WO2018029143A1

WO2018029143A1 - Method for obtaining materials, resulting materials, and uses of said materials

Info

Publication number: WO2018029143A1
Application number: PCT/EP2017/069944
Authority: WO
Inventors: France Thevenieau; Carine MANGEON; Estelle Renard; Valérie LANGLOIS
Original assignee: Avril; Centre National De La Recherche Scientifique; Université Paris-Est Créteil Val De Marne (Upec)
Priority date: 2016-08-08
Filing date: 2017-08-07
Publication date: 2018-02-15

Abstract

The invention relates to a method for repairing a material, comprising: a step of uniformly mixing at least one terpene with at least one polyunsaturated carbon compound, and a heating step in the presence of oxygen.

Description

Method of obtaining materials, materials as such and their uses

The invention relates to materials, the process for obtaining these materials and the use of these materials. In particular, the invention relates to biosourced materials.

In recent decades, the development of bio-based molecules to replace petroleum-derived compounds has been growing steadily, reducing dependence on fossil fuels and reducing the ecological impact of the industry. chemical oil.

In this context, vegetable oils have been widely studied in order to produce polymers because of their biobased nature, their ecological character and the great flexibility of their long carbon chain. However, because of their aliphatic structure, polymers derived from vegetable oils have limited themomechanical properties.

Terpenes are biobased chemical compounds that enhance the structure of materials. Terpenes represent a wide range of abundant and affordable hydrocarbons that do not interfere with agricultural resources. Raw or purified, terpenes are generally used as perfumes or fragrances. Terpenes are also very good solvents and a thinner for stains and varnishes.

Although terpenes are involved in many catalytic processes, only a few have been studied for their use in polymer synthesis.

The invention therefore aims to provide a method for synthesizing novel biobased polymers having mechanical and thermal properties suitable for many uses.

Another object of the invention is to provide materials obtained by this method. Yet another object of the invention is to provide uses, whether medical or not, of biobased materials obtained.

Also, the invention relates to a method for preparing an elastic and flexible crosslinked material, comprising:

a uniform mixing step

at least one terpene comprising at least two conjugated double bonds and a composition comprising at least one polyunsaturated carbon compound comprising at least one carbon chain comprising at least 5 carbon atoms, or

at least one terpene and a composition comprising at least one compound polyunsaturated carbon comprising at least one carbon chain comprising at least 5 carbon atoms, said at least one carbon chain comprising at least two conjugated double bonds

said at least one terpene and said composition being mixed in proportions ranging from 40:60 to 60:40, especially 50:50, and

a heating step at a temperature ranging from 85 ° C to 185 ° C in the presence of oxygen for at least 20 hours.

The invention is based on the surprising finding made by the inventors that in the presence of oxygen, a mixture of oil and terpene can, after heating, give an elastic and flexible material, without the need to use solvent or catalyst. The reaction, as detailed in the examples, involves both Diels-helper reactions (involving conjugated double bonds and oxidation reactions.) These two types of reaction concurrently contribute to the formation of lattices. aforementioned properties of flexibility and elasticity.

By "elastic" material is meant in the invention a material that can temporarily deform under the action of a force and then return to its original form at rest.

By "flexible" material is meant in the invention a material that can bend or bend easily, which has a certain flexibility.

By "polyunsaturated carbon compound comprising at least one carbon chain" is meant in the invention a chemical compound having at least two unsaturation, that is to say at least two C = C double bonds. These double bonds are called conjugated, that is to say that the molecule consists of atoms linked by covalent bonds with at least one delocalized π bond. In other words, two double bonds are called conjugate if in the same molecule they are separated by a single bond.

The carbon compound, which essentially comprises carbon and hydrogen atoms, but which may comprise O, N, halogen atoms, comprises at least one unsaturated carbon chain.

This means that the compound can be linear (it therefore includes a carbon chain), but also cyclic. Preferably, if it is cyclic, it comprises at least one unsaturated linear portion or radical.

Compounds corresponding to this definition are polyunsaturated hydrocarbons having at least 5 carbon atoms, polyunsaturated carboxylic acids having at least 5 carbon atoms, polyunsaturated fatty acids, or any hydrocarbon having at least 5 carbon atoms and which may exhibit or several functions ether, alcohol, acid, amine, amide, ketone, or other. In addition, the compounds may be carboxylic acid ethers, such as monoacyl glycerol, diacyl glycerol or polyunsaturated triacyl glycerol.

The preferred compounds are polyisoprene or polyunsaturated fatty acids, especially polyunsaturated C10-C25 fatty acids, or the corresponding monoacyl, diacyl or triacyl glycerol.

The polyunsaturated fatty acids C10-C25 are fatty acids comprising a carbon chain comprising 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms. carbon, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, 20 carbon atoms, 21 carbon atoms, 22 carbon atoms, 23 carbon atoms, 24 carbon atoms or 25 carbon atoms.

In the particular case of diacyl glycerol or triacyl glycerol, which have respectively two or three fatty acids, the compound will be said to be polyunsaturated if one of the fatty acids has at least two conjugated unsaturations, the other fatty acid (s) possibly having no unsaturation C = C. Of course, if one, two or, where appropriate, three of the fatty acids have at least two conjugated double bonds, these compounds will be particularly advantageous.

As is shown in the examples, the particular proportions of terpene and said composition are essential for imparting beneficial physicochemical properties to the reaction product.

The proportion of terpene of composition varies from 40:60 to 60:40, which means that 40% by weight of the terpene reaction mixture is added 60% by weight of the composition (40:60), or 60% by weight of the composition. % by weight of the terpene reaction mixture is added 40% by weight of the composition (60:40).

The proportions covered by the invention are thus as follows:

Terpene (%) Composition (%) Ratio

40 60 40: 60

41 59 41: 59

42 58 42: 58

43 57 43: 57

44 56 44: 56

45 55 45: 55

46 54 46: 54

47 53 47: 53

48 52 48: 52

49 51 49: 51 Terpene (%) Composition (%) Ratio

50 50 50: 50

51 49 51: 49

52 48 52: 48

53 47 53: 47

54 46 54: 46

55 45 55: 45

56 44 56: 44

57 43 57: 43

58 42 58: 42

59 41 59: 41

60 40 60: 40

To achieve the crosslinking between the terpene and the aforementioned composition the reaction takes place in the presence of oxygen. Advantageously, the atmosphere comprising oxygen is an oxygen-enriched or oxygen-enriched atmosphere. In this atmosphere, the oxygen present is advantageously in the form of dioxygen. Even more advantageously, the oxygen-containing atmosphere is ambient air or is an atmosphere comprising an amount of oxygen at least equal to that present in the ambient air (ie about 20% of the gas volume).

The reaction is carried out by heating the terpene / composition mixture at a temperature ranging from 85 ° C to 185 ° C, i.e. at a temperature of 85 ° C, 86 ° C, 87 ° C, 88 ° C 89 ° C, 90 ° C, 91 ° C, 92 ° C, 93 ° C, 94 ° C, 95 ° C, 96 ° C, 97 ° C, 98 ° C, 99 ° C, 100 ° C, 101 ° C ° C, 102 ° C, 103 ° C, 104 ° C, 105 ° C, 106 ° C, 107 ° C, 108 ° C, 109 ° C, 110 ° C, 111 ° C, 112 ° C, 113 ° C 114 ° C., 115 ° C., 116 ° C., 117 ° C., 118 ° C., 119 ° C., 120 ° C., 121 ° C., 122 ° C., 123 ° C., 124 ° C., 125 ° C. C, 127 ° C, 128 ° C, 129 ° C, 130 ° C, 131 ° C, 132 ° C, 133 ° C, 134 ° C, 135 ° C, 136 ° C, 137 ° C, 138 ° C 139 ° C, 140 ° C, 141 ° C, 142 ° C, 143 ° C, 144 ° C, 145 ° C, 146 ° C, 147 ° C, 148 ° C, 149 ° C, 150 ° C, 151 ° C. C, 152 ° C, 153 ° C, 154 ° C, 155 ° C, 156 ° C, 157 ° C, 158 ° C, 159 ° C, 160 ° C, 161 ° C, 162 ° C, 163 ° C 164 ° C, 165 ° C, 166 ° C, 167 ° C, 168 ° C, 169 ° C, 170 ° C, 171 ° C, 172 ° C, 173 ° C, 174 ° C, 175 ° C, 176 ° C. ° C, 177 ° C, 178 ° C, 179 ° C, 180 ° C, 181 ° C, 182 ° C, 183 ° C, 184 ° C or 185 ° C.

It is particularly advantageous to carry out the reaction at about 100 ° C for at least 38 hours.

Advantageously, the invention relates to the aforementioned method comprising a step of uniform mixing of at least one terpene comprising at least two double conjugated bonds and a composition comprising at least one polyunsaturated carbon compound comprising at least one carbon chain comprising at least 5 carbon atoms.

In this configuration, the conjugated double bonds of terpene will be capable of forming a ring with a double bond composition comprising at least one polyunsaturated carbon compound, by a Diels Aid reaction.

Advantageously, the invention relates to the aforementioned method comprising a step of uniform mixing of at least one terpene and a composition comprising at least one polyunsaturated carbon compound comprising at least one carbon chain comprising at least 5 carbon atoms, said at least one chain carbon containing at least two conjugated double bonds.

In this configuration, the conjugated double bonds the composition comprising at least one polyunsaturated carbon compound will be capable of forming a ring with a double bond of terpene, by a Diels Aid reaction.

Even more advantageously, the invention relates to the process as defined above, in which said terpene is chosen from farnesene, β-myrcene, ocimene and myrcenol, or else vitamin A, the formulas of which are the following: farnesene -farnesene

oocimene

These terpenes all have conjugated double bonds, and may form a ring with a double bond of another molecule by the Diels Aider reaction.

Even more advantageously, the invention relates to the process as defined above, said composition comprising at least one compound is a composition comprising or consisting of one or more vegetable oils, in particular a vegetable oil such as rapeseed oil, oleic rapeseed oil, sunflower oil, especially a rapeseed oil or a sunflower oil, or a mixture thereof. In the invention, vegetable oil is understood to mean a fatty substance extracted from an oleaginous plant. The term "oleaginous plant" means any plant whose seeds, nuts or fruits contain lipids or fatty acids.

A fatty substance is a substance composed of molecules with hydrophobic properties. Fatty substances are mainly composed of fatty acids and triglycerides which are esters consisting of a molecule of glycerol and three fatty acids. The other components form what is called unsaponifiable.

The extraction of vegetable oil by traditional methods often requires various preliminary operations, such as dehulling. After these operations, the crop is ground into a paste. The dough, or sometimes the whole fruit, is boiled in the presence of water and stirring until the oil is separated. These traditional methods have a low efficiency rate.

Modern methods of oil recovery include breaking and pressing steps, as well as dissolving in a solvent, most commonly hexane. Extraction of the oil with a solvent is a more efficient method than pressing. The residue left after extraction of the oil (cake or flour) is used as animal feed.

Crude vegetable oils are obtained without additional treatment other than degumming or filtration. To make them fit for human consumption, edible vegetable oils are refined to remove impurities and toxic substances, a process involving bleaching, deodorization and cooling. The oils contemplated in the plant invention include crude, refined or fractionated oils or by-products derived from the extraction of oils.

With few exceptions, and unlike animal fats, oils Vegetables contain predominantly unsaturated fatty acids of two kinds: monounsaturated (such as palmitic acid, oleic acid or erucic acid) and polyunsaturated (such as linoleic acid).

Even more advantageously, the invention relates to the process as defined above, said composition comprising at least one compound is a composition comprising or consisting of one or more oils comprising at least one of the following fatty acids: rumenic acid, parinaric acid, eleostearic acid, punicic acid, calendrical acid or conjugated linoleic acids, the formulas of which are as follows:

Rumenic acid

rinarique

Β-Eleostearic acid

the calendar acid

Rumenic acid ((9Z, 11E) -octadeca-9, 11-dienoic acid) is a conjugated linoleic acid found especially in dairy products.

The parinaric acid (octadeca-9, 11, 13,15-tetraenoic acid) is found in Atuna seeds, whose main constituents are 46% α-parinaric acid and 34% α-parinaric acid. eléostéarique, and in garden balsamines, where it accounts for more than 29% of fatty acids.

The α-eleostearic acid, in addition to the Atuna seeds (see above), is found in tung oil (where it accounts for 80% of the fatty acids) and the bitter oil (where it accounts for 60% fatty acids).

Punic acid (acid (9Z, 11E, 13Z) -octadeca-9, 11, 13-trienoic) is found mainly in pomegranate seeds and gourd seeds.

The calendrical acid (acid (8E, 10E, 12Z) -octadeca-8, 10, 12-trienoic) is found in the marigolds, of the genus Calendula.

In one advantageous embodiment, the invention relates to the process as defined above, in which the said at least one terpene is chosen from farnesene or β-myrcene and the said composition comprising at least one polyunsaturated carbon compound is a rapeseed oil. or sunflower.

Also, it is particularly advantageous in the invention to implement the above-mentioned method by mixing:

- farnesene with sunflower or rapeseed oil, or

- β-myrcene with sunflower or rapeseed oil.

Of course, oil mixtures (rapeseed and sunflower) can also be considered. It is the same for mixtures of farnesene and myrcene.

The invention also relates to a resilient and flexible crosslinked material, in particular in the form of an elastic and flexible film, obtainable by the method as defined above. Advantageously, the invention relates to a resilient and flexible crosslinked material, in particular in the form of an elastic and flexible film, consisting essentially of a network of fatty acids on which are grafted at the level of unsaturations, terpenes, the proportion of terpene and fatty acid ranging from 40:60 to 60:40.

The elastic material according to the invention is characterized in particular by a glass transition temperature ranging from 20 to 75 ° C, preferably from 20 to 65 ° C.

In the advantageous case where the material according to the invention essentially consists of myrcene and sunflower oil, in a proportion ranging from 40: 60 to 60: 40, this material has a glass transition temperature ranging from 25 to 65 ° C. C, especially from 30 ° C to 65 ° C. Advantageously, a material consisting essentially of 50% myrcene and 50% sunflower oil has a glass transition temperature of about 45 ° C.

In the advantageous case where the material according to the invention consists essentially of farnesene and sunflower oil, in a proportion ranging from 40: 60 to 60: 40, this material has a glass transition temperature ranging from 20 to 40 ° C. C, especially from 20 ° C to 35 ° C. Advantageously, a material consisting essentially of 50% myrcene and 50% sunflower oil has a glass transition temperature of about 22 to about 29 ° C.

The elastic material according to the invention is furthermore characterized in particular by the following physicochemical properties:

an average number of crosslinks per unit volume of 105 to 125 mol / m ³ , especially for materials containing myrcene, and / or

a storage module of 0.85 to 1.2 MPa.

The invention also relates to the use of a material as defined above, for the preparation of biodegradable and / or compostable food containers, packaging, coatings, in particular surface coatings, for the preparation of parts. injected or manufactured by extrusion or for the preparation of surface coatings, in particular for the manufacture of interior coatings for vehicles, or for its use as a material for the release of active principles of a medicament or additive in animal nutrition .

In particular, the invention relates to a material mentioned above for the controlled release of an active molecule or a drug in an animal, in particular man.

The advantage of such a material is that it is able to retain a therapeutically effective compound and restore it gradually during therapy. Because of its composition (oil and terpene) this compound is particularly suitable for use in human therapy, because it presents only very few risks to health. The material according to the invention is advantageously useful for the delivery of active compounds, in particular hydrophobic compounds, such as anticancer, anti-inflammatory, anti-emetic, antihypertensive agents, sex hormones and steroids, or essential oils and their active compounds. More specific examples are:

for anticancer agents: paclitaxel, docetaxel, camptothecin, doxorubicin, daunomycin, cisplatin, 5-fluorouracil, mitomycin, methotrexate, and etoposide;

for the anti-inflammatory agents: indomethacin, ibuprofen, ketoprofen, flubiprofen, dichlofenac, piroxicam, tenoxicam, naproxen, acetyl salicylic acid and acetaminophen;

- for the anti fungal agents: itraconazole, ketoconazole and amphotericin,

- for the sex hormones: testosterone, estrogen, progesterone, and estradiol;

for the steroid hormones dexamethasone, prednisolone, betamethasone, triamcinolone acetonide and hydrocortisone,

for antihypertensive agents: captopril, ramipril, terazosin, minoxidil, and parazosin,

- for antiemetics: ondansetron and granisetron,

- for antibiotics: metronidazole and fusidic acid, cyclosporins, prostaglandins; and biphenyl dimethyl dicarboxylic acid.

Also, one aspect of the invention relates to a medicament comprising an active ingredient contained in an envelope, the envelope being of a material as defined above.

Another aspect relates to a method of treating a condition comprising administering to a needy individual a drug contained in a material as defined above for controlled or continuous administration.

The invention furthermore relates to a material as defined above, as a pharmaceutical agent for the preparation of a medicament capable of being administered continuously in an animal or an individual.

The invention also relates to a material as defined above, for its use in human or animal surgery.

As mentioned above, because of its composition, the material can easily be used for the preparation of prosthetic coating, subcutaneous implants or to place in the peritoneal cavity to distribute over a long period of time, so continuous, a drug or a pharmaceutical composition, or a mixture of drugs.

The invention will be better understood in the light of the following figures and examples LEGEND OF FIGURES

Figure 1 represents a graph showing a Raman spectrum (deviation in cm ^-1 ) of β-myrcene (M100; A) and polymyrcenes (PM100) with (B) and without (C) O2 after 140h reaction at 100 °. C. The characteristic peaks are indicated by arrows Figure 2 is a graph showing the conversion of the double bonds of myrcene during the reaction at 100 ° C. The abscissa represents the time in hours and the axis of the ordered the conversion percentage.

Figure 3 is a graph showing the conversion of double bonds of myrcene (A) and polymyrene (B after 3h) during the reaction at 100 ° C. The axis represents the wave number in cm ^"1 .

4 shows a graph showing a Raman spectrum (deviation in cm ^-1 ) of the material S 50 M 50 at the beginning of the reaction (A, R = 0.18), after 140 h of reaction at 100 ° C. in the presence of 0 ₂ (B, R = 0.40) and after 140h of reaction at 100 ° C in the presence of 0 ₂ (C, R = 0.17).

FIG. 5 represents a Fourier transform infrared spectrum (FT IR) of the S50M50 polymers before the reaction (A), 68h after the start of the reaction at 100 ° C. in the presence of oxygen (B) and 48h after the beginning of the reaction. the reaction at 100 ° C in the absence of oxygen (B)

Figure 6 is a graph showing mass loss versus time curves for different materials PS100, PM100 and S50M50. The x-axis represents the temperature in ° C and the y-axis represents the mass loss in percent.

Figures 7A and 7B show the evolution of thermomechanical properties of materials PS100, SeoM ₂ o, SeolVUo, S50M50 and S20M80.

FIG. 7A represents the evolution as a function of the temperature (in ° C.) of the Tanô damping factor.

FIG. 7B represents the evolution as a function of the temperature (in ° C.) of the conservation module E '.

Figure 8 shows graphs showing different mechanical properties of the materials S20M80, S30M70, S40M60, S50M50 and S60M40: A: Young's modulus in MPa, B: the tensile strength in MPa and C: elongation at break in% .

Figure 9 is a graph showing the conversion of the double bonds of farnesene (A) and polyfarnesene (B after 72 hours) during the reaction at 100 ° C. The axis represents the wave number in cm ^"1 .

Figures 10A to D show photographs showing the macroscopic properties of the different materials.

Figure 10A is a photograph showing the brittle appearance of a F100 material (100% farnesene).

Figure 10B is a photograph showing the flexibility of a material S50F50 (50% oil - 50% farnesene).

Figure 10C is a photograph showing the elasticity of a S50F50 material (50% oil - 50% farnesene).

Figure 10D is a photograph showing the tearable appearance of a S100 material (100% oil).

11 shows a graph showing a Raman spectrum (deviation in cm ^-1 ) of the material F 50 M 50 at the beginning of the reaction (A), after 192 h of reaction at 100 ° C in the presence of O (B) and after 192 h of reaction at 100 ° C in the presence of C> 2 (C).

Figures 12A and 12B show the evolution of thermomechanical properties of materials PS100, S80F20, S70F30 and S50F50.

FIG. 12A represents the change as a function of the temperature (in ° C.) of the conservation module E '.

FIG. 12B represents the evolution as a function of the temperature (in ° C.) of the Tanô damping factor.

Figure 13 is a graph showing the rate of swelling (q; ordinates) of S50F50 material in eugenol over time (in hours).

Figure 14 is a graph showing the release of eugenol in water (in mg / L, ordinate) of the S50F50 material over time (in hours).

Figures 15A to D show photographs showing the macroscopic properties of the different materials.

Figure 15A is a photograph showing the brittle appearance of an M100 material (100% myrcene).

Figure 15B is a photograph showing the flexibility of a S50M50 material (50% oil - 50% myrcene).

Figure 15C is a photograph showing the elasticity of a S50M50 material (50% oil - 50% myrcene).

Figure 15D is a photograph showing the tearable appearance of a S100 material (100% oil).

Figure 16 is a graph showing the swelling rate (q; ordinates) of material S50F50 (curve with triangles) and material S50M50 (diamond curve) in eugenol over time (in hours). EXAMPLES

EXAMPLE 1 Example of Material Composed of Myrcene and Sunflower Oil

In recent decades, the development of bio-based molecules to replace petroleum products have continued to increase.

In this ecological context, vegetable oils have been intensively studied in order to synthesize polymers because of their renewable nature. However, because of the great flexibility of the fatty acid alkyl chains, the vegetable oil-based polymers have reduced thermomechanical properties.

In order to overcome these drawbacks, the inventors have proposed to prepare more "ecological" networks by taking advantage of the Diels Aider reaction, in the absence of catalyst and solvent.

Myrcene and sunflower oil have been used without further chemical modifications. The inventors thus obtained and described a new class of materials in the form of a network, and the optimal proportions of each of the components was evaluated by the inventors.

Materials and methods

products

Myrcene was obtained from Sigma-Aldricht and was used without further purification. Sunflower oil was graciously supplied by Lesieur (Coudekerque, France), and used as is. The sunflower oil comprises palmitic acid (6.25%, stearic acid (3.89%), oleic acid (25.62%) and linoleic acid (62.71%). ).

Synthesis of the oil and myrcene network SxM100-x

Sunflower oil and myrcene are mixed uniformly with different bulk ratios at room temperature with a magnetic stirrer to obtain a homogeneous solution.

A network obtained with 0.5 grams of myrcene and 0.5 g of oil will be noted S50M50. After stirring, the mixture was placed in a silicone mold (5 x 2.5 cm) to form a film of constant thickness and the solution was cured in an oven at 100 ° C for varying times.

Equipment

¹ H spectra were recorded using a BRUKER AVANCE II NMR Spectrophotometer at 400 MHz. Peak solvent (Chloroform, 7.26ppm) was used as a reference. The FTIR spectra were obtained using a Bucker TENSOR 27 (Digi Tect DLATGS detector, 32 scans, 4 cm ^-1 ) in the range of 500 to 4000 cm ^-1 . Raman's investigative spectrometry was performed using a LabRam HR spectrophotometer from Horiba Jobin Yvon (Lonjumeau France) equipped with a laser emitting at 633 nm. The thermal and decomposition characteristics of the materials were determined by thermal gravimetric analysis (TGA) using a Setaram Setsys Evolution 16 device, at a temperature ranging from 20 to 800 ° C with a heating level of 10. ° C per minute under a flow of air at 20mL / min. The Mechanical properties were implemented in an Instrom 5965 universal test machine with a displacement rate of 2mm / min at room temperature (23 ° C ± 2 ° C). Dynamic, mechanical and thermal (MDTA) analyzes were performed with a Texas Instruments DMA Q800 at a frequency of 1 Hz in a traction configuration.

Results

Polymyrene synthesis PM100

Firstly, polymyrene PM100 was prepared by Diels Aider reaction at 100 ° C without solvent or catalyst. In order to test the effect of time on the polymyrene structure, the reaction was studied at different times, from 0 to 140h. Figure 1 shows the Raman spectrum of the monomer, myrcene M100 and polymyrene PM100.

Asymmetric bands -CH2 and -CH3 appear as broad bands at 2915 cm ^-1 . The chemical structure of PM100 was confirmed with the disappearance of the band at 3011 cm ^-1 , corresponding to the aliphatic band = CH of C1, C3 and C4 (spectrum not shown) .The Raman bands at 1635 and 1670 cm ^-1 are characteristics of the conjugates C1 = C2 and C3 = C4, and unsaturated C7 = C8 insuptions of M 100. After three hours of reaction at 100 ° C, a new band at 1656 cm- ¹ appeared, this band being characteristic of the presence of unsaturated groups in a cycle attesting to the reaction of Diels Aider. In the same period, the inventors observed the decrease in the C1 = C2 and C3 = C4 bands. Figure 2 shows the conversion of double bonds at the beginning of the reaction. The conversion was calculated by the band intensity ratio of the unsaturated groups and the band at 1433 cm ^-1 , the intensity of which remains constant during the reaction.

The content of C7 = C8 seems to be constant because of the low reactivity of this type of unsaturation. On the contrary, there is a rapid decrease in the proportion of conjugated double bonds C1 = C2 and C3 = C4, and at the same time an increase of C2 '= C3' which corresponds to the appearance of unsaturation in the cycle. Hexatomic formed during the reaction of Diels Help.

After 24h reaction in the presence of oxygen, a wide band at 1713 cm ^-1 , characteristic of oxidation products appears when it was not present in the context of the same reaction in the absence of oxygen. Due to the different sensitivity between FTIR and Raman spectrometry, the oxidized groups are easily detectable at 3400, 1713 and 1050 cm- ¹ after 3 hours reaction in the form of broad and intense absorption bands (Figure 3). Also, the PM100 polymyrene formation obtained at 100 ° C. is due to two main reactions which are, respectively, Diels Aider reactions, as evidenced by Raman spectroscopy, and reactions. simultaneous crosslinking due to the presence of oxygen capable of reacting with unsaturated groups, as evidenced by FTIR spectroscopy.

Preparation of networks composed of sunflower oil and myrcene SxM100-x

Networks were prepared using different proportions of myrcene, from 20 to 80% by weight in order to evaluate the importance of the incorporation of vegetable oil on the properties of the networks, in particular the mechanical properties.

On the one hand, sunflower oil comprises at least 1.5 unsaturated groups capable of increasing the crosslinking density by reaction of Diels Aider with myrcene, but on the other hand this eight contains fatty acids having long carbon chains. which increases the flexibility of the system. The Raman spectrum of an S50M50 array is shown in FIG. 4. The 1655 and 1740 cm-1 bands correspond to the double bond and the ester group of sunflower oil while the bands at 1635 and 1670 cm -1 are representative. myrcene. As a result, the spectrum of the S50M50 network clearly shows the different unsaturated groups of myrcene and sunflower oil with distinct Raman displacements. The intensities of these bands changed during the reaction and the reaction proportions were estimated by determining a R value defined by the ratio of the intensity of the band at 1740 cm ^-1 and 1433 cm ^-1 . The R values range from 0.18 (due to the presence of a 1740 cm-1 band characteristic of the ester group of the oil) to 0.40 after 140 hours of reaction in the presence of oxygen. The increase in the ratio showed the importance of the formation of oxidized products. In the absence of oxygen, the R ratio (1.80) is constant throughout the reaction, up to 140 hours. The inventors have been able to estimate the importance of the presence of oxygen during the formation of the network and the formation of the oxidized products. By FTIR, the bands at 891, 1594 and 3093 cm ^-1 , characteristic of the double bonds, decrease with or without oxygen. Large and intense bands appear after 3 hours of reaction at 3400 and 1194 cm ^-1 . These bands are characteristic of the oxidation products and are not observed when the reaction is carried out in the absence of oxygen (see FIG. 5). Although the presence of oxygen leads to side reactions other than the Diels Aider reaction, it turns out that the films obtained are very smooth, of homogeneous appearance and have interesting characteristics of flexibility.

Need for Diels-Alder reactions to obtain materials

To verify the necessity of the Diels-Alder reactions to obtain the materials according to the invention, the inventors carried out tests using mixtures of sunflower oil and compounds not comprising conjugated double bonds:

- limonene of the following formula

to obtain a material S50L50,

- geraniol of following formula

to obtain a SsoGso-

Limonene and geraniol are not capable of initiating Diels-Alder reactions in the presence of sunflower oil (the fatty acids of which do not have conjugated double bonds). The reactions were conducted under the conditions mentioned above.

The materials S50L50 and S50G50 are substantially identical to the S100 materials, that is to say, soft and easily tearable.

This demonstrates the need for Diels-Alder reactions to impart elastic properties to the materials of the invention.

Studies of the rheological and mechanical properties of synthesized networks SxM100-x

The stability of sunflower oil PS100, myrcene PM100 and S50M50 network was studied by TGA thermal gravimetric analyzes (FIG. 6). S50M50 has three-stage degradation characteristics, with a first stage occurring between 200 and 350 ° C, followed by a step between 375 and 450 ° C and a third step of 450 to 500 ° C. The initial thermal decomposition (5% weight loss) occurs above 300 ° C demonstrating that the network has moderate thermal stability.

Characterizations of the mechanical dynamics of the cured networks were performed using DMA type analyzes. DMA thermograms for cured systems containing 0% to 80% myrcene are shown in Figures 7A and 7B. The conservation modulus E 'is correlated with the molecular packing density due to a better settlement of the chain fragments. The highest value of E 'at 25 ° C is 1000 MPa, obtained with 80% by weight of myrcene. This value is significantly decreased (3 MPa) when the sunflower oil content is about 80%. This is correlated with the free movement of polymer chains in networks that contain more vegetable oil and are therefore not less crosslinked. The tanô curve shows a maximum that is attributed to be the Tg of hardened networks. Each network has a simple Tg, which shows that all systems are compatible and homogeneous, except the S20M80 network which seems less defined. The data clearly show a decrease in the Tg of the cured networks correlated with the increase in the amount of sunflower oil in the formulation. The highest value, 92.3 ° C, is obtained for the S20M80 network whereas a decrease in Tg is observed for the SeolVbo network which reaches 19.8 ° C. Flexibility is attributable to the introduction of vegetable oil units into the network. However, the curves show a wide region of glass transition temperature for all materials. This behavior is characteristic of thermosetting materials derived from vegetable oils, because of the plasticizing effect of the fatty acid chains. According to rubber elasticity theory, equation (1) was used to describe the relationship between Me (mean molecular weight of a segment between crosslinking points) and ve (the crosslinking density in mol cm ^-3 ) with the storage modulus (Ε ') of rubber-coated thermosetters:

Me = 3dRT / E '= d / ve

where E ', d, R and T are respectively the storage modulus (MPa) at a Tg of + 30 ° C, the density of the network (0.99 g cm ^-3 ), the gas constant (8.314 J. Mo K ^"1 ), and the temperature (K) The crosslinking densities, ve (average number of crosslinks per unit volume) were calculated for different concentrations of myrcene.

^S 100 13.8 0.37 46.8

^S 80 ^M 20 19.8 0.61 75.7

^S 60 ^M 40 30.5 0.91 109.4

^S 50 ^M 50 46.7 0.96 1 10, 1

S ₅₀ M ₅₀ (96h) 62, 1 1, 08 1 17.7

^S 20 ^M 80 92.3 1, 45147, 1

Table 1 shows the thermal and mechanical properties of the S _x Mi ₀ ox gratings

The value of E 'at + 30 ° C was taken to ensure that the networks were in a rubbery state. PS100 material composed only of vegetable oil has the highest average molar mass of segments between the crosslinking points, MC, since the resulting network is only formed by the crosslinking reactions in the presence of oxygen. It is clear that the crosslinking densities increase with myctene content from 46.8 to 174.1 mol. m ^-3 . In theory, myrcene has three reactive double bonds capable of reacting in Diels Aider reactions and crosslinking reactions. Although the molar masses between the crosslinking points decrease by 21141 g. mol ^"1 for SeolVbo at 6732 g, mol ^{" 1} for S20M80, these values are always greater than the molar mass of myrcene and spin-on oil. Therefore, it is possible to consider that not all double bonds are engaged in one of these reactions but that the resulting gratings have the ability to form films easily except for the PM100 polymers. This material is too fragile to form homogeneous films and to measure its mechanical properties by DMA. This increase in cross-linking is simultaneously correlated with the decrease in Me and the increase in Tg. The Tg reaches 92.3 ° C when the myrcene content is about 80%. As a result, the myrcene unit is smaller than that of fatty acid, which decreases the distance of the crosslinks. In contrast, fatty acid units contain more flexible aliphatic chains and a greater amount of free volume.

Figure 8 shows the elastic properties of the different networks. Although the mechanical performance of the S20M80 network with a high tensile modulus (97 MPa) and a high tensile strength (8.8 MPa) is very interesting, this material shows significant fragility.

So, the S50M50 network is the most promising material combining good mechanical properties and remarkable flexibility. In comparison, the properties of this material are totally different from those obtained by crosslinking by UV irradiation of modified myrcene and tung oil because of the lower crosslinking density obtained with the process according to the invention compared to the polymerization initiated. by the UV. The networks obtained according to the invention are surprisingly homogeneous and flexible and have a high elongation at break up to 108%, whereas this elongation at break does not exceed 11% in the systems obtained by radiation crosslinking. UV.

conclusions

The networks obtained from myrcene and sunflower oil have been successfully obtained in an environmentally friendly catalytic process using a green chemical process using neither solvent nor catalyst. The presence of oxidation reactions is also responsible for the formation of the lattice as has been demonstrated with Raman and FTIR spectroscopies. The materials obtained are very homogeneous and this method makes it possible to obtain a wide variety of networks having glass transition temperatures ranging from 19.8 to 92.3 ° C. The use of myrcene which is a terpene containing three double bonds and sunflower oil is a very good strategy for developing networks without catalyst or solvent. To reinforce the mechanical properties of these networks it is necessary to carry out additional studies, in particular concerning the incorporation of lignin which is an attractive raw material which would give a significant added value to this material. However, lignin has the ability to act as a stabilizer and antioxidant because of its similar structure to hindered phenols preventing the thermo-oxidative aging of these materials during their use.

Example 2 Example of Material Composed of Farnesene and Sunflower Oil

In a second series of experiments, the inventors manufactured materials from farnesene and sunflower oil under the experimental conditions described in Example 1.

Polyfarnesene PF100 was prepared by a Diels Aider reaction at 100 ° C without solvent or catalyst.

After 24 hours of reaction in the presence of oxygen, a broad band at 1713 cm ^-1 , characteristic of the oxidation products. The reaction of farnesene on itself at 100 ° C leads to the reduction of double bonds and the appearance of oxidized products (FIG. 9):

Wide OH band at 3429 cm ^"1

Band C = 0 to 1711 cm ^-1

COC band at 1039 cm ^"1 .

The appearance of the different materials tested is shown in FIGS. 10A to D.

The Raman spectra of the S50F50 material before the reaction after 192 hours of reaction at 100 ° C with or without O2 are shown in Figure 11.

The bands present at 1585, 1632 and 1667 cm ^-1 are characteristic of the double bonds of farnesene, while the band at 1655 cm ^-1 is characteristic of the double bonds present in sunflower oil.

The double bonds decrease after 192 hours of reaction in the absence of oxygen, which makes it possible to affirm that a Diels-Alder reaction occurs.

In the presence of oxygen, this decrease is much more marked.

The formation of a film is therefore the combination between Diels-Alder reactions (thanks to the presence of conjugated double bonds of farnesene and the double bonds of the oils) as well as oxidation reactions in the presence of oxygen.

In the absence of oxygen, the inventors obtained a very viscous gel. A movie is not obtained only in the presence of oxygen. The oxygen of the air is therefore essential to form the material

Characterizations of the mechanical dynamics of cured networks comprising farnesene were performed using DMA type analyzes. DMA thermograms for cured systems containing 0% to 80% farnesene are shown in Figures 12A and 12B. The conservation modulus E 'is correlated with the molecular packing density due to a better settlement of the chain fragments. E 'increase with the amount of farnesene in the material. The tanô curve shows a maximum that is attributed to be the Tg of hardened networks. Each network has a simple Tg, which shows that all systems are compatible and homogeneous.

The glass transition temperatures obtained are as follows:

Tg (° C)

Like the materials comprising myrcene, the networks obtained from farnesene and sunflower oil have been successfully obtained using an environmentally friendly catalytic process using a green chemical process using neither solvent nor catalyst.

Example 3 Use of a Material According to the Invention

In order to test the properties of the materials obtained, the inventors evaluated properties of the S50F50 materials.

In a first approach, the inventors tested the swelling capacity of the materials. The results are shown in Figure 13.

The degree of swelling q (q = [(weight of the inflated network - initial mass) / mass of the inflated network] x 100) measured over time shows that the material swells significantly in apolar solvents as well as in terpenes such as than eugenol. The material is capable of trapping up to 250% of its mass in eugenol.

In a second step, exploiting the properties of eugenol (inhibition of bacterial growth in E. coli and S. aureus at a minimum concentration of 900 mg / L), the inventors tested the release of eugenol and previously tested in swelling tests.

Films (0.2 g) were immersed in 5 ml of eugenol solution in water (6 g). mg / mL) for 30min. Absorption (mass change) after 30 min was 8%.

Then the film's ability to release eugenol in water was monitored over a period of 720h (1 month) at room temperature. The release rate was analyzed by gas chromatography (GC) (Figure 14).

The starting material (F50S50) contains trapped eugenol (Amasse = 8%). After 720h, the material released up to almost 1000mg / L of eugenol.

These results show that the materials of the invention can be used as a reservoir or as a material for the release of active principles, in particular medicinal active principles.

Example 3 Comparison of Swelling Properties of Materials S50M50 and SsoFso-

According to Flory's theory of swelling, the swelling of a material is related to: i) elasticity, ii) affinity for the solution, and iii) crosslinking density. For this purpose, the inventors have tested the swelling of the materials S50M50 and SsoFso. Since these networks consist of hydrophobic compounds, swelling in the presence of organic compounds is expected. Essential oils are an important source of mono-aromatic compounds covering a broad spectrum of chemical structures. Among them, eugenol, extracted from clove oil, of the following formula:

is an interesting and easily available phenolic compound.

The biological properties of eugenol due to its phenol group have been used for a very long time to make dental resins or to increase the antibacterial properties of biopolymers.

The incorporation of eugenol in S50M50 and S50F50 films according to the invention at room temperature has been tested by the inventors in order to prepare new biopolymers having antibacterial properties or to have a material capable of delivering the eugenol.

The diffusion rate of eugenol in the film depends on the nature of the terpene as indicated by the results in Figure 16.

The swelling rate is very fast for materials comprising farnesene, about 120% by weight in two hours, while it is only 25% by weight at the same time for the compounds comprising myrcene. These The results are explained by the structure of the polymers: the crosslinking points are 17074 g. mol ^"1 for the S50M50 whereas it is only 8994 g. mol ^{" 1} for the

The invention is not limited to the embodiments presented and other embodiments will become apparent to those skilled in the art.

Claims

claims

A process for preparing an elastic and flexible crosslinked material, comprising:

a uniform mixing step

at least one terpene comprising at least two conjugated double bonds and a composition comprising at least one polyunsaturated carbon compound comprising at least one carbon chain comprising at least 5 carbon atoms, or at least one terpene and a composition comprising at least one polyunsaturated carbon compound comprising at least one carbon chain comprising at least 5 carbon atoms, said at least one carbon chain comprising at least two conjugated double bonds

said at least one terpene and said composition being mixed in proportions ranging from 40:60 to 60:40, especially 50:50, a heating step at a temperature ranging from 85 ° C to 185 ° C in the presence of oxygen during at least 20 hours.

Process according to claim 1, comprising a step of uniform mixing of at least one terpene comprising at least two conjugated double bonds and a composition comprising at least one polyunsaturated carbon compound comprising at least one carbon chain comprising at least 5 carbon atoms.

Process according to claim 1, comprising a step of uniform mixing of at least one terpene and a composition comprising at least one polyunsaturated carbon compound comprising at least one carbon chain comprising at least 5 carbon atoms, said at least one carbon chain comprising at least minus two conjugated double bonds.

A process according to claim 1 or claim 2 wherein said terpene is selected from farnesene, β-myrcene, ocimene and myrcenol

A process according to any one of claims 1, 2 or 4, said composition comprising at least one compound is a composition comprising or consisting of one or more vegetable oils.

The method of claim 5, wherein said vegetable oil is an oil of choice among rapeseed oil, oleic rapeseed oil and sunflower oil.

The method of claim 5, wherein said oil is rapeseed oil, sunflower oil, or a mixture thereof.

8. The method of claim 1 or 3, said composition comprising at least one compound is a composition comprising or consisting of one or more oils comprising at least one of the following fatty acids: rumenic acid, parinaric acid, the eleostearic acid, the punicic acid the calendrical acid or the conjugated linoleic acids.

9. Method according to any one of the preceding claims, wherein said at least one terpene is selected from farnesene or β-myrcene and said composition comprising at least one polyunsaturated carbon compound is a rapeseed oil or sunflower. 10. elastic and flexible crosslinked thermoplastic material, in film form, obtainable by the process as defined in any one of claims 1 to 9.

1 1. Use of a material as defined in claim 10, for the preparation of biodegradable and / or compostable food containers, packaging, coatings, especially surface coatings, for the preparation of parts injected or manufactured by extrusion or for the preparation of surface coatings, in particular for the manufacture of interior coatings for vehicles, or for its use as a material for the release of active ingredients of a drug or a food additive.

12. Material according to claim 10 for its use in human or animal surgery.

13. Medicament comprising an active ingredient contained in an envelope, said envelope being made of a material according to claim 10.