FR3080377A1 - PROCESS FOR THE PREPARATION OF ALIPHATIC POLYESTERAMIDES - Google Patents

Abstract

The application relates to a process for preparing an aliphatic polyesteramide comprising a step b) of polycondensation of an aliphatic dioldiamide and an aliphatic dicarboxylic acid in the presence of a distannoxane catalyst for preparing aliphatic polyesteramides having improved thermomechanical properties.

Description

Process for the preparation of aliphatic polyesteramides

The present invention relates to a process for the preparation of aliphatic polyesteramides and the aliphatic polyesteramides obtained.

Polyesters are appreciated for their low impact on the environment, thanks to their biodegradability and the possibility of preparing them from renewable resources. However, their mechanical properties are not always sufficient, which is troublesome for many applications (for example polycaprolactone).

On the contrary, polyamides form a network of hydrogen bonds between the amide functions which gives them a high cohesive energy density, which results in high mechanical properties. They are however not or little biodegradable.

In this context, the preparation of polyesteramides is sought after because they are likely to have improved mechanical and thermal properties compared to polyesters, while being biodegradable, and potentially derived from renewable resources. Advantageously, the thermal and mechanical properties can be adapted by varying the density of amide function by adjusting the length of the monomer units.

The simplest route for polyesteramide synthesis is the polycondensation of a dicarboxylic acid and an amino alcohol. In this case, a recurring unit carrying an ester function and an amide function is produced, but without any control over the insertion of the amino alcohol into the polyesteramide, therefore without control over the microstructure of the polymer (diagram 1). However, the thermomechanical properties are directly impacted by the microstructure of the polyesteramide.

n HOOC COOH + n HO NH ₂

Scheme 1: Preparation of polyesteramides from a dicarboxylic acid and an amino alcohol.

Processes for the preparation of aromatic or partially aromatic polyesteramides have been described, for example by Mansour et al. European Polymer Journal 46, 814-820, 2010. However, the preparation of aliphatic polyesteramide is much less described in the literature.

The copolymerization by ring opening of Γε-caprolactone and εcaprolactam is also a means of preparing a polyesteramide with good control of the directional insertion of the monomers. However, the monomers are inserted into the chain statistically, eliminating any possibility of modulation of the structure and therefore of the mechanical properties. In addition, this synthetic route is difficult to generalize to other monomers.

Synthetic routes from prepolymers have been developed, but most of these studies have led to the synthesis of block copolymers, generally having the properties of thermoplastic elastomers. The insertion of amino acid into a polyester backbone has also been reported, but the optimal goal of the alternative copolymer has barely been achieved, and improvement in mechanical properties has not been demonstrated.

Some studies report the preparation of polyesteramides from dioldiamide.

Application WO 98/32779 describes a process for preparing polyesteramides comprising the following two steps:

- reaction of a monoalkanolamine with a diacid halide to form a dioldiamide,

- reaction of the dioldiamide with a diacid halide in a solvent and in the presence of Sb ₂ O ₃ as catalyst. This reaction releases HCl which can be trapped by an acid acceptor such as triethanolamine.

This process is however difficult to implement on an industrial scale because of the HCl formed.

US Patent 2,946,769 describes the preparation of polymers from diols and a dicarboxylic acid, the diol possibly being a dioldiamide. The polymerization is carried out in two stages: reaction under nitrogen at 100-300 ° C at atmospheric pressure, then reduction of the pressure to 1-3 mm Hg at the same temperature. A heptafluorobutyric acid catalyst is used. The implementation of the reduced pressure process induces higher costs than a process carried out at room temperature.

The development of a process for the preparation of alternative aliphatic polyesteramides to those mentioned above which is simple, can be carried out under mild conditions (in particular at atmospheric pressure), which can be carried out with monomers having different chain sizes and which makes it possible to obtaining polyesteramides of high degree of polymerization is sought.

Furthermore, US Pat. No. 6,350,850 describes a process for the preparation of polyesters from a dicarboxylic acid and a diol in the presence of a distannoxane catalyst and a non-solvent. The use of an amide-carrying diol is not suggested. The preparation of a polyesteramide either. However, the transposition to the preparation of polyesteramides is not trivial because the presence of amide functions is likely to have an impact on the polymerization, in particular on the efficiency of the catalyst. In addition, the regularity of the chain of a polyesteramide, in particular of the amide / ester function sequences, is essential because it directly affects its properties. In addition, the directionality of the sequences must be controlled in order to optimize the number and the energy of the interchain hydrogen bonds, which will directly affect the cohesive energy of the polymer and therefore its mechanical properties. This problem does not exist for a polyester which only includes ester functions.

In order to solve the problems of the prior art mentioned above, according to a first object, the invention relates to a process for the preparation of an aliphatic polyesteramide comprising a step b) of polycondensation of an aliphatic dioldiamide and a diacid aliphatic carboxylic acid in the presence of a distannoxane catalyst.

The distannoxane catalyst typically has the formula (I):

R ¹ R

II

X-Sn-O-Sn-Y

12

RR (i) in which:

R ¹ , R ² , R ³ and R ⁴ independently represent a linear, cyclic or branched alkyl comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, and

- X and Y independently represent an isothiocyanate, a halogen, a hydroxyl, an alkoxyl comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, said alkoxyl being optionally substituted by one or more hydroxyl, or an acyloxyl comprising from 2 to 10 carbon atoms, preferably from 2 to 5 carbon atoms, said acyloxyl optionally being interrupted by a carboxy group.

In formula (I), the following embodiments can be considered, independently or combined with each other:

R ¹ , R ² , R ³ and R ⁴ independently represent methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, a heptyle and octyl. C4 alkyls, in particular n-butyl, are particularly preferred.

R ¹ , R ² , R ³ and R ⁴ are identical.

R ¹ , R ² , R ³ and R ⁴ represent n-butyl.

the halogen is chosen from chlorine, bromine and iodine, preferably chlorine,

- the alkoxyl is chosen from methoxyl, ethoxyl, propoxyl, isopropoxyl, butoxyl, isobutoxyl, s-butoxyl, t-butoxyl, pentoxyl, hexoxyl and octoxyl.

the alkoxyl is substituted by one or more hydroxyl (s) and is in particular chosen from 2-hydroxyethoxyl, 2-hydroxypropoxyl, 3-hydoxypropoxyl and 4hydroxybutoxyl.

- the acyloxyl is chosen from acetoxyl, propionyloxyl, butyryloxyl, valeryloxyl and hexanoyloxyl.

- the acyloxyl is interrupted by a carboxy group is especially chosen from 2carboxypropionyloxyle, 3-carboxypropionyloxyle and 4-carboxybutyryloxyle.

- X and Y are independently chosen from an isothiocyanate, a halogen, a hydroxyl

For example, the distannoxane catalyst is chosen from 1-chloro-3-hydroxy-

1.1.3.3- tetra-n-butyldistannoxane, 1,3-dichloro-1,1,3,3-tetra-n-butyldistannoxane, 1, 3-diisothiocyanate-1,1,3,3-tetra-n- butyldistannoxane, and 1-hydroxy-3-isothiocyanate-

1.1.3.3- tetra n-butyldistannoxane. 1-chloro-3-hydroxy-1,1,3,3-tetrabutyldistannoxane (CHTD) is the preferred catalyst.

This catalyst can be synthesized by synthetic routes known to those skilled in the art, for example from alkyltin oxide and / or alkyltin halide.

The distannoxane catalyst can be in the form of a dimer of formula (II) below: there F T s - l 1 "" " ί K (II)

whose groups R ¹ , R ² , R ³ , R ⁴ , X and Y are as defined above.

Generally, the distannoxane catalyst is used in a molar proportion of 0.0001 to 5%, especially 0.0005 to 5 mol%, preferably 0.001 to 1%, relative to the dicarboxylic acid.

In the sense of the request, by “aliphatic”, one understands non-aromatic.

The aliphatic dicarboxylic acid used in step b) generally has the formula (III):

HOOC-L-COOH (III), in which L represents:

an alkylene comprising from 1 to 20 carbon atoms, in particular from 1 to 18 carbon atoms, preferably from 2 to 10 carbon atoms,

an alkenylene comprising from 2 to 20 carbon atoms, in particular from 2 to 18 carbon atoms, preferably from 2 to 10 carbon atoms or

an alkynylene comprising from 2 to 20 carbon atoms, in particular from 2 to 18 carbon atoms, preferably from 2 to 10 carbon atoms, said alkylene, alkenylene or alkynylene may be linear, cyclic or branched and said alkylene, alkenylene or alkynylene which can be interrupted by one or more groups -O-, -S- or - (C = O) -.

The aliphatic dicarboxylic acid is especially chosen from malonic acid, succinic acid, 2,3-dimethylsuccinic acid, glutaric acid, 3,3dimethylglutaric acid, 3-methyladipic acid, adipic acid , pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14tetradecanedicarboxylic acid, 1,15-pentadecanedicarboxylic acid, 1,16hexadecanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cis acid -4 cyclohexene-1,2-dicarboxylic acid, trans-4-cyclohexene-1,2-dicarboxylic acid, 4,5dimethylcyclohexa-1,4-diene-1,2-dicarboxylic acid, maleic acid, l trans-βhydromuconic acid, (Z) octadec-9-enedioic acid, fumaric acid, diglycolic acid 3,3'-oxydipropionic acid, 4,4'-oxydibutyric acid, 5,5'-oxidivaleric acid, 6,6'-oxydicaproic acid, 8,8'-oxydicaprylic acid, 6-oxoundecanedioic acid, 5-oxododecanedioic acid, 5-oxotetradecanedioic acid, l 5oxohexadecanedioic acid, 6-oxododecanedioic acid, 6-oxotridecanedioic acid, 3-oxotetradecanedioic acid, 2-oxotetradecanedioic acid, 2,2,13,13tetramethyl-7-oxotetradecanedioic acid, acid 6-oxopentadecanedioic acid, 6oxoheptadecanedioic acid, 7-oxotetradecanedioic acid, 7oxopentadecanedioic acid, 10-oxononadecanedioic acid and mixtures thereof, succinic acid being particularly preferred (L then representing -CH ₂ -CH ₂ -).

The aliphatic dioldiamide used in step b) generally has the formula ^(IV): ° \\ L // °

H (D ₁ OH

X-N-X

HH (IV) in which X ¹ and X ² and X ³ independently represent:

an alkylene comprising from 1 to 20 carbon atoms, in particular from 1 to 18 carbon atoms, preferably from 2 to 10 carbon atoms,

an alkenylene comprising from 2 to 20 carbon atoms, in particular from 2 to 18 carbon atoms, preferably from 2 to 10 carbon atoms or

an alkynylene comprising from 2 to 20 carbon atoms, in particular from 2 to 18 carbon atoms, preferably from 2 to 10 carbon atoms, said alkylene, alkenylene or alkynylene may be linear, cyclic or branched and said alkylene, alkenylene or alkynylene which can be interrupted by one or more groups -O-, -S- or - (C = O) -.

The following embodiments can be considered, independently or in combination with each other:

X ¹ and X ³ contain the same number of atoms and / or the same number of carbon atoms, and preferably X ¹ and X ³ are identical,

X ¹ and X ³ independently represent a linear alkylene or a linear alkenylene comprising from 1 to 20 carbon atoms, in particular from 2 to 18 carbon atoms, preferably from 2 to 10 carbon atoms,

L and X ² contain the same number of atoms and / or the same number of carbon atoms, and preferably L and X ² are identical,

L and X ² contain the same number of carbon atoms nLX2 and X ¹ and X ³ contain the same number of carbon atoms nx1X3, with n _x1X3 = n _LX2 - 2,

L and X ² independently represent a linear alkylene or a linear alkenylene comprising from 1 to 20 carbon atoms, in particular from 2 to 18 carbon atoms, preferably from 2 to 10 carbon atoms.

Preferably, the aliphatic dioldiamide is N, N'-bis (2hydroxyethyl) butanediamide) (HEBDA).

Diagram 2 illustrates the polycondensation of step b):

HO ° ^S \ 1 /

X-N H, 0

OH

N- X ³

H

HO

OH

R ¹

R ³

X-Sn-O-Sn-Y

O,

H-PO \ 1, X-N

H

OH + H ₂ O (X) of

1.00 diacid to 1.20, molar

Diagram 2: reaction diagram of step b)

Generally, at the start of step b), an aliphatic dicarboxylic molar ratio relative to the aliphatic dioldiamide is in particular from 1.00 to 1.10 mol, preferably from 1.00. Apart from the stoichiometric ratio, the degree of polymerization is generally lower.

Preferably, step b) is a polycondensation by mass and / or in the presence of a non-solvent and / or in the presence of a solvent, preferably a polycondensation by mass. Typically, step b) comprises a step b1) of mass polycondensation, and a step b2) of polycondensation in the presence of a non-solvent, step b2) preferably being carried out after step b1).

Mass polycondensation is carried out in the absence of solvent or non-solvent (in addition to the water which forms during the polycondensation). Typically, the reaction medium at the start of step b) (or b1)) consists of aliphatic dicarboxylic acid, aliphatic dioldiamide and distannoxane catalyst. When the polycondensation begins, the reaction medium generally consists of aliphatic dicarboxylic acid, aliphatic dioldiamide, distannoxane catalyst, water, polyesteramide and possibly by-products of the polycondensation.

By "non-solvent" is meant a solvent in which neither the aliphatic dioldiamide, nor the aliphatic diacid, nor the aliphatic polyesteramide are soluble. By "non-soluble" is meant that the solubility of each of these compounds in the non-solvent is less than 1 g / L, in particular less than 0.5 g / L, preferably less than 0.1 g / L .

By "solvent" is meant a solvent in which the aliphatic dioldiamide and the aliphatic diacid are soluble. By "soluble" is meant that the solubility of each of these compounds in the solvent is greater than 1 g / L, in particular greater than 2 g / L, preferably greater than 5 g / L.

When step b) is carried out in the presence of a non-solvent, the medium is biphasic, with a phase comprising the aliphatic dicarboxylic acid and the aliphatic dioldiamide and the polyesteramide formed, and a phase comprising the nonsolvent. Advantageously, the water produced during the condensation passes into the non-solvent phase.

A non-solvent which has a boiling point above 100 ° C is preferable. In addition, a non-solvent having a boiling point close to the temperature of step b) is preferable. More particularly, the non-solvent can be chosen from n-octane, nnonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, npentadecane, decaline, benzene, trimethylbenzene, xylene, their isomers, quinoline, diphenyl ether and a mixture of these, preferably decaline.

The solvent is for example N-methyl-2-pyrrolidone (NMP).

The non-solvent or solvent content is preferably from 0.1 to 10 parts by weight, in particular from 0.2 to 5 parts by weight relative to 1.0 part by weight of the total (aliphatic dicarboxylic acid and dioldiamide) . Below 0.1 parts by weight of non-solvent, the elimination of the water produced during the polycondensation is less. Contents greater than 10 parts by weight lead to an increase in cost.

The use of the non-solvent leads to the formation of a two-phase medium which minimizes the contacting of the water produced during the reaction (mainly in the phase comprising the non-solvent) and of the polyesteramide formed, which promotes polycondensation, limits degradation by hydrolysis of the polyesteramide formed and allows obtaining a polyesteramide of high degree of polymerization.

The use of a solvent makes the mixture of aliphatic dioldiamide and aliphatic dicarboxylic acid more homogeneous.

The temperature of step b) is appropriately chosen according to the starting materials used, knowing that too low temperatures lead to too low kinetics, and a too high temperature is likely to favor the secondary reactions and / or degradation. and / or elimination of one of the monomers. Generally, step b) is carried out at a temperature of 80 to 280 ° C., preferably from 100 to 200 ° C. The polycondensation in mass or in the presence of solvent is preferably carried out at a temperature above 100 ° C., and / or the polycondensation in the presence of non-solvent is preferably carried out at a temperature above the boiling point of the non-solvent azeotrope / water. These conditions favor the elimination of water, and therefore polycondensation and obtaining a polyesteramide with a high degree of polymerization.

In order to facilitate the elimination of water, it can be distilled during step b). When step b) is a polycondensation in the presence of a non-solvent, the distillation is typically an azeotropic distillation.

Step b) (and steps b1 and b2)) is preferably carried out in the molten state, that is to say at a temperature higher than the highest temperature between the melting temperature of the aliphatic dioldiamide, the melting temperature of the aliphatic dicarboxylic acid and the melting temperature of the aliphatic polyesteramide. Melting temperatures can be determined by differential scanning calorimetry.

The reaction time of step b) (and of steps b1 and b2)) is also chosen appropriately depending on the starting materials used. It is generally from 30 min to 200 hours, preferably from 1 h to 10 h.

Step b) is generally carried out at atmospheric pressure (1 bar), which is an important advantage in terms of cost.

In particular in the absence of non-solvent, the process may include, after step b), a step c) of recovery of the polyesteramide formed. The polyesteramide can easily be recovered by adding a non-solvent for the polyesteramide, which induces its precipitation. It can then be filtered.

The process can comprise, before step b), a step a) of preparation of the aliphatic dioldiamide by reaction of at least one monoalkanolamine with an aliphatic dicarboxylic acid.

This step a) is particularly easy to carry out when, in formula (IV) above, X ¹ and X ³ are identical. Typically, step a) comprises the reaction of a monoalkanolamine of formula (V):

HO-X ¹ -NH ₂ (V) in which X ¹ is as defined above, with an aliphatic dicarboxylic acid of formula (VI):

HOOC-X ² -COOH (VI) in which X ² is as defined above.

Diagram 3 illustrates the reaction diagram of step a).

Ο. , 0

HO \ 1

X — ΝΗ ₂ (V)

Diagram 3: reaction diagram of step a)

The aliphatic dicarboxylic acid is preferably chosen from the aliphatic dicarboxylic acids described above for step b). Preferably, the aliphatic dicarboxylic acid used in step a) is identical to that used in step b).

The monoalcanolamine is especially chosen from ethanolamine, 3-amino-1propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 2-amino2-methyl -1-propanol, 3-aminomethylcyclohexylmethanol, 4 aminomethylcyclohexylmethanol, 5-amino-2, 2-dimethyl-1-pentanol and mixtures thereof, preferably ethanolamine.

O.

, 0

HO

HO

OH

X-N H

OH

NX ¹

H

Preferably, the aliphatic dicarboxylic acid is succinic acid and the monoalcanolamine is ethanolamine, the aliphatic dioldiamide formed then being N, N'bis (2-hydroxyethyl) butanediamide) (HEBDA), as illustrated in diagram 4:

eiridriuidinirie _{succinic acid} N, N'-bis (2-hydroxyethyl) butanediamide) (HEBDA)

Diagram 4: Reaction diagram for the preparation of HEBDA

Ethanolamine and succinic acid are advantageously from renewable sources. When the aliphatic dicarboxylic acid used in step b) is succinic acid, the process (steps a) and b)) advantageously uses starting materials obtained from renewable sources.

Step a) is generally carried out with a molar ratio of the monoalkanolamine relative to the aliphatic dicarboxylic acid of 2.00 to 30.00, in particular from 4.00 to 25 mole, preferably 20 mol.

Step a) is carried out in the presence of a solvent or in the absence of solvent, preferably in the absence of solvent.

Stage a) typically lasts from 1 hour to 48 hours, preferably from 5 hours to 30 hours.

Step a) is generally carried out at a temperature of 50 to 250 ° C, preferably from 100 to 200 ° C.

Step a) is preferably carried out at atmospheric pressure (1 bar).

Typically, at the end of step a), the reaction medium consists of a mixture of aliphatic dioldiamide, monoalkanolamine (generally introduced in excess), water and optionally solvent, and optionally by-products.

The method may include a step a1) of recovery of the aliphatic dioldiamide. For example, at the end of step a), a non-solvent for the aliphatic dioldiamide is added to induce its precipitation, then it is filtered. Alternatively, at the end of step a), vacuum evaporation is carried out in order to evaporate the monoalkanolamine and the water.

Preferably, steps a) and b) are implemented in the same reactor (“one-pot” synthesis in English).

For example, the method comprises step a) as defined above, whereby a mixture is obtained comprising the aliphatic dioldiamide and the monoalcanolamine, then a step a1) of removing the excess of the monoalcanolamine, typically by vacuum evaporation, then step b) as defined above, these steps preferably being carried out in the same reactor. Thus, to carry out step b), it suffices to add the aliphatic dicarboxylic acid to the reaction medium obtained at the end of step a1).

Advantageously, the method according to the invention allows the preparation of aliphatic polyesteramides comprising units of different chain lengths, and therefore a modulation of the thermomechanical properties to order, depending on the need.

According to a second object, the invention relates to polyesteramides capable of being obtained by the process according to the invention.

These polyesteramides typically have the formula (X):

(X) in which X ¹ , X ² , X ³ , L are as defined above and n is the degree of polymerization of the polyesteramide.

For example, they have the following formula (XI), and are typically derived from succinic acid (used as the aliphatic dicarboxylic acid in steps a) and b)) and from ethanolamine, these two starting materials advantageously being derived of renewable resources:

^H + (D ^ (CH ₂ ) ₂ - ^ O — H (ch ₂ ) ₂ -n N- (CH ₂ ) ₂ (CH ₂ ) ₂ —H-oh (XI)

These polyesteramides are advantageously biodegradable, have a high molar mass and a melting temperature (measurable by differential scanning calorimetry), which implies a certain crystallinity due to a controlled microstructure.

This high crystallinity and this high molar mass allow the thermomechanical properties of the polyesteramides to be generally improved compared to the polyesteramides prepared by the processes of the prior art.

In particular, the polyesteramides obtained from succinic acid (used as aliphatic dicarboxylic acid in steps a) and b)) have:

better thermal performance than poly (butylene succinate) (PBS), which presages more applications than those of PBS, and

- a thermal performance close to that of polypropylene which has many applications.

The following examples illustrate the invention.

Examples

A. Step a): preparation of dioldiamides

Example 1: Synthesis of N, N’-bis (2-hydroxyethyl) butanediamide (HEBDA)

9.784 g (82.9 mmol) of succinic acid (melting point = 188 ° C) and 100 mL (1.657 mol, 20 eq.) Of ethanolamine were initially introduced into a 250 mL flask with stirring. The mixture was heated to 160 ° C with stirring. The solution became clear in a few minutes. After 5 hours of reaction, the reaction was terminated. The reaction medium was cooled, then the solution was precipitated in 1 L of chloroform. The insoluble product was filtered, washed with 500 ml of fresh chloroform, then dried. The expected product was obtained with a yield of 78.5% (13.29 g) with high purity (100%). Purity and structure are confirmed by ¹ H, ¹³ C NMR and HSQC experiments. The white crystalline product is stable up to a T ₅ o _{/ o} of 205 ° C. (value corresponding to a weight loss of 5%) and its melting point is 144 ° C.

Example 2 Synthesis of N, N’-bis (2-hydroxyethyl) pentanediamide (HEPDA)

Example 1 was repeated using 10.95 g (82.9 mmol) of glutaric acid (melting point = 98 ° C) and 100 mL (1.657 mol, 20 eq.) Of ethanolamine. The reaction was terminated after 9 hours of reaction. After cooling the reaction medium and adding 30 ml of EtOH, part of the excess ethanolamine was removed in vacuo. Precipitation was induced by adding 100 mL of CH ₂ CI ₂ ; However, a second precipitation by adding a mixture (50/50) EtOH / CH ₂ CI ₂ was necessary to remove all of the ethanolamine. Thus, a yield of 54% of a colorless product was obtained (9.85 g). The structure of N, N'-bis (2-hydroxyethyl) pentanediamide and its purity (100%) were verified by NMR ( ¹ H, ¹³ C and HSQC). The melting point of the compound is 117 ° C and T ₅ o _{/ o} is equal to 253 ° C.

Example 3 Synthesis of N, N’-bis (2-hydroxyethyl) hexanediamide (HEHDA)

Example 1 was repeated using 6.053 g (41.4 mmol) adipic acid (melting point = 152 ° C) and 50 mL (0.828 mol, 20 eq.) Ethanolamine. The reaction was stopped after 24 hours of reaction. It was over. As in Example 1, precipitation was induced by adding 1 liter of CHCI ₃ . After filtration, the insoluble compound was washed with 500 ml of CHCl ₃ and dried. 6.97 g (72.5%) of pure N, N'-bis (2hydroxyethyl) hexanediamide were obtained. The NMR characterizations ( ¹ H, ¹³ C and HSQC) are in agreement with the expected structure. The melting point and T ₅ o _{/ o} are 135 ° C and 261 ° C respectively.

Example 4 Synthesis of N, N’-bis (2-hydroxyethyl) octanediamide (HEODA)

Example 1 was repeated using 14.43 g (82.8 mmol) of suberic acid (melting point = 137 ° C) and 100 mL (1.657 mol, 20 eq.) Dethanolamine. The reaction was stopped after 24 hours of reaction. It was over. The reaction medium was cooled to 65 ° C and precipitated in 1 liter of CHCl ₃ . After filtration, the insoluble compound was washed with 500 ml of CHCl ₃ and then dried. A yield of 67.5% of a pure, colorless product (14.45 g) was obtained. The structure and purity of N, N'-bis (2hydroxyethyl) octanediamide were checked by NMR ( ¹ H, ¹³ C and HSQC). The melting point and T ₅ o _{/ o} are respectively 140 ° C and 271 ° C.

Example 5 Synthesis of N, N’-bis (2-hydroxyethyl) decanediamide (HEDDA)

Example 1 was repeated using 16.77 g (82.9 mmol) of sebacic acid (melting point = 141 ° C) and 100 mL (1.657 mol, 20 eq.) Dethanolamine. The reaction was stopped after 26 hours of reaction. It was over. After cooling the flask, 500 ml of EtOH were added to crystallize the product. Then, this was filtered off, washed with 150 ml of fresh EtOH and dried. 18.6 g (77.8%) of pure white N, N'-bis (2hydroxyethyl) decanediamide were obtained and characterized by NMR ( ¹ H, ¹³ C and HSQC). The melting point of the compound is 146 ° C and T ₅ o _{/ o} is 280 ° C.

Example 6: Synthesis of (Z) N, N'-bis (2-hydroxyethyl) octadec-9-enediamide (HED18: 1DA) Example 1 was repeated using 12.94 g (41.4 mmol) of octadec-9enedioic acid (Z) (melting point = 68 ° C) and 50 mL (0.828 mol, 20 eq.) of ethanolamine. The reaction was stopped after 24 h of reaction. It was over. The reaction medium was cooled, then 250 ml of EtOH were added to crystallize the product. Then, this was separated by filtration, washed with 100 ml of fresh EtOH and dried. Thus, a yield of 75.6% of a colorless product was obtained (12.20 g). The structure and purity of (Z) N, N'-bis (2-hydroxyethyl) octadec-9-enediamide were verified by NMR ( ¹ H, ¹³ C and HSQC). The melting point of the compound is 119 ° C and T ₅ o _{/ o} is equal to 294 ° C.

B. Step b): polycondensation

In the following examples, the temperatures T ₅ o _{/ o} were measured by metric thermog ravi analysis on a TGA Q50 device from the company TA Instrument by heating the samples from 20 ° C. to 500 ° C. with an increase in temperature of 10 ° C. / min. The temperatures T _g , T _c and T _m were determined by differential scanning calorimetry (DSC) on a DSC Q2000 device, TA Instrument, Jacobs • Monomer procedure:

Cycle 1: Initial temperature 25 ° C, isotherm lean 2 min, increase to 200 ° C with a ramp of 20 ° / min

Cycle 2: Isothermal for 2 min, then cooling down to -10 ° C at 20 ° C / min • Polyesteramide procedure:

Cycle 1: Initial temperature 25 ° C, isotherm lean 2 min, increase to 200 ° C with a ramp of 20 ° / min

Cycle 2: Isothermal for 10 min, then cooling down to -80 ° C to 50 ° C / min

Cycle 3: Isothermal for 2 min, increase from 10 ° C / min to 200 ° C

Cycle 4: Isotherm for 2 min, then cooling down to -80 ° C at 10 ° C / min Cycles 3 and 4 were repeated a second time, and were used to determine the values of the thermal characteristics.

Steric Exclusion Chromatography (SEC) was performed on a VE 2001 GPC Solvent / Sample module, Viscotek GPC max, Jacobs.

B.1. Comparative examples: with other catalysts

Example 7 Synthesis of PA from HEBDA and Succinic Acid in the Presence of Ti (OBu) ₄ as Catalyst

The polymerization was carried out by polycondensation of an equimolar mixture of succinic acid and HEBDA. The polycondensation was carried out in two stages using titanium tetrabutoxide (Ti (OBu) ₄ ) as catalyst.

1.50 g (12.73 mmol) of succinic acid, 2.60 g (12.73 mmol) of HEBDA and 1 ml of N-methyl-2-pyrrolidone (NMP) were introduced into a Schlenk bicol tube glass with stirring. The mixture heated to 160 ° C quickly became clear and was stirred for 2 hours under a stream of nitrogen. Then, Ti (OBu) ₄ in solution in toluene was added (0.1 mol% relative to succinic acid).

During the second polycondensation step, the reaction mixture was heated to the final temperature (170 ° C) and a dynamic vacuum was applied for 4 h in order to distill the traces of water. Then, the reaction medium was cooled, dissolved in 1.5 ml of N-methyl-2-pyrrolidone (NMP) and precipitated in 400 ml of MeOH. After filtration, 0.389 g of polymer was obtained (yield of 11%), the thermal properties of which are: T ₅ o _{/ o} = 262 ° C; T _g = -5 ° C; T _c = 41 ° C; T _m = 158 ° C.

Example 8 Synthesis of PA from HEHDA and Adipic Acid in the Presence of Ti (OBu) ₄ as Catalyst

Example 7 was repeated using 2.0 g (13.7 mmol) of adipic acid and 3.17 g (13.7 mmol) of HEHDA without introducing a solvent. At the end of the two-step polymerization procedure, the mixture was dissolved in 15 mL of NMP and precipitated in 1.5L of MeOH. After filtration and drying, 1.34 g of polymer were recovered (yield of 29%). The polymer was characterized by ¹ H NMR, ¹³ C. The signals of the protons of the terminal chains made it possible to determine the molar mass of the polymer (M _n = 9300 g / mol). The thermal properties are: T ₅ o _{/ o} = 268 ° C; T _g = -14 ° C; T _c = 102 ° C; T _m = 122 ° C.

Example 9 Synthesis of PA from HEODA and Suberic Acid in the Presence of Ti (OBu) ₄ as Catalyst

Example 7 was repeated using 2 g (11.5 mmol) of suberic acid and 2.99 g (11.5 mmol) of HEODA without introducing a solvent. At the end of the two-step polymerization procedure, the mixture was dissolved in 15 mL of DMSO and precipitated in 1L of MeOH. After filtration and drying, 0.85 g of polymer was obtained (yield of 19%). The polymer was characterized by ¹ H NMR, ¹³ C. The thermal properties are: T ₅ o _{/ o} = 263 ° C; T _g = -11 ° C; T _c = 105 ° C; T _m = 137 ° C.

Example 10 Synthesis of PA from HEDDA and Sebacic Acid in the Presence of Ti (OBu) ₄ as Catalyst

Example 7 was repeated using 2.03 g (10 mmol) of sebacic acid and 2.88 g (10 mmol) of HEDDA without introducing a solvent. At the end of the two-step polymerization procedure, the mixture was dissolved in 10 mL of DMSO and precipitated in 1L of MeOH. After filtration and drying, 3.55 g of polymer were obtained (yield of 79%). The polymer was characterized by ¹ H NMR, ¹³ C. The thermal properties are: T ₅ o _{/ o} = 266 ° C; T _g = -27 ° C; T _c = 106.5 ° C; T _m = 130 ° C

Example 11 Synthesis of PA from HED18: 1 DA and (Z) octadec-9-enedioic acid (D18: 1) in the presence of Ti (OBu) ₄ as catalyst

Example 7 was repeated using 1.99 g (6.4 mmol) of D18: 1 and 2.55 g (6.4 mmol) of HED18: 1DA without introducing a solvent. At the end of the two-step polymerization procedure, the mixture was dissolved in 40 mL of THF and precipitated in 1L of MeOH. After filtration and drying, 3.56 g of polymer were recovered (yield of 82%). The polymer was characterized by ¹ H NMR, ¹³ C. The molecular weight of the polymer was determined by steric exclusion chromatography (SEC) in THF using a calibration with polystyrene. M _n is equal to 12000 g / mol with a dispersity of 1.97. The thermal properties are: T ₅ o _{/ o} = 266 ° C; T _g = 27 ° C; T _c = 106.5 ° C; T _m = 130 ° C

Example 12 Synthesis of PA from HED18: 1DA and D18: 1 in the Presence of Triazabicyclodecene (TBD) as Catalyst (Green Catalyst)

The polymerization was carried out by polycondensation of an equimolar mixture of D18: 1 and HED18: 1DA. The polycondensation was carried out in two stages using triazabicyclodecene (TBD) as catalyst.

0.40 g (1.28 mmol) of D18: 1 and 0.51 g (1.28 mmol) of HEBDA were initially introduced into a glass bicol Schlenk tube with stirring. The mixture heated to 160 ° C. quickly becomes clear and was stirred for 2 hours under a stream of nitrogen.

Then, the TBD catalyst in a toluene solution was added (10 mol% relative to the diacid). During the second polycondensation step, the reaction mixture was heated to the final temperature (190 ° C) and a dynamic vacuum was applied for 3 h. Then, the reaction medium was cooled, dissolved in 1 ml of NMP and precipitated in 400 ml of MeOH. After filtration, 0.354 g of polymer was obtained (yield of 41%). The polymer was characterized by NMR. The molar mass determined by SEC in THF using a polystyrene calibration is equal to 10200 g / mol with a dispersity of 1.67. The thermal properties are: T ₅ o _{/ o} = 301 ° C; T _g = - 33 ° C; T _c = 29 ° C; T _m = 67 ° C

Example 13 Synthesis of PA from HED18: 1DA and Succinic Acid in the Presence of Triazabicyclodecene (TBD)

Example 12 was repeated using 0.40 g (3.39 mmol) of succinic acid and

1.35 g (3.39 mmol) of HED18: 1DA. Then, the reaction medium was cooled, dissolved in 1 ml of NMP and precipitated in 400 ml of MeOH. After filtration, 0.203 g of polymer were obtained (yield of 13%). The polymer was characterized by NMR. The molar mass determined by SEC in THF using a polystyrene calibration is equal to 6600 g / mol with a dispersity of 1.24.

The thermal properties are: T ₅ o _{/ o} = 293 ° C; T _g = - 36 ° C; T _c = -12 ° C and 22 ° C; T = 59 ° C

B.2. Example according to the invention: with a distannoxane catalyst

Example 14 Synthesis of PA from HEBDA and Succinic Acid Using 1-Chloro-3-Hydroxy-1,1,3,3-Tetrabutyldistannoxane (CHTD) as Catalyst

The CHTD catalyst was synthesized as follows: 14.91 g (59.9 mmol) of dibutyltin oxide, 6.07 g (20 mmol) of dibutyltin dichloride and 200 ml of ethanol (95%) were placed in a 500 mL flask fitted with a condenser. The mixture was stirred and heated at reflux for 6 h. At the end of the reaction, the solvent was removed. The white solid thus obtained was reduced to powder. It was left in the ambient atmosphere overnight, then recrystallized from hexane. After filtration and drying, the powder (18.66 g, 89%) was characterized: T ₅ o _{/ o} = 216 ° C; T _c = 121 ° C; T _m = 106 ° C - 136 ° C.

The melt polymerization of succinic acid and HEBDA was carried out using a 1/1 molar ratio and the CHTD catalyst synthesized previously. So,

2.36 g (20.0 mmol) of succinic acid, 4.08 g (20.0 mmol) of HEBDA and 106.8 mg (2 mmol) of CHTD were initially introduced into a 50 mL flask fitted with a Dean

Stark and a refrigerant. The mixture was stirred at 140 ° C for 1 hour. The mixture became homogeneous after 15 min. Then it was heated at 160 ° C for 45 minutes and 4 mL of decalin was added. The system was agitated under these conditions for 48 hours. After cooling the reaction medium to room temperature, 70 ml of 5 MeOH were introduced into the flask, which was left stirring overnight. The polymer was collected by filtration and dried. 0.51 g of polymer were obtained (yield of 9%). The thermal properties of the polymer are: T _g = -11 ° C; T _c = 38 ° C; T _m = 152 ° C.

Claims (13)

1.- Process for the preparation of an aliphatic polyesteramide comprising a step b) of polycondensation of an aliphatic dioldiamide and of an aliphatic dicarboxylic acid in the presence of a distannoxane catalyst. 2, - Process according to claim 1, in which the distannoxane catalyst has the formula (I): R ¹ R ³ X-Sn-O-Sn-Y 12 L R R (i) in which: R ¹ , R ² , R ³ and R ⁴ independently represent a linear, cyclic or branched alkyl comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, and - X and Y independently represent an isothiocyanate, a halogen, a hydroxyl, an alkoxyl comprising from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, said alkoxyl being optionally substituted by one or more hydroxyl, or an acyloxyl comprising from 2 to 10 carbon atoms, preferably from 2 to 5 carbon atoms, said acyloxyl optionally being interrupted by a carboxy group. 3.- Method according to claim 1 or 2, wherein the aliphatic dicarboxylic acid has the formula (III): HOOC-L-COOH (III), in which in which L represents: an alkylene comprising from 1 to 20 carbon atoms, in particular from 1 to 18 carbon atoms, preferably from 2 to 10 carbon atoms, an alkenylene comprising from 2 to 20 carbon atoms, in particular from 2 to 18 carbon atoms, preferably from 2 to 10 carbon atoms or an alkynylene comprising from 2 to 20 carbon atoms, in particular from 2 to 18 carbon atoms, preferably from 2 to 10 carbon atoms, said alkylene, alkenylene or alkynylene may be linear, cyclic or branched and said alkylene, alkenylene or alkynylene which can be interrupted by one or more groups O-, -S- or - (C = O) -. 4, - Method according to any one of claims 1 to 3, in which the aliphatic dioldiamide has the formula (IV): C> 7 ° ^ho \ 1 / XN NX ³ (IV) HH in which X ¹ and X ² and X ³ independently represent: an alkylene comprising from 1 to 20 carbon atoms, in particular from 1 to 18 carbon atoms, preferably from 2 to 10 carbon atoms, an alkenylene comprising from 2 to 20 carbon atoms, in particular from 2 to 18 carbon atoms, preferably from 2 to 10 carbon atoms or an alkynylene comprising from 2 to 20 carbon atoms, in particular from 2 to 18 carbon atoms, preferably from 2 to 10 carbon atoms, said alkylene, alkenylene or alkynylene may be linear, cyclic or branched and said alkylene, alkenylene or alkynylene which can be interrupted by one or more groups -O-, -S- or - (C = O) -. 5. - Method according to any one of claims 1 to 4, wherein the aliphatic dioldiamide is N, N'-bis (2-hydroxyethyl) butanediamide) (HEBDA) and / or the aliphatic dicarboxylic acid is succinic acid . 6. - Method according to any one of claims 1 to 5, wherein step b) is a mass polycondensation. 7. - Method according to any one of claims 1 to 6, comprising, before step b), a step a) of preparation of the aliphatic dioldiamide by reaction of at least one monoalkanolamine with an aliphatic dicarboxylic acid. 8. - Process according to claim 7, in which at least one monoalkanolamine has the formula (V): HO-X ¹ -NH ₂ (V) in which X ¹ is as defined in claim 4. 9. A method according to claim 7 or 8, wherein the aliphatic dicarboxylic acid of step a) has the formula (III) as defined in claim 3, the aliphatic dicarboxylic acid of step a) preferably being identical to the aliphatic dicarboxylic acid of step b). 10. - Method according to any one of claims 1 to 9, wherein steps a) and / or b) is (are) carried out at atmospheric pressure. 11, - Method according to any one of claims 7 to 10, wherein steps a) and b) are carried out in the same reactor. 12, - Polyesteramide capable of being obtained by the process according to any one of claims 1 to 11. 13. - Polyesteramide according to claim 12, of formula (X): (X) in which: - L is as defined in claim 3, - X ¹ , X ² , and X ³ , L are as defined in claim 4, and - n is the degree of polymerization of the polyesteramide.