EP2297082A1

EP2297082A1 - Method for preparing polymer bioplasticizers

Info

Publication number: EP2297082A1
Application number: EP09745840A
Authority: EP
Inventors: Sophie Rouzeau; Catherine Pinel; Gabriella Fogassy; Georges Gelbard; Philippe Cassagnau
Original assignee: Tissage et Enduction Serge Ferrari SA
Current assignee: Centre National de la Recherche Scientifique CNRS; Universite Claude Bernard Lyon 1 UCBL; Serge Ferrari SAS
Priority date: 2008-05-16
Filing date: 2009-05-15
Publication date: 2011-03-23
Also published as: WO2009138508A1; FR2931159A1; FR2931159B1

Abstract

The invention relates to a method for preparing a composition containing at least one fatty acid ester, characterised in that the method comprises reacting a compound or a mixture of compounds having formula (II) with a carboxylic anhydride having formula (III) in the presence of a catalyst, said catalyst being selected from the group comprising the following catalysts: homogenous or heterogeneous quaternary ammoniums, heterogeneous acids, homogenous or heterogeneous bases, and mixtures thereof.

Description

PROCESS FOR THE PREPARATION OF POLYMER BIOPLASTIFIERS

The technical field of the invention is the synthesis of plasticisers of polymers.

The present invention relates to a process for the preparation of polyester compositions derived from fatty acid esters of plant origin, the compositions obtained by this process and their uses as bioplasticizers of polymers such as PVC (polyvinyl chloride). 0 Plasticized PVC has long been used in many domestic and industrial applications. The properties of PVC can be modified by the addition of miscible compounds of lower molecular weight leading to a homogeneous material. These compounds, called "plasticizers" give the PVC various properties according to the proportion added to the polymer. For indication, soft PVC is distinguished from rigid PVC by the proportion of plasticizer, which varies from 15 to 60%.

The main plasticizers of PVC are mainly phthalates and adipates. The most common PVC plasticizer is octyl phthalate (DOP). This product is derived from petroleum derivatives and has the disadvantage of migrating over time.

Several other compounds are already used as substituents of octyl phthalate but none of them has properties as effective as a plasticizer. Most of these molecules come from petrochemicals and are therefore less and less available. In addition, their preparation processes use polluting and toxic chemicals such as solvents and organic acids.

It is therefore desirable to have plasticizers derived from raw materials that are not petroleum derivatives, but rather from resources that are more acceptable from an ecological and economic point of view and that are otherwise available and have little or no toxicity. Thus, we already know bioplasticizers for PVC from agricultural resources, which are renewable raw materials, biodegradable, abundant and do not contribute to the increase of atmospheric CO ₂ . The agricultural resources used as raw materials for bioplasticizers are esters of fatty acids derived from vegetable oils. They have the advantage of being already highly functionalized and therefore require fewer synthesis steps than hydrocarbons to be converted into finished products.

Patent applications disclose methods for synthesizing polyester-based bioplasticizers from epoxidized fatty acid oils or esters.

In DE-A-4433958, the synthesis is carried out by acid hydrolysis of the epoxides to diols followed by acylation with acids or anhydrides. An application of the products obtained as PVC plasticizers is also described.

In EP-A-0 341 548, the synthesis is carried out by direct acylation using carboxylic anhydride and in the presence of a carboxylic acid and / or sulfuric acid catalyst.

The processes described in these patents use strong acids which are dangerous when going to scale and which require neutralization.

OBJECTIVES OF THE INVENTION

An object of the present invention is to provide a novel process for the preparation of polymer plasticizers which uses non-toxic and recyclable reagents.

Another object of the invention is to provide a new process for the preparation of polymer plasticizers which uses compounds from widely available agricultural resources.

In addition, an object of the invention is to provide a process for the preparation of polymer plasticizers which requires few steps and which takes place without a solvent.

Yet another object of the invention is to obtain compositions which have plasticizing properties of polymers comparable to those of products derived from petroleum resources. BRIEF DESCRIPTION OF THE INVENTION

However, after extensive research, the applicant has discovered that it is possible to transform vegetable oil derivatives which are renewable, biodegradable, abundant and inexpensive raw materials into compositions comprising esters of low-hydroxylated fatty acids. having properties of PVC bioplasticizers very close to those of octyl phthalate, without being toxic. In addition, few synthetic steps are required to transform these raw materials into finished products.

The term "heterogeneous" means in particular that the species concerned is grafted onto a solid support and "homogeneous" means, for example, that the species is soluble, in solution or in suspension. The term "traces" means in particular that the amounts are less than 5% by weight, preferably less than 1% by weight.

This is why the subject of the present invention is a process for preparing a composition comprising at least one fatty acid ester of formula (I) below:

in which

R is an acyl group of formula where R "is a linear, branched or cyclic alkyl group having from 1 to 16 carbon atoms,

R 'is a linear or branched alkyl group containing from 1 to 16 carbon atoms,

• (n + x + m) is greater than or equal to 6, X is 1, 2 or 3,

• and (n + m) is greater than or equal to 3,

characterized in that a compound or a mixture of compounds of the following formula (II) is reacted:

in which R ', n, x and m are as defined above, with at least one carboxylic anhydride of formula (III) below:

wherein R "is as defined above, in the presence of a catalyst, said catalyst being selected from the group consisting of the following catalysts: homogeneous or heterogeneous quaternary ammoniums, heterogeneous, basic homogeneous or heterogeneous acids and mixtures thereof.

Another subject of the invention is a composition based on ester (s) of fatty acid of formula (I) described above and comprising traces of quaternary ammonium.

Yet another subject of the invention is the use of a composition based on fatty acid ester (s) of formula (I) as described above, obtained or not by the process according to the invention. as a plasticizer for polymer, preferably PVC.

In addition, the subject of the present invention is also a polymer plasticized with a fatty acid ester (s) composition of formula (I) as described above, obtained or not by the process of the invention. . Also, an object of the invention is a method of manufacturing a coated yarn or fabric in which a fabric is coated or a yarn is sheathed with a plasticized polymer described above.

DETAILED DESCRIPTION OF THE INVENTION

In the process according to the invention, the reaction is an epoxide-opening acylation reaction which takes place advantageously without a solvent. In addition, the reaction is preferably carried out in an aprotic medium. In still other preferred conditions of implementation of the invention, the reaction takes place at a temperature greater than 70 ⁰ C, preferably greater than 100 ⁰ C. The temperature accelerates the speed of the acylation reaction.

Preferably, the catalyst is selected from the group consisting of quaternary, basic ammonium catalysts and mixtures thereof.

The heterogeneous acidic catalysts are chosen for example from the group comprising HY zeolites, Y-Al ₂ O ₃ , TiO ₂ and ZrO ₂ and preferably they are chosen from the group consisting of these compounds.

For example, the homogeneous basic catalysts are selected from Lewis or Bronsted bases, in the group comprising potassium carbonate, potassium hydroxide and pyridine. Preferably, they are selected from the group consisting of these compounds. For their part, the heterogeneous basic catalysts are chosen for example from the group comprising CaO and NaY zeolite and, preferably, they are chosen from the group consisting of these.

In other preferred conditions for carrying out the process described above, the catalyst is a quaternary ammonium salt of formula R ' ₄ N ⁺ X ^" in which:

The groups R ¹ are identical or different groups to each other, chosen from the following groups: linear or branched alkyls, substituted or unsubstituted by one or more heteroatoms, containing from 1 to 20 carbon atoms, preferably from 1 to 16 carbon atoms, aryls, substituted or not by one or more heteroatoms, comprising 5 to 8 carbon atoms, aralkyls, substituted or not by one or more heteroatoms, comprising from 5 to 20 carbon atoms, alkylaryls, substituted or not by one or more heteroatoms, comprising from 5 to 20 carbon atoms, And X ^" is a contranion selected from the group consisting of carboxylates, halides, sulfates, carbonates, phosphates.

Preferably, the quaternary ammonium salt catalyst has the formula

R 1 1W xτ + X ^" in which:" the groups R ¹ are groups that are identical to or different from each other, chosen from: linear or branched alkyls, substituted or unsubstituted by one or more heteroatoms, comprising from 1 to 16 atoms of carbon o aryls, substituted or unsubstituted by one or more heteroatoms, comprising from 5 to 8 carbon atoms,

Contranion X ^" is a halide or an acetate.

More preferably, X ^" is selected from the group consisting of Cl ^" , Br ^" and CH ₃ CO (X, and more preferably still, X ^" is a Cl ^" .

Preferably, the homogeneous quaternary ammonium salts are chosen from the group consisting of the following compounds: tetrabutylammonium chloride, tetramethylammonium chloride, tetrapentylammonium bromide, cetyltrimethylammonium chloride, cetylpyridinium chloride, imidazolinium salts and their mixtures.

The heterogeneous quaternary ammonium salts are chosen from macroporous anionic resins such as a crosslinked styrene-divinylbenzene copolymer functionalized with quaternary ammonium groups marketed under the brand name. AMBERLYST® A-26, poly (styrene-codivinylbenzene) functionalized with quaternary ammonium chlorides marketed under the tradename AMBERJET® 4200 and mixtures thereof.

In the above process, it is preferable to use, for one equivalent of compound of formula (I),

From 0.8 to 10 equivalents of carboxylic anhydride, preferably from 1 to 5 equivalents, and still more preferably about 1.2 equivalents,

• 0.01 to 0.10 equivalents of catalyst, preferably of 0.02 to 0.07 equivalents and in particular about 0.05 equivalents.

According to a particular embodiment of the process of the invention, the compound or the mixture of compounds of formula (II) is prepared by epoxidation of a compound of formula (IV) below:

in which R ', n, x and m are as defined above,

with a peracid, preferably formed extemporaneously,

this compound or this mixture of compounds of formula (IV) being itself prepared by transesterification of a compound or a mixture of compounds of formula (V) below:

in which n, x and m are as defined above,

with an alcohol of formula R'OH in the presence of a catalyst of formula R'OM, in which R 'is as defined above and M is chosen from alkalis and alkaline earth metals, preferably Na.

Preferably, the compound or mixture of compounds of formula (IV) is used directly in the synthesis of the compound or mixture of compounds of formula (II). The products marketed by NOVANCE® are mixtures of fatty acid esters of vegetable origin which can be used for the direct synthesis by acylation of the fatty acid ester mixtures according to the invention. For example, LUBRIROB® 301.01 is predominantly methyl linoleate.

According to another embodiment of the process, the compound or the mixture of compounds of formula (II) is prepared by transesterification of a compound or a mixture of compounds of formula (VI) below:

in which n, x and m are as defined above,

with an alcohol of formula R'OH in the presence of a catalyst of formula R'OM, in which R 'is as defined above and M is chosen from alkalis and alkaline earth metals, preferably Na,

this compound or this mixture of compounds of formula (VI) being itself prepared by epoxidation of a compound or a mixture of compounds of formula (V) below: wherein n, x and m are as defined above, with a peracid, preferably formed extemporaneously.

Preferably, the compound or mixture of compounds (VI) is used directly for the synthesis of the compound or mixture of compounds of formula (II). In this case, it may be a compound or a mixture of compounds sold by the company COGNIS®. For example, EDENOL® B 316 SPEZIAL is epoxidized linseed oil, mainly epoxidized methyl linolenate. EDENOL® D 82S is epoxidized soybean oil, mainly epoxidized methyl linoleate.

The peracid, preferably formed extemporaneously, is for example formic peracid, obtained by reaction between formic acid and hydrogen peroxide.

The compound or the mixture of compounds of formula (V) described above comprises one or more fatty acid triglycerides of plant origin, in particular vegetable oils. Preferably, the triglycerides of fatty acids used come from sunflower oil.

A purification stage of the compound of formula (I) or of the mixture of compounds of formula (I) obtained after acylation is optionally carried out. For example, filtration is carried out on activated carbon. Washing with water can also be done to remove the catalyst.

The process according to the invention requires few steps and takes place without solvent, which has advantages for the transposition on an industrial scale in terms of cost and respect for the environment. The composition according to the invention is characterized in that it comprises at least one fatty acid ester corresponding to the following formula (I):

in which

R is an acyl group of formula R " where R "is a linear, branched or cyclic alkyl group having from 1 to 16 carbon atoms,

R 'is a linear or branched alkyl group containing from 1 to 16 carbon atoms,

• (n + x + m) is greater than or equal to 6,

X is 1, 2 or 3,

And (n + m) is greater than or equal to 3, and quaternary ammonium salts in the form of traces.

Preferably, in the formula (I) described above, the groups R 'and R "are linear or branched alkyl groups having from 1 to 8 carbon atoms and especially from 1 to 4 carbon atoms, and:

• (n + x + m) is greater than 11, • x is 1 or 2,

• and (n + m) is greater than 9.

R 'is preferably selected from the group consisting of: methyl, ethyl and 2-ethylhexyl and R "is preferably selected from the group consisting of: methyl, ethyl, propyl and butyl.

According to a particular embodiment, the composition according to the invention comprises the products obtained by the process of the invention. The composition according to the invention, obtained or not by the process of the present invention, has very interesting properties and qualities. It is endowed in particular with remarkable plasticizing properties of polymer materials, in particular PVC (polyvinyl chloride). In addition, this composition according to the invention is not toxic, which is advantageous for the polymer materials plasticized by the latter.

APPLICATIONS OF THE COMPOSITIONS ACCORDING TO THE INVENTION

The properties of the compositions according to the invention are illustrated below in the experimental part. Said properties justify the use of the composition comprising at least one fatty acid ester, preferably obtained by the method described above, as a plasticizer for a polymer, in particular PVC. The applications of plasticized polymers, in particular plasticized PVC, by the plasticizing composition of the invention are the same as those of plasticized polymers, in particular plasticized PVC, by the products commonly used, including octyl phthalate.

In addition, the invention relates to son or fibers coated with plasticized polymer, preferably plasticized PVC, by the composition especially obtained by the process according to the invention as well as substrates whose surfaces are coated with such plasticized PVC. . The substrates may be fabrics, non-woven substrates, floor coverings, wood, etc.

The present invention also relates to a woven or non-woven fibrous substrate comprising at least one layer of plasticized polymer, preferably plasticized PVC as defined above.

The preferred conditions of implementation of the method described above also apply to the other objects of the invention referred to above, in particular to the products derived from the use of the plasticizing compositions according to the invention, in particular those obtained by this method. process. EXPERIMENTAL PART PROCESS

The following examples illustrate this application:

FIG. 1 represents the viscosity and elasticity modules of the material according to example 3, as a function of temperature, FIG. 2 represents the viscosity and elasticity moduli of the material according to example 4, depending on the FIG. 3 represents the viscosity and elasticity moduli of the material according to example 6, as a function of temperature, FIG. 4 represents the viscosity and elasticity modules of the reference material DINP, as a function of the temperature. .

Example 1 Preparation of Composition 1

• Step 0:

A composition comprising predominantly ethyl oleate was prepared from vegetable oil according to the following reaction scheme:

- _0H NaOMe _ca

In a 500 ml flask equipped with a condenser containing 200 g of rapeseed oil, a solution of 500 mg of NaOMe in 23 g of MeOH is introduced. The medium is vigorously stirred for 20 minutes at 25 ° C. The glycerol formed is separated, then a new solution of NaOMe / MeOH is stirred again for 20 minutes at 25 ° C. The crude ester is separated and then washed with water to remove excess catalyst and methanol. The ester is finally dried over Na ₂ SO ₄ .

According to Gas Chromatography (GC) analysis, the composition obtained is as follows:

• Step 1 :

The composition obtained in step 0 is epoxidized according to the following reaction scheme:

epoxidation methyl oleate obtained in step 0

In a 500 ml flask equipped with a condenser, 100 g of the above fatty ester prepared (predominantly methyl oleate) and 3.8 ml (0.1 mol) of formic acid are stirred with a mechanical stirrer. 104 ml (1 mol) of H ₂ O ₂ (35%) are slowly added and then heated at 70 ^° C. for 14 hours. After the reaction, the mixture is cooled, diluted with diethyl ether, then it is washed with 30 ml H ₂ O and then with a saturated solution of Na ₂ CO ₃ and finally a saturated solution of NaCl. The organic phase is dried (MgSO ₄ ), then filtered and the solvent evaporated. GC analysis shows that the reaction is complete. The yield of the reaction is 86%.

• 2nd step :

The composition obtained in step 1 is acylated to give the composition 1 according to the following reaction scheme: Epoxy methyl oleate obtained in Step 1 Composition 1

In a 500 ml flask, equipped with a condenser, a mixture of 100 g of epoxidized fatty acid prepared above, 54 ml (0.53 mol) of acetic anhydride and 5.5 g (0.02 mol ) of tetrabutyl ammonium chloride are stirred and heated at 130 ⁰ C for 6h. After the reaction the mixture is cooled, diluted with diethyl ether, then washed with H ₂ O, then with saturated Na ₂ CO _{3 solution} and finally with saturated NaCl solution. The resulting solution is colored (dark brown). It is then filtered on activated charcoal and on basic Al ₂ O ₃ (3X) which makes it possible to eliminate the impurities, and then the evaporated solvent. GC analysis shows that the reaction is complete. The yield of the reaction is 41%.

Example 2 Preparation of Composition 2

• Step 1 :

A composition comprising at least one epoxidized fatty acid ester by transesterification from epoxidized soybean oil marketed by COGNIS OLEOCHEMICALS® was prepared according to the following reaction scheme:

In a 500 ml flask, a mixture of 160 g of epoxidized soybean oil (EDENOL® D 82 S), 50 ml of methanol and 700 mg of MeONa are stirred vigorously at 70 ^° C. for 7 h. After cooling, 25 ml are again added of MeOH and 1.4 g of MeONa, and the mixture is heated for 9 hours at 70 ^° C. At the end of the reaction, the mixture is cooled and washed with saturated NaCl solution. The organic phase is dried over MgSO ₄ . Yield = 98%. According to Gas Chromatography (GC) analysis, the resulting composition is as follows

• 2nd step

A composition 2 comprising mainly at least one fatty acid ester comprising four lateral acetate groups by acylation was prepared from the composition obtained in step 1. epoxy methyl linoleate obtained in step 1 Composition 2

In a 500 ml flask, 100 g of epoxidized fatty ester prepared in step 1, 72 ml of acetic anhydride and 5.5 g of Bu ₄ NOAc are heated for 18 h at 130 ^° C. After reaction, the mixture is cooled, extracted with ethyl acetate, washed with H ₂ O, saturated Na ₂ CO ₃ and finally saturated NaCl. After filtration on activated charcoal (CECA, L3S) for decolorization and drying over MgSO ₄ , the solvent is evaporated. GC and NMR analyzes show total conversion Example 3 Preparation of the Composition 3

• Step 1 .

A composition comprising at least one epoxidized fatty acid ester by epoxidation from 2-ethylhexyl ester of oleic acid predominantly mono-unsaturated was prepared according to the following reaction scheme

epoxidation 2-ethylhexyl oleate

According to the analysis by gas chromatography (GC) oleate, starting from 2-ethylhexyl acrylate, sold by the company NOVANCE® as the LUBRIROB® 01 808, has the following composition ^•

In a 500 ml flask equipped with a condenser, 100 g of starting material (mainly oleate of 2-ethylhexyl) and 3.8 ml (0.1 mol) of formic acid are stirred with a mechanical stirrer 104 ml. (1.2 mol) of H ₂ θ ₂ (35%) are slowly added and then heated at 70 ^° C. for 16 h. After the reaction, the mixture is cooled, extracted with diethyl ether, then it is washed with 30 ml H ₂ O and then with a saturated solution of Na ₂ CO ₃ and finally a saturated solution of NaCl The organic phase is dried (MgSO ₄ ), then filtered and the solvent is evaporated in a rotavapor. The GC analysis shows that the reaction is complete. The yield of the reaction is 76%. • 2nd step :

A composition 3 comprising a fatty acid ester comprising two side acetate groups by acylation was prepared from the composition obtained in step 1. Epoxidized 2-ethylhexyl oleate obtained in Step 1 Composition 3

In a 500 ml flask equipped with a condenser, a mixture of 100 g of epoxidized fatty acid prepared above, 53 ml (0.56 mol) of acetic anhydride and 5.5 g (0.02 mol ) of tetrabutyl ammonium chloride are stirred and heated at 130 ⁰ C for 14h. After the reaction the mixture is cooled, diluted with diethyl ether, then it is washed with H ₂ O and then with a saturated solution of Na ₂ CO ₃ and finally a saturated solution of NaCl. The resulting solution is colored (dark brown). It is then filtered on activated charcoal and on basic Al ₂ O ₃ (3X) which makes it possible to eliminate the impurities, and then the evaporated solvent. GC analysis shows that the reaction is complete. The yield of the reaction is 44%.

Example 4 Preparation of Composition 4

Step 1: A composition comprising a mixture of epoxidized fatty acid esters from a mixture based on predominantly mono-unsaturated oleic methyl and ethyl esters was prepared according to the following reaction scheme:

epoxydaton methyl oleate

According to analysis by gas chromatography (GC), the starting mixture marketed by the company NOVANCE under the name ESTOROB® 802.11 has the following composition:

In a 500 ml flask equipped with a condenser, 100 g of methyl oleate and ethyl oleate mixture and 7.6 ml (0.2 mol) of formic acid are stirred with a mechanical stirrer. 104 ml (1 mol) of H ₂ O ₂ (35%) are slowly added and then heated at 70 ^° C. for 14 hours. After the reaction, the mixture is cooled, extracted with diethyl ether, then it is washed with 30 ml H ₂ O and then with a saturated solution of Na ₂ CO ₃ and finally a saturated solution of NaCl. The organic phase is dried (MgSO ₄ ), then filtered and the solvent evaporated. GC analysis shows that the reaction is complete. The yield of the reaction is 87%.

• 2nd step :

A composition 4 comprising, for the most part, a mixture of fatty acid esters comprising two lateral acetate groups from the composition obtained in step 1 according to the following reaction scheme:

O O

O A-, acylation -A ^

Composition obtained in step 1

Compositon 4 In a 500 ml flask equipped with a condenser, a mixture of 100 g of epoxidized fatty acid prepared above, 45 ml (0.47 mol) of acetic anhydride and 6.4 g (0.02 mol ) of tetrabutyl ammonium bromide are stirred and heated at 130 ^° C. for 6h30. After the reaction the mixture is cooled, diluted with diethyl ether, then it is washed with H ₂ O, then with a saturated solution of Na ₂ CO ₃ and finally with a saturated solution of NaCl. The solution obtained is colored (brown dark) It is then filtered on activated charcoal and basic Al ₂ O ₃ (3X) which eliminates impurities, and then the solvent is evaporated. The GC analysis shows that the reaction is complete. The reaction yield is 62%.

Example 5 Preparation of Composition 5

• Step 1

A composition was prepared from a mixture of oleic acid methyl ester predominantly mono-unsaturated according to the following reaction scheme:

epoxidation methyl oleate

According to analysis by gas chromatography (GC), the starting mixture, marketed by the company NOVANCE under the name LUBRIROB® 926.65 has the following composition:

In a 500 ml flask equipped with a condenser, 100 g of the above-mentioned epoxidized fatty ester (predominantly methyl oleate) and 3.8 ml (0.1 mol) of formic acid are stirred with mechanical stirrer. 104 ml (1 mol) of H ₂ θ ₂ (35%) are slowly added then heated at 70 ⁰ C for 14h. After the reaction, the mixture is cooled, diluted with diethyl ether, then it is washed with 30 ml H ₂ O and then with a saturated solution of Na ₂ CO ₃ and finally a saturated solution of NaCl. The organic phase is dried (MgSO ₄ ), then filtered and the solvent evaporated. GC analysis shows that the reaction is complete. The yield of the reaction is 86%.

• 2nd step :

A composition comprising a mixture of fatty acid esters comprising two lateral acetate groups from the composition obtained in step 1 was prepared according to the following reaction scheme:

Composition obtained in step 1 Composition 5

Tests of different catalysts:

Different catalysts were tested in the acylation reaction.

• Tetrabutyl ammonium chloride

In a 500 ml flask, equipped with a condenser, a mixture of 100 g of epoxidized fatty acid prepared above, 54 ml (0.53 mol) of acetic anhydride and 5.5 g (0.02 mol ) of tetrabutyl ammonium chloride are stirred and heated at 130 ⁰ C for 6h. After the reaction the mixture is cooled, diluted with diethyl ether, then washed with H ₂ O, then with saturated Na ₂ CO _{3 solution} and finally with saturated NaCl solution. The resulting solution is colored (dark brown). It is then filtered on activated charcoal and on basic Al ₂ O ₃ (3X) which makes it possible to eliminate the impurities, and then the solvent is evaporated. GC analysis shows that the reaction is complete. The yield of the reaction is 41%. . AMBERLYST® A-26

In a 10 ml flask equipped with a condenser, a mixture of 500 mg of epoxidized fatty acid prepared above, 300 μl of acetic anhydride and 120 mg of AMBERLYST® A-26 are stirred and heated to 130 ° C. ⁰ C for 6h. After the reaction, the mixture is cooled and filtered. It is diluted with diethyl ether, then washed with H ₂ O, then with a saturated solution of Na ₂ CO ₃ and finally with a saturated solution of

NaCl. GC analysis indicates a conversion of 72 O / 70.

. Γ-Al ₂ O ₃ In a 5 ml flask, a mixture of 313 mg of epoxidized fatty acid prepared above, 238 μl of acetic anhydride and 50 mg of 7-Al ₂ O ₃ are stirred and heated to 130 ^° C. during 3h. After the reaction, the mixture is cooled and filtered. It is diluted with diethyl ether, then washed with H ₂ O, then with a saturated solution of Na ₂ CO ₃ and finally with a saturated solution of NaCl. GC analysis indicates a conversion of 50%.

. CaO

In a 5 ml flask, a mixture of 100 mg of epoxydodecane, 50 μl of acetic anhydride and 25 mg of CaO are stirred and heated at 100 ^° C. for 24 hours. After the reaction, the mixture is cooled and filtered. It is diluted with diethyl ether, then washed with H ₂ O, then with a saturated solution of Na ₂ CO ₃ and finally with a saturated solution of NaCl. GC analysis indicates a conversion of 63%.

• Pyridine - In a 5 ml flask, a mixture of 185 mg of epoxydodecane, 105 μl of acetic anhydride and 0.02 ml of pyridine are stirred and heated at 100 ^° C. for 3 h. After the reaction, the mixture is cooled and filtered. It is diluted with diethyl ether, then washed with H ₂ O, then with a saturated solution of Na ₂ CO ₃ and finally with a saturated solution of NaCl. GC analysis indicates a conversion of 93%. - In a 5 ml flask, a mixture of 208 mg of methyl oleate,

100 mg of acetic anhydride and 27 mg of pyridine are stirred and heated at 130 ^° C. for 24 hours. After the reaction, the mixture is cooled and filtered. It is diluted with diethyl ether, then washed with H ₂ O, then with a saturated solution of Na ₂ CO ₃ and finally with a saturated solution of NaCl. GC analysis indicates a conversion of 96%.

Example 6 Preparation of Composition 6

• Step 1 :

A composition was prepared from a mixture of predominantly di-unsaturated linoleic acid methyl ester according to the following reaction scheme:

epoxidation Methyl liπolèate

According to analysis by gas chromatography (GC), the starting mixture sold by NOVANCE® under the name LUBRIROB® 301.01 has the following composition:

In a 500 ml flask equipped with a condenser, 100 g of methyl linoleate and 8 ml (0.2 mol) of formic acid are stirred with a mechanical stirrer.

1 10 ml (1.3 mol) of H ₂ θ ₂ (35%) are slowly added then heated at 70 ⁰ C for

14h. After the reaction, the mixture is cooled, diluted with diethyl ether, then it is washed with 30 ml H ₂ O and then with a saturated solution of Na ₂ CO ₃ and finally a saturated solution of NaCl. The organic phase is dried (MgSO ₄ ), then filtered and the evaporated solvent. GC analysis shows that the reaction is complete. The yield of the reaction is 97% (light yellow liquid).

• 2nd step :

A composition 6 was prepared from the composition obtained in step 1 according to the following reaction scheme:

OO _O ≈ a ^w cyjr, l <a-t ^{^"i"} o, n,

Composition obtained in step 1 Composition 6

In a 500 ml flask equipped with a condenser, a mixture of 100 g of epoxidized fatty acid prepared above, 106 ml (1.1 mol) of acetic anhydride and 11 g

(0.04 mol) of tetrabutyl ammonium chloride are stirred and heated at 130 ^° C. for 6h30. After the reaction the mixture is cooled, extracted with diethyl ether, then it is washed with H ₂ O, then with a saturated solution of Na ₂ CO ₃ and finally with a saturated solution of NaCl. The resulting solution is colored (dark brown). It is then filtered on activated charcoal and on basic Al ₂ O ₃ (3X) which makes it possible to eliminate the impurities, and then the solvent is evaporated. GC analysis shows that the reaction is complete. The yield of the reaction is 46% (yellow oil).

Example 7 Preparation of Composition 7

A composition 7 was prepared from the composition obtained in step 1 of example 5 according to the following reaction scheme:

o o acylation Jl X ^

Composition Obtained in Step 1 of Example 5 Composition 7

In a 50 ml flask equipped with a condenser, a mixture of 10 g of epoxidized fatty acid prepared in step 1 of example 4, 5 ml of propanoic anhydride and 461 mg of tetrabutyl ammonium chloride are stirred and heated at 130 ^° C. for 15h. After the reaction the mixture is cooled, diluted with diethyl ether, then washed with H ₂ O, then with saturated Na ₂ CO _{3 solution} and finally with saturated NaCl solution. The resulting solution is colored (dark brown). GC analysis shows that the reaction is complete.

Example 8: Production of "plastisols" (PVC + plasticizer)

By "plastisol" is meant a liquid paste consisting of a dispersion of particles of one or more types of PVC (or other polymer) in a plasticizer.

The following composition is produced: (100 percent PVC resin) PVC 100 Thermal Stabilizer (tin type here) 2

Pigment 10

Plasticizer 50

The plasticizers are compositions 3 and 4 of fatty acid esters (liquids) obtained in Preparations 3 and 4, the PVC is in powder form. The liquid thermal stabilizer allows the PVC to be cooked without degrading. The thermal stabilizer is a derivative of Sn tin or a metal salt.

The plasticizer, the thermal stabilizer, the pigment and the PVC are introduced in order. Then the mixture is kneaded until a homogeneous paste (plastisol) is obtained.

This is then coated on silicone paper and baked in an oven for 1 minute 30 seconds at 190 ^° C. EXPERIMENTAL PART

Tests on plastisols made:

The tests are carried out on the plastisols obtained, each time in comparison with a reference. The reference is a Plasticizer / PVC 1/2 w / w sample with di-isononyl phthalate (DINP).

Tests A:

Brookfield Viscosity: standardized test NF EN ISO 2555, the viscosity is measured after 2 minutes at 30 rpm at 25 ° C.

Percentage elongation NF EN ISO 527-3: allows to evaluate the plasticizing power of the plasticizer within the PVC, the more important it is, the more the composition is plasticizing.

Red Congo NF ISO 182-1: standardized test that allows to evaluate the static thermal stability of a product, we obtain a time in seconds, the longer it is, the better the thermal stability.

Test results A

The results of the tests A show that the plasticizing characteristics of the compositions 3, 4 and 6 are close to or better than those of the DINP reference. Test B:

Rheological test (linear viscoelasticity, measurement of the complex shear modulus as a function of temperature (T)) with a Rheometer: RHEOMETRICS MECHANICAL

SPECTROMETER® (AR 2000).

At room temperature, the plastisol is a suspension of PVC grains in the plasticizer. As the temperature is increased, the viscosity decreases. Beyond a temperature T, the plasticizer begins to diffuse in the PVC grains leading to an interpenetration thereof. This rheological phenomenon is evidenced by the measurement of the shear complex modulus (viscosity) called G * (w) as a function of temperature. The curves obtained contain all the information on the plasticizing power of the compound. The test consists in measuring, at a fixed loading frequency w = l rad / s, the variations of the complex shear modulus G * (G * (w) = G '(w) + j G "(w) where G (w) is the elastic modulus and G "(w) the viscous modulus) with temperature. The initial temperature of the test is the ambient temperature (25 ° C.) and the maximum temperature is 150 ^° C. This variation of temperature is ensured by a heating rate of 5 ° C. per minute. The rheometer measures the modulus of elasticity G 'and viscosity G "as a function of temperature T.

The gelling start temperature is determined by the first crossing of the modules G '(w) and G "(w) The gelling temperature corresponds to the temperature at the plateau reached by G' at high temperature.

These points are essential to the definition of the viscosity characteristics of plasticizers.

The reference sample prepared with DINP starts to gel at

At 80 ^° C., the gelation is around 125 ° C. with a modulus of elasticity of 3.62 × 10 ⁵ Pa. The values of the compositions 3, 4 and 6 are compared with those of the reference to determine the plasticizing characteristics. The goal is to get a curve near or better than the reference. Test B results:

The curves produced for composition 3 (FIG. 1), composition 4 (FIG. 2) and composition 6 (FIG. 3) are comparable to those of reference (FIG. 4). The composition 4 has better plasticizing characteristics than the reference.

Claims

A process for preparing a composition comprising at least one fatty acid ester of formula (I) below:

in which

R 'is a linear or branched alkyl group containing from 1 to 16 carbon atoms,

• (n + x + m) is greater than or equal to 6,

X is 1, 2 or 3,

• and (n + m) is greater than or equal to 3,

in which R ', n, x and m are as defined above, with at least one carboxylic anhydride of formula (III) below: wherein R "is as defined above, in the presence of a catalyst, said catalyst being selected from the group consisting of the following catalysts: homogeneous or heterogeneous quaternary ammoniums, heterogeneous, basic homogeneous or heterogeneous acids and mixtures thereof.

2. Method according to claim 1 characterized in that the catalyst is a quaternary ammonium salt of formula R ^ N ⁺ X ^" in which:

The groups R ¹ are groups which are identical to or different from one another, chosen from: linear or branched alkyls, substituted or unsubstituted by one or more heteroatoms, comprising from 1 to 20 carbon atoms, preferably from 1 to 16 carbon atoms, carbon, aryls, substituted or not by one or more heteroatoms, comprising from 4 to 8 carbon atoms, aralkyls, substituted or not by one or more heteroatoms, containing from 5 to 20 carbon atoms, alkylaryls, substituted or unsubstituted by one or more heteroatoms, having 5 to 20 carbon atoms, and X ^" is a contranion selected from the group consisting of carboxylates, halides, sulfates, carbonates, phosphates.

3. Process according to claim 2, characterized in that the quaternary ammonium salt catalyst corresponds to the formula R 1 N ⁺ X ^" in which: the groups R 1 are identical or different groups to each other, chosen from: o alkyls linear or branched, substituted or unsubstituted by one or more heteroatoms, comprising from 1 to 16 carbon atoms; aryls, substituted or not by one or more heteroatoms, comprising from 5 to 8 carbon atoms, • contranion X- is a halide or an acetate.

4. Method according to one of claims 1 to 3 characterized in that the compound or the mixture of compounds of formula (II) is prepared by epoxidation of a compound of formula (IV) below:

wherein R ', n, x and m are as defined in claim 1,

with a peracid,

this compound or mixture of compounds of formula (IV) being itself prepared by transesterification of a compound or a mixture of compounds of formula (V) below:

wherein n, x and m are as defined in claim 1, with an alcohol of formula R'OH in the presence of a catalyst of formula R'OM, wherein R 'is as defined in claim 1 and M is selected from alkaline and alkaline earth metals, preferably Na.

5. Method according to one of claims 1 to 3 characterized in that the compound or the mixture of compounds of formula (II) is prepared by transesterification of a compound or a mixture of compounds of formula (VI) below:

in which n, x and m are as defined in claim 1,

with an alcohol of formula R'OH in the presence of a catalyst of formula R'OM, in which R 'is as defined in claim 1 and M is chosen from alkalis and alkaline earth metals, preferably Na,

this compound or this mixture of compounds of formula (VI) being itself prepared by epoxidation of a compound or a mixture of compounds of formula (V) below:

wherein n, x and m are as defined in claim 1, with a peracid.

6. Composition characterized in that it comprises at least one fatty acid ester corresponding to the following formula (I):

in which

R 'is a linear or branched alkyl group containing from 1 to 16 carbon atoms,

• (n + x + m) is greater than or equal to 6,

X is equal to 1, 2 or 3, and (n + m) is greater than or equal to 3, and quaternary ammonium salts in the form of traces.

7. Use of a composition obtained by the process as defined in one of claims 1 to 5 or a composition as defined in claim 6, as a plasticizer for a polymer, preferably polyvinyl chloride (PVC). .

8. Plasticized polymer, preferably plasticized PVC by using a composition obtained by the process as defined in one of claims 1 to 5 or a composition as defined in claim 6.

9. A method of manufacturing a coated yarn or fabric characterized in that one sheathed a yarn or coated a fabric with a plasticized polymer, preferably a plasticized PVC as defined in claim 8.

10. Woven or non-woven fibrous substrate comprising at least one layer of plasticized polymer, preferably plasticized PVC as defined in claim 8.