mixture reach 26C 2 finish the reaction at

290X du ' - ;., i at atmospheric pressure. The copolyamides are extrud* ' i the reactor, cooled in a cold water bath to get a strand and then pelletized,

/50 mol/mol, we started the reaction by mixing 49.89 g (0, 1767 mol) of Nylon 6T salt (stoichiometric salt of terephthalic acid and hexamethylene diamine), 66,61 g (0, 1768 mol) of hexamethylene diamine at 30,85% in water. 28,34 g {0, 77 mol) of THFD _ ' <^< > ; u >r #ater and 2g of an anti-foamr · nt,

[00128] P 60/40 mol/mol, we started the reaction by mixing 28 61 g

(0, 172 mol) of terephthalic. acid, 50 39 g (0,287 mol) of 1 .10-diaminodecane (purity=98%), - ~ " ¹ , - lol)^{■ 1} DC A. 86.62 g of water and 2g of an anti-foaming agent. Table 3. Properties of copolyamides synthesized usi ^:DCA cis/trans 95/5.

^''Determined at t OX/min

[00129] THFDCA can be used in polyphthalamide to modulate the thermal properties of PA 6T

Claims

1. Polyamide comprising < sating unit of formula I below:

(I) in which

3resents a covalent bond or a divalent hydrocarbon-based group chosen from saturated or unsaturated aliphatics, saturated or unsaturated cycloaliphatics, aromatics, arylaliphatics and alkylaromatics.

Polyamide according to Claim 1 , in which R is chosen from linear or branched aikyl groups having from 1 to 36 carbon atoms, preferably a linear alkyl group having from 4 to 14 carbon atoms.

Polyamide according to Claim i or 2, in which is chosen from: -{CH₂)₄-, -(CH₂)₅- - (CH_z)_e-_p -(CH₂)-CH(CH3)-(CH₂)₃-, -(CH₂)₁₀- and -(CH₂)_{i r}.

Polyamide according to Claim 1. in which R ts a divalent aromatic hydrocarbon-based group comprising from 6 to 18 carbon atoms, preferably the groups 1 ,4-benzene. 1 ,3- benzene and -(CH₂)-Ph~(CH₂)- in positions 13 and i .4.

Polyamide according to any one of Claims 1 to 4, characterized in that it is a homopoiyamide consisting entirely of the repeating unit of formula I,

Polyamide according to any one of Claims t to 4, characterized in that it is a copolymer comprising other repeating units different from the unit of formula I, the said repeating units different from the unit of formula f originating from comonorners such as dicarboxylic acids, diamines, amino acids and/or lactams,

Polyamide according to Claim 6, characterized m that it is a copolymer^' chosen in group constituted of^' PA 6T/6TF. PA10T/10TF. PA6T/6TF/66, PA66/6TF r and PA610/6TF Process for preparing a poiyamide according to any one of Claims 1 to . characterized in that it comprises a po!yconclensation reaction between:

at least one dicarboxylic acid or at least one carboxy!ic acid diester, at least one dinitrile or at least one acyl dichloride of respective formulae IV, IV, IV" and IV" below:

where Ri and f¾, which are identical or different, are chosen from C1 -C4 alkyis;

(IV") and

o at least one diamine of formula V below:

H₂N-R-NH₂ (V)

with R as defined in one of Claims 1 to 4 ^, Process according to Claim 8, characterized in that at least one diamine of formula V is btobased according to standard AST D6866. 0^, Process according to either of Claims 8 and 9. characterized in that it comprises a polycondensation reaction between:

- at least one dicarboxylic acid of formula !V below:

and

o at least one diamine of formula V below:

H₂N-R-NH₂ (V)

with R as defined in one of Claims 1 to 4.

1 1 Process according to any of Claims 8 to 10. characterized in that at least the dicarboxylic acid of formula IV is biobased according to standard ASTM D6866. 12. Use of the polyamide according to any one of Claims 1 to 7, for making articles by moulding, injection-moulding, injection/blow-moulding, extrusion/blow-moulding, extrusion or spinning.

13. Articles obtained from the polyamide according to any one of Claims 1 to 7, the said articles being mouldings or extrudates, yarns, fibres, filaments or films.

14. Composition comprising at least the polyamide as defined in any one of Claims 1 to 7, and optionally reinforcing fillers and/or various additives.