FR2939440A1 - Composite material having altered isotopic rate, useful e.g. for packaging of electronic components, and fabrication of fuel lines, comprises one polymer reinforced by fibers, fibrils and/or carbon nanotubes having bioresource carbon - Google Patents

Abstract

Composite material having altered isotopic rate comprises at least one polymer reinforced by fibers, fibrils and/or carbon nanotubes, where the fibers, fibrils and/or carbon nanotubes comprises at least 20 mass%, preferably at least 50 mass% of bioresource carbon and the polymer is obtained from at least one bioresource monomer. An independent claim is included for preparation of the composite material having altered isotopic level comprising: polymerizing at least one monomer having altered isotopic level, mixing the obtained polymer with fibers, fibrils or carbon nanotubes having altered isotopic level; and forming and optionally cross linking of the polymer, by molding, injecting, extruding, extrusion blowing; or mixing at least one monomer with fibers, fibrils or carbon nanotubes having altered isotopic level, polymerizing the mixture, and forming and optionally crosslinking of the polymer by molding, injecting, extruding, extrusion-blowing.

Description

1

BIOREWARE COMPOSITE MATERIALS AND PROCESS FOR THEIR PREPARATION

The present invention relates to novel composite materials based on polymers and fibers, carbon fibrils and / or nanotubes, obtained from bioressourced raw materials, as well as their manufacturing process. Fibers, fibrils and carbon nanotubes are recognized today as reinforcing materials with great advantages, because they allow to improve the mechanical properties (in particular the resistance to elongation and to the breaking) and / or thermal and / or the conductivity of the polymer matrices incorporating them, while being very light. They can replace metals in many applications. Carbon nanotubes have a hollow structure consisting of one or more graphitic sheets arranged concentrically about a longitudinal axis. For nanotubes composed of a single sheet, we speak of SWNT (acronym for Single Wall Nanotubes) and for nanotubes composed of several concentric layers, this is called MWNT (acronym for Multi Wall Nanotubes). The multiwall nanotubes may for example comprise from 5 to 15 sheets and more preferably from 7 to 10 sheets. For their part, carbon fibrils generally have a mean diameter ranging from 50 nm to 1 μm, higher than that of carbon nanotubes. They consist of more or less organized graphitic zones (or turbostratic stacks) whose planes are inclined at variable angles with respect to the axis of the fiber. They are often hollow in the central axis. 2

Finally, carbon fibers are materials consisting of fibers 5 to 10 μm in diameter, of which carbon is the main chemical element. Other atoms are usually present such as oxygen, nitrogen, hydrogen and less often sulfur. The carbon atoms are linked together and form graphitic type crystals more or less parallel to the axis of the fiber. Several thousand of these fibers are twisted together to form a strand. These strands can be used alone or in the form of fabric. The origin of carbon fibers dates back to 1958, when they were proposed by Union Carbide. The first fibers were of poor quality but rapid improvements were obtained using polyacrylonitrile (PAN) as a precursor. Synthesis of carbon fibers from PAN typically comprises a step of firing the fiber at about 300 ° C, in order to oxidize it slightly, after which the fiber is placed in an inert atmosphere under argon or nitrogen at a temperature of the order of 2000 ° C in an electric oven. After this step, the fiber contains about 95% carbon. Subsequent processing at higher temperatures increases its thermal conductivity and modulus. It is therefore understood that carbon fibers are very energy-intensive products, due to the high temperatures required during their manufacture. This energy consumption is not offset by their ability to allow the manufacture of lighter vehicles and consequently to reduce energy consumption in transport applications. In countries where electricity production comes mainly from the consumption of fossil resources, this energy expenditure is accompanied by an increase in energy consumption.

the emission of greenhouse gases, which is particularly damaging to the environment. To reduce this emission, it is not easy to act on the process of synthesis of carbon fibers. On the other hand, the Applicant has discovered that it is possible to use raw materials with a lower environmental impact than the PAN conventionally used in the synthesis of carbon fibers, in particular biobased raw materials.

In a similar manner, carbon nanotubes (or CNTs) can be manufactured by various methods such as electric discharge, laser ablation, chemical vapor deposition (abbreviated CVD) or physical vapor deposition (abbreviated PVD). ).

According to the Applicant, the most promising method of manufacturing CNTs in terms of CNT quality, reproducibility of CNT characteristics, and productivity is the CVD process. This process involves injecting a source of carbon-rich gas into a reactor containing a high temperature metal catalyst; in contact with the metal, the gas source decomposes into graphitic plane NTC and hydrogen. In general, the catalyst consists of a catalytic metal such as iron, cobalt, nickel, molybdenum, supported by a solid substrate, in the form of grains, and chemically inert, such as alumina, silica, magnesia or carbon, or in the form of an easily removable organic polymer after obtaining the nanotubes.

The gaseous sources of carbon generally used are methane, ethane, ethylene, acetylene, benzene which, again, come mainly from fossil resources. To anticipate supply difficulties related to these resources, the Applicant has proposed an alternative method, described in application EP 1 980 530, aimed at obtaining NTCs from carbon sources of renewable origin, in particular bioethanol. On the other hand, the manufacture of the polymer matrices in which the CNTs are intended to be introduced often makes use of petrochemistry, so that, although it constitutes a considerable progress, the solution proposed by the Applicant does not allow for completely free from dependence on oil resources. There remains therefore the need to propose new composite materials based on polymers and fibers, carbon fibrils and / or nanotubes, obtained from bioressourced raw materials without affecting their mechanical, electrical and / or thermal properties. In this context, the subject of the invention is composite materials based on polymers reinforced with fibers, carbon fibrils and / or nanotubes, said fibers, fibrils and / or carbon nanotubes containing at least 20%, preferably at least 50% by weight of bioresourced carbon and said polymers being obtained from at least one bioressourced monomer, namely non-fossil. The composite materials according to the invention are characterized in that they comprise bioressourced carbon, that is to say 14C, both in the polymer matrix and in the reinforcements that constitute the fibers, fibrils and / or nanotubes of carbon, and at a level equal to that present in the CO2 of the atmosphere.

Indeed, all the carbon samples drawn from contemporary or living organisms, and in particular from plant material, are a mixture of three isotopes: 2C, 3C and 14C in a ratio 14C / 12C kept constant by continuous exchange of carbon in the high atmosphere or ionosphere and which is equal to 1.2 x 10 12. Although 14C is radioactive and its concentration decreases over time, its half-life is 5730 years, so it is estimated that the 14C content is constant from the extraction of the plant material to the manufacture of materials from it and even until the end of their use. Thus, the materials that comprise bioresourced carbon have a 14C / 12C isotope ratio different from the 14C / 12C isotope ratio for the same material prepared from fossil material such as petroleum. Thus, in the present application, the bioressourced materials are called modified isotopic rate. More specifically, it is considered that the fibers, fibrils and / or carbon nanotubes used in the composite materials of the invention have an isotopic ratio of their 14C content to their 12C content which is greater than 10-12. also that the composite material of the invention contains 14C such that the ratio 14C / 12C is in the range of 0.2 x 10-12 to 1.2 x 10 12, preferably 0.6 x 10 The content of 14C can be measured, for example, according to the following techniques: 1) By liquid scintillation spectrometry: this method consists in counting R particles resulting from the decay of 14C. The radiation R from a sample of known mass (number of known carbon atoms) is measured for a certain time. This proportional to the number of atoms so determine. The 14C present in I3- radiation, which in contact with the (scintillator) give rise to "radioactivity" is 14 C, that one can sample emits liquid scintillating photons. These 6

photons have different energies (between 0 and 156 Kev) and form what is called a 14C spectrum. According to two variants of this method, the analysis relates either to the CO2 previously produced by the carbon sample in an appropriate absorbent solution, or to benzene after prior conversion of the carbon sample to benzene. 2) By mass spectrometry the sample is reduced to graphite or gaseous CO2, analyzed in a mass spectrometer. This technique uses an accelerator and a mass spectrometer to separate 14C ions from 12C and thus to determine the ratio of the two isotopes. These methods of measuring the 14C content of the materials are precisely described in ASTM D 6866 (including D6866-06) and ASTMD 7026 (including 7026-04) standards. These methods measure the 4C / 12C ratio of a sample and compare it with the 4C / 12C ratio of a 100% bioressourced reference sample (for which the 14C / 12C ratio is 1.2 x 10-12), to give a relative percentage of bioressourced carbon in the sample. The measurement method preferentially used in the case of the composites according to the invention is the mass spectrometry described in the ASTM D6866-06 standard (accelerator mass spectroscopy). The polymers used in the composite materials according to the invention are obtained by polymerization of at least one bioressourced monomer. Such a bioressource monomer is advantageously derived from the dehydration of an alcohol obtained by alcoholic fermentation of a product of plant origin. 7 This plant-based product may in particular be chosen from sugars, starch and plant extracts containing them, among which mention may be made of beetroot, sugar cane, cereals such as wheat, barley, sorghum or maize, as well as potatoes, or residues of these vegetable materials without this list being exhaustive. It can alternatively be biomass (mixture of cellulose, hemicellulose and lignin). The fermentation is then obtained, for example using Saccharomyces cerevisiae or its mutant, ethanol. In a less preferred variant, the plant material may be a source of cellulose, such as straw, wood or paper, which may lead by fermentation, in particular using Clostridium thyrobutylicum or acetobutylicum or their mutants, to the production of propanol and / or butanol. The plant material used is generally in hydrolysed form before the fermentation stage. This preliminary hydrolysis step thus allows, for example, the saccharification of starch to transform it into glucose, or the transformation of sucrose into glucose. These fermentation processes are well known to those skilled in the art. They include for example the fermentation of vegetable matter in the presence of one or more yeasts or mutants of these yeasts (microorganisms naturally modified in response to chemical or physical stress), followed by distillation to recover alcohol , in particular ethanol, in the form of a more concentrated aqueous solution which is then treated in order to further increase its molar concentration of alcohol such as ethanol. The alcohol obtained can optionally be purified. In particular, ethanol is generally obtained in a mixture 8

with heavier alcohols, called Fusel alcohols, the composition of which depends on the plant material used and the fermentation process. These generally comprise about 50% of iso-amyl alcohol (C5) and a few percentages of C3 and C4 alcohols (iso-butanol). It is therefore preferred according to the invention to purify the alcohol produced by fermentation, for example by absorption on molecular sieve type filters, carbon black or zeolites.

The alcohol obtained by fermentation is dehydrated to a mixture of alkene and water. This dehydration step is generally carried out in the presence of a catalyst, which may in particular be based on silicalite in the case of propanol or alumina in the case of ethanol. An example of a catalyst suitable for the dehydration of ethanol is in particular marketed by the company EUROSUPPORT under the trade name ESM 110. It is an undoped trilobal alumina containing little residual Na2O (usually 0.04%). Those skilled in the art will be able to choose the optimal operating conditions for this dehydration step. By way of example, it has been demonstrated that a ratio of the volume flow rate of liquid ethanol to the catalyst volume of 1 hr -1 and a mean temperature of the catalytic bed of 400 ° C led to an almost total conversion of the ethanol with an ethylene selectivity of the order of 98%. The alkene obtained in this stage of the process may optionally consist of a mixture of alkenes, in particular in the case where the alcohol produced by fermentation consisted of a mixture of ethanol and Fusel alcohols and was not purified at the end of the fermentation step. It is therefore advantageous in this case to provide a step of purification of the alkenes obtained at 9

the result of the dehydration step, for example by absorption on molecular sieve type filters, carbon black or zeolites. The bioresourced or modified isotopic alkene thus obtained can be used both to be converted into carbon nanotubes by passage over a powdery catalyst, advantageously in a fluidized bed, and to be converted into polymers. Thus, the bioresourced alkenes are in particular ethylene, propylene, butadiene, iso-butene, n-butene and isoprene. They can be converted into different polymers, especially after having undergone polymerization possibly preceded by chlorination and / or oxidation treatment.

Starting from the bioresourced ethylene, polyethylene, polyvinylchloride can be obtained by chlorination and then polymerization, polyesters by oxidation, followed by hydration and addition of terephthalic acid, polystyrene by polymerization with benzene, styrene-rubber. butadiene by polymerization with benzene and butadiene. From propylene bioressourcé, one can obtain in particular polypropylene, polyurethane by oxidation, polyacrylonitrile by treatment with nitric acid and polymerization. It is also possible to prepare epoxies and epoxy derivatives. In particular it is possible to obtain Bisphenol A and its derivatives, including diglycidyl ether Bisphenol A which represents about 90% of useful epoxies. Other biobased monomers may also be used such as amides and entities resulting from the reaction of a bioressourced acid and / or amine. 10

The composite material according to the invention can therefore comprise a wide variety of polymers, which are bioressourced thermoplastic, thermosetting or rubbery polymers (elastomers).

More particularly, the modified bioressource or modified isotopic polymer is chosen from the group comprising polyethylene, polypropylene, polybutadiene, polyamides, polyesters, polyurethanes, epoxies, bisphenol A polymers and their derivatives. Advantageously, the composite material (NTC + polymer) contains more than 50% or more than 75% and up to 100% of bioressourced carbon. A particularly interesting application of composite materials according to the invention is the polyurethane paint having a very good electrical resistivity. This is obtained using a composite according to the invention wherein the modified isotopic rate polymer is polyurethane, the latter being reinforced by carbon nanotubes modified isotopic rate. This modified isotopic rate polyurethane can be obtained by the following method: 1. alcoholic fermentation of a plant material and dehydration, whereby modified isotopic rate ethylene is obtained; 2. oxidation of the ethylene obtained according to step 1, whereby is obtained modified isotopic ethylene oxide; 3. hydration of the ethylene oxide obtained in step 2, whereby is obtained altered isotopic ethylene glycol; 11

4. polymerization of the ethylene glycol obtained in step 3 with isocyanate, whereby is obtained polyurethane isotopic altered. The polyurethane thus obtained is mixed with modified isotopic carbon nanotubes as prepared according to the process described in the patent application EP 1 980 530, and a bioresourced polyurethane paint having excellent properties of electrical resistivity is obtained.

According to another embodiment, the composite material of the invention comprises a modified isotope-modified bisphenol A diglycidyl ether resin (DGEBA) which is reinforced with modified isotopic carbon fibers, fibrils and / or nanotubes. This material is very suitable for applications requiring low electrical resistivity, since this is less than 106 Ohm. cm. In this embodiment, the monomer is the diglycidyl ether of bisphenol A modified isotopic rate which is mixed with carbon fibers, fibrils and / or nanotubes modified isotopic rate, and then polymerized in the presence of a diaminodiphenylsulfone. The modified isotopic rate nanotubes are as prepared according to the process described in EP 1 980 530. The modified isotopic carbon fiber or fibrils are prepared according to the process described in French Patent Application No. 08 55703 which comprises: ) the synthesis of acrolein from glycerol of plant origin, preferably in liquid or gaseous phase at 250-350 ° C and 1 to 5 bar, in the presence of molecular oxygen and preferably an acid solid catalyst, or according to the method described in US 2008/119663, 12

b) the ammoxidation of acrolein to obtain acrylonitrile, c) the polymerization of acrylonitrile to homo- or copolymer of acrylonitrile (PAN), d) the transformation of PAN into PAN fibers, e) l partial oxidation of PAN fibers, and f) carbonization of partially oxidized PAN fibers. In this process, the glycerol used in step a) can be obtained as a by-product of a transesterification of triglycerides of vegetable origin, that is to say a by-product of the manufacture of biodiesel from vegetable oil. The ammoxidation step b) is well known to those skilled in the art and can in particular be carried out according to one or the other of the processes described in FR 1 410 967, DE-1 070 170 or GB-709 337. In step c) of the process, the acrylonitrile may be homopolymerized or copolymerized with at least one other possibly bioressoured monomer, preferably an acrylic monomer, such as methyl acrylate, methyl methacrylate or acrylic acid. which allows better control of thermal effects in the subsequent step (e) (Gupta, AK et al., JMS-Rev.Macromol.Chem.

Phys. C31, 1991). Step d) of the process can be carried out in several ways. The PAN may be mixed with at least one plasticizer such as an alkyl carbonate, in particular ethylene carbonate (ethylene glycol ester of carbonic acid), and then heated to 110-160 ° C. for soften and inject it through a fine die, so that it falls back into a bath, consisting for example of water, where it coagulates and solidifies in the form of fibers or 13

can dissolve the PAN in a solvent (DMSO, DMF, DMA or aqueous solution of inorganic salts) and inject it by a fine die into a receiving chamber or drying oven where, after evaporation of the solvent, the polymer forms a solid fiber . The fibers thus obtained are washed and stretched until the desired fiber diameter is obtained. Stretching also makes it possible to align the molecular species, which will subsequently facilitate, during carbonization, a correct formation of the carbon-carbon bonds and will ensure that the fiber has a high degree of strength. Partial oxidation step e) is carried out by heating at 200-300 ° C for a few tens of minutes the PAN fibers in the presence of air, in order to modify their atomic arrangement and polar surface functions are created; they pass from a plastic state to a thermally stable infusible state. The carbonization step (f) is conducted by heating the fibers resulting from step (e) to a temperature of between 1200 and 1500 ° C. in an oven swept with an inert gas and maintained at a pressure greater than the pressure. to prevent air from entering the oven. Carbonization can optionally be carried out at two different temperatures, for better control of the entire process.

The fibers resulting from this process can then be subjected to a sizing treatment to protect them during transport, weaving or winding. This treatment consists in applying to the fibers a coating material chosen to be compatible with the adhesion agents used in the manufacture of the composites and which may for example be selected from epoxy resins, polyesters or polyurethanes. 14

Bisphenol A di-glycidyl ether is obtained by reaction of modified isotopic epichlorohydrin and modified isotopic rate bisphenol A. On the one hand, the modified isotopic epichlorohydrin can be obtained by the following method: 1. alcoholic fermentation of a plant material and optionally purification, whereby modified isotopic ethanol is obtained; 2. oxidation of the ethanol obtained in step 1, in the presence of copper, whereby modified isotopic ethanal is obtained; 3. reaction of the ethanal obtained in step 2 with CH3MgCl, whereby modified isotopic propanol is obtained; 4. dehydration in sulfuric acid medium at 180 ° C, whereby modified isotropic isopropylene and water are obtained; Reaction of the isopropylene obtained in step 4 with chlorine, whereby modified isotopic chloropropylene is obtained; 6. reaction of the chloropropylene obtained in step 5 with hydrochloric acid, whereby is obtained modified epichlorohydrin isotopic rate. On the other hand, the modified isotopic Bisphenol A can be obtained by the following method: 1. Reaction of benzene with modified isotopic propylene in the presence of phosphoric acid to obtain isopropylbenzene; 2. oxidation of the isopropylbenzene obtained in step 1 in the presence of silver and then hydration with sulfuric acid to give modified isotopic acetone and phenol; 15

3. reaction of phenol-modified isotopic acid acetone in acidic medium and in the presence of peroxide and sodium disulfide (Na2S2) to give modified isotopic bisphenol A.

Other polymers of industrial interest can be obtained from bioresourced material and are therefore modified isotopic rate polymers which are used in the composition of the composite materials of the invention.

It may be homopolymers or block copolymers, gradients or statistics, formed for example of at least two modified isotopic monomers as described above. The invention also relates to the process for preparing modified isotopic composite material described above, which comprises: 1. the polymerization of at least one modified isotopic monomer; 2. mixing the polymer obtained in step 1 with modified isotopic carbon fibers, fibrils or nanotubes; 3. the shaping of the mixture (and optionally the crosslinking of the polymer), by molding, injection, extrusion, extrusion blow molding.

According to another embodiment, the process for preparing modified isotopic composite material described above comprises: 1. the mixture of at least one modified isotopic monomer with modified isotopic carbon fibers, fibrils or nanotubes; 2. the polymerization of said mixture of step 1; 16

3. The shaping of the polymer obtained in step 2, and optionally its crosslinking, by molding, injection, extrusion, extrusion blow molding. In all cases, the CNTs and the polymer can be mixed solvent or melt. It is preferred to use a high shear mixer such as a twin-screw extruder or a co-kneader (molten route) or a rotor-stator system (solvent route). The mixer may further contain at least one dispersing agent to promote the dispersion of CNTs in the polymer, as described in patent applications FR No. 07 02871, FR No. 07 02874 and FR 07 03621. Composite materials with isotopic rate modified according to the invention can be used in all applications where their non-natural equivalents are used, for example for the packaging of electronic components, for the manufacture of gasoline lines (fuel line), coatings (coating) or antistatic paints, in thermistors, electrodes for supercapacities, etc. The invention will be described in more detail with reference to the following examples which are given purely by way of illustration and in no way limitative. EXAMPLES Example 1: Preparation of polyethylene reinforced with CNT. Step a): Preparation of Ethylene Ethanol obtained by fermentation of biomass using Saccharomyces cerevisiae is introduced into a vaporizer, then preheated in a heat exchanger before being injected at the top of a reactor of 127mm diameter containing a catalytic bed heated to 300-400 ° C and consisting of a layer of alumina ESM110 EUROSUPPORT, 17 representing a volume of 12700cm3 and a mass of 6500g, the volume flow ratio of ethanol to volume of catalyst being 1h-1. The mixture of water and ethylene produced in the reactor is sent to a heat exchanger where it is cooled, then it is sent to a gas-liquid separator where ethylene and water (possibly mixed with by-products) ) are separated. Step b): polymerization 205 g of ethylene prepared in step a) above at 1800 bar are introduced into a reactor at 230 ° C. A solution of 0.26 g of t-butyl peroxide sold under the trademark Luperox DI and 14 g of propanal in 200 ml of heptane is prepared. 3 cm3 of this solution is introduced into the reactor and allowed to react for 20 minutes with stirring. After decompression of the reactor, the polyethylene is recovered in powder form. Step c) Extrusion To 17.46 g of polyethylene powder obtained in step b) above, 0.54 g of nanotubes prepared according to the process described in Example 2 of EP 1 980 530 are added. DSM microcompounder for 10 minutes at 280 ° C. The product obtained is then extruded in the form of a rod, the resistance of which is measured with silver lacquer, computed by calculation to a volume resistivity. For comparison, the following 3 materials are prepared using the protocol of steps b and c with the following differences: ## EQU1 ## The 0.54 g of CNTs prepared according to the process described in Example 2 of EP 1 980 530 are replaced by 0.54 g of NTC marketed by ARKEMA under the trade name Graphistrength C100; 18 lb material: the 17.46 g of polyethylene obtained in step b) are replaced by 17.46 g of polyethylene of fossil origin; 1c material: the 0.54 g of CNTs prepared according to the process described in Example 2 of EP 1 980 530 are replaced by 0.54 g of CNTs marketed by ARKEMA under the trade name Graphistrength C100 and the 17.46 g of polyethylene obtained in step b) are replaced by 17.46g of polyethylene of fossil origin.

For each of these materials, a resistivity of 1000 +/- 150 ohm.cm is obtained.

Claims (14)

REVENDICATIONS1. Modified isotopic composite material comprising at least one polymer reinforced with carbon fibers, fibrils and / or nanotubes, said carbon fibers, fibrils and / or nanotubes containing at least 20%, preferably at least 50% by mass of carbon bioressourcé and said polymer being obtained from at least one bioressource monomer. 2. Composite material according to claim 1, characterized in that the carbon fibers, fibrils and / or nanotubes contain at least 0.2 x 10 -10% by weight of 14C, preferably at least 0.6 x 10- 10 mass of 14C. 3. composite material according to claim 1 or claim 2, characterized in that it contains 4C such that the ratio 14C / 12C is in the range of 0.2 x 10-12 to 1.2 x 10 -12, preferably ranging from 0.6 x 10-12 to 1.2 x 10-12 4. Composite material according to any one of claims 1 to 3, characterized in that the polymer is a thermoplastic polymer, thermosetting or rubbery. 5. Material according to any one of claims 1 to 4, characterized in that the polymer is selected from the group comprising polyethylene, polypropylene, polybutadiene, polyamides, polyesters, polyurethanes, epoxies, polymers bisphenol A and their derivatives. 6. Composite material according to claim 5, characterized in that the polymer is a polyurethane modified isotopic rate obtained by the following method: 1. alcoholic fermentation of a plant material and dehydration, whereby one obtains ethylene modified isotopic rate; 2. oxidation of the ethylene obtained according to step 1, whereby is obtained modified isotopic ethylene oxide; 3. hydration of the ethylene oxide obtained in step 2, whereby modified isotopic rate ethylene glycol is obtained; 4. polymerization of the ethylene glycol obtained in step 3 with isocyanate, whereby modified isotopic polyurethane is obtained. 7. Composite material according to claim 6, characterized in that it has an electrical resistivity of less than 106 Ohm.cm. 8. composite material according to claim 5, characterized in that the monomer is di-glycidyl ether bisphenol A which is obtained by reaction of modified isotopic epichlorohydrin and bisphenol A modified isotopic rate. 9. Composite material according to claim 8, characterized in that the modified isotopic epichlorohydrin is obtained by the following method: 1. alcoholic fermentation of a plant material and optionally purification, whereby one obtains ethanol modified isotopic rate; 2. oxidation of the ethanol obtained in step 1, in the presence of cooking, whereby is obtained ethanal modified isotopic rate; Reaction of the ethanal obtained in step 2 with CH 3 MgCl, whereby modified isotopic propanol is obtained; 4. dehydration in sulfuric acid medium at 180 ° C, whereby modified isotropic isopropylene and water are obtained; Reaction of the isopropylene obtained in step 4 with chlorine, whereby modified isotopic chloropropylene is obtained; 6. reaction of the chloropropylene obtained in step 5 with hydrochloric acid, whereby is obtained modified epichlorohydrin isotopic rate. 10. Composite material according to claim 8 or 9, characterized in that Bisphenol A is prepared by the following method: 1. reaction of benzene with isotopic propylene modified in the presence of phosphoric acid to obtain isopropylbenzene; 2. oxidation of the isopropylbenzene obtained in step 1 in the presence of silver and then hydration with sulfuric acid to give modified isotopic acetone and phenol; 3. Addition of modified isotopic acetone and phenol in acidic medium and in the presence of peroxide and Na2S2 to give modified isotopic bisphenol A. 11. Process for preparing modified isotopic composite material according to any one of claims 1 to 10, comprising: 1. the polymerization of at least one modified isotopic monomer; 2. mixing the polymer obtained in step 1 with modified isotopic carbon fibers, fibrils or nanotubes; 3. shaping, and optionally crosslinking, by molding, injection, extrusion, extrusion blow molding. 22 A process for preparing a modified isotopic composite material according to any one of claims 1 to 10, comprising: 1. mixing at least one monomer with modified isotopic carbon fiber, fibrils or nanotubes; 2. the polymerization of the mixture of step 1; 3. shaping, and optionally crosslinking, of the polymer of step 2, by molding, injection, extrusion, extrusion blow molding. 13. Method according to any one of claims 1 to 10, characterized in that the monomer is bisphenol A diglycidyl ether modified isotopic rate which is mixed with carbon fibers, fibrils and / or nanotubes modified isotopic rate , then polymerized in the presence of a diaminodiphenylsulfone. 14. Use of the composite material according to any one of claims 1 to 10, or prepared according to the process of claims 11 or 13, in applications for packaging electronic components, manufacturing fuel lines (fuel line), of coatings (coating) or antistatic paints, in thermistors or electrodes for supercapacities.