FR2975400A1 - USE OF SUPRAMOLECULAR POLYMER FOR THE MANUFACTURE OF A FIRE RESISTANT MATERIAL. - Google Patents

Abstract

The present invention relates to the use, for the manufacture of a fire-resistant material, of at least one supramolecular polymer obtainable by the reaction of at least one at least one trifunctional compound (A) carrying first and second functions with: at least one compound (B) bearing, on the one hand, at least one reactive group capable of reacting with the first functions of (A) and, on the other hand, at least one associative group; and at least one at least one bifunctional compound (C) whose functions are capable of reacting with the second functions of the compound (A) to form ester, thioester or amide bridges.

Description

Use of a supramolecular polymer for the manufacture of a fire-resistant material

The present invention relates to the use of supramolecular polymers for the manufacture of a fire-resistant material. Flame retardant compositions, also known as flame retardants, are intended to delay the onset of ignition of materials, exposed to a heat source or directly exposed to a flame, and to prevent their development and spread. . The halogenated flame retardant compositions comprising bromine and its derivatives are known. Their mechanism of action is notably based on the slowing down of free radical reactions in flames caused by bromine in the gas phase. Their disadvantage is that when exposed to fire, these compositions give off halogenated vapors, such as in particular bromine vapors. However, the inhalation of such halogenated, highly reactive products is toxic. Their use must therefore be avoided both for health reasons and for the protection of the environment. Other flame retardant known compositions are based on phosphorus, and more particularly based on organic phosphate (such as melanin phosphates) or inorganic (such as ammonium polyphosphate). These compositions have the advantage of being much less aggressive because they are free of halogenated compounds and have no adverse effects on health and the environment. However, for a good efficiency, they require the addition of ammonium chloride, which has the disadvantage of being corrosive. Other flame retardant compositions include borates. The latter generally act in synergy with other flame retardants, and in particular with brominated flame retardants. Consequently, the use of borates does not make it possible to overcome the undesirable effects caused by halogens. There is therefore a permanent need for new fire-resistant materials, not having the disadvantages mentioned above.

So-called supramolecular polymers are materials comprising compounds associated by non-covalent bonds, such as hydrogen, ionic and / or hydrophobic bonds. An advantage of these materials is that these physical bonds are reversible, especially under the influence of temperature or by the action of a selective solvent. Some of them also have elastomer properties. Unlike conventional elastomers, these materials have the advantage of being able to be fluidized above a certain temperature, which facilitates their implementation, in particular the good filling of the molds, as well as their recycling. Some of these supramolecular polymers are, moreover, constituted of molecules linked in networks exclusively by reversible physical bonds. Despite the relatively modest physical bonding forces of the molecules of such a supra-molecular network, these materials are, like conventional or conventional elastomers, capable of exhibiting dimensional stability over very long times and recovering their initial shape after large deformations. . They can be used to manufacture, for example, gaskets, thermal or acoustic insulators, tires, cables, sheaths, shoe soles, packaging, patches (cosmetic or dermo-pharmaceutical), dressings, elastic clamps, vacuum tubes, or tubes and hoses for transporting fluids. Supramolecular materials have already been described by the Applicant. More particularly, the Applicant has already described supramolecular materials having the behavior of elastomers.

A self-healing elastomeric supramolecular material is, moreover, disclosed in WO 2006/087475. It comprises molecules containing at least three associative functional groups, such as imidazolidone groups, capable of forming several physical bonds and which can be obtained by reacting urea on the product of the reaction of a polyamine with triacids. The materials obtained according to the teachings of the documents WO 03/059964 and WO 2006/087475 contain triacids covalently linked via amide functions to intermediate junctions and / or termini consisting of the reaction product of the polyamine. with urea and which therefore contain many associative groups, that is to say containing NH and C = 0 functions capable of associating with each other by hydrogen bonds. Specifically, the publication of P. CORDIER, L. LEIBLER, F. TOURNILHAC and C. SOULIE-ZIAKOVIC in Nature, 451, 977 (2008) mentions that a polymer synthesized according to the procedure described in WO 2006/087475 comprises amidoethylimidazolidone terminations and di (amidoethyl) urea and diamidotetraethyl triurea junctions. It is understood that because of the synthesis process of these 4 materials, the chemical natures of the aforementioned junctions and terminations are interdependent, in that it is not possible to vary the nature of the amidoethylimidazolidone termination without affecting that of the two junctions. The document entitled "Versatile One-Pot Synthesis of Supramolecular Plastics, and Self-Healing Rubbers" by Damien MONTARNAL, François TOURNILHAC, Manuel HIDALGO, Jean-Luc COUTURIER, and Ludwik LEIBLER appeared in "Journal of the American Chemical Society," 131 ( 23). 7966; June 17, 2009 discloses an alternative method for obtaining supramolecular polymers, including those having elastomeric properties of the type of those published by P. CORDIER et al. This method makes it possible, among other things, to break the interdependence of the chemical natures between the junctions and the terminations of the supramolecular network. It thus becomes possible to control the chemical nature of the terminations independently of that of the junctions.

These self-healing polymers have enormous advantages, such as being easily processable, being predominantly from renewable raw materials, being self-healing. The Applicant has now found that supramolecular polymers also have excellent fire resistance. The subject of the present invention is therefore the use, for the manufacture of a fire-resistant material, of at least one supramolecular polymer obtainable by the reaction of at least one at least one trifunctional compound (A) carrying first and second functions with: at least one compound (B) bearing, on the one hand, at least one reactive group capable of reacting with the first functions of (A) and, on the other hand, at least one associative group ; and at least one at least one bifunctional compound (C) whose functions are capable of reacting with the second functions of the compound (A) to form ester, thioester, amide bridges. The inventors have shown that the compositions which are the subject of the invention, comprising a supramolecular polymer, have excellent fire resistance. In particular, the compositions which are the subject of the invention make it possible to significantly improve the ability of supramolecular polymers to resist a flame (Examples 4 and 5). As a preamble, it will be noted that the expression "included between" must be interpreted, in the present description, as including the boundaries cited. For the purpose of the present invention, the term "fire-resistant material" is intended to mean a material having a high resistance to flame propagation, good thermal stability, and a high capacity not to generate flames when it comes into contact with incandescent bodies or spreading flames. Preferably, said material is classified V2, very preferably V1 or VO according to IEC 60695-11-10, edition 1.1, 08-2003 method B ("Test flames, horizontal and vertical test methods to the 50W flame) described in Example 4.

By "manufacture of a material" is meant in the sense of the present invention not only the manufacture of an object which proves, in itself fire-resistant but also coating, coating, or encapsulation an existing object, to make it fire resistant.

Supramolecular Polymers The reagents used for the manufacture of the supramolecular polymers used in the present invention will now be described in more detail. As indicated above, the supramolecular polymer is capable of being obtained by the reaction of at least one at least trifunctional compound (A) carrying first and second functions with: at least one compound (B) carrying, on the one hand, at least one reactive group capable of reacting with the first functions of (A) and, on the other hand, at least one associative group; and at least one at least one bifunctional compound (C) whose functions are capable of reacting with the second functions of the compound (A) to form ester or thioester or amide bridges. By "associative groups" is meant groups capable of associating with each other by hydrogen bonds, advantageously by 1 to 6 hydrogen bonds. Examples of usable associative groups are imidazolidinyl, triazolyl, triazinyl, bis-ureyl, ureido-pyrimidyl. It is preferred that the average number of terminal associative groups per molecule of the supramolecular polymer is at least 3. It is advantageously at most 6. These are covalently linked to the molecule. By "covalently" is meant that the associative groups are connected to the terminal functions of the molecule either via a direct bond or, preferably, via a chain, especially alkylene. By "reactive groups" or "functions" is meant chemical functions capable of reacting with other chemical functions to form covalent bonds, leading in particular to the formation of ester, thioester, amide, urea or urethane bridges and in particular ester and amide bridges. A "bifunctional" compound refers to a compound having two identical or different reactive functions. An "at least trifunctional" compound refers to a compound carrying at least three identical or different reactive functions. By "fragment" is meant in the sense of the invention a unit of a molecule located between two or three bridges as defined above. A "bifunctional" moiety is obtainable from a bifunctional compound and a "trifunctional" moiety is obtainable from a trifunctional compound. The molecules of the supramolecular polymer comprise at least bifunctional fragments, advantageously bifunctional, and at least trifunctional fragments, advantageously trifunctional. Preferably, the compound (A) represents at most 50% by weight relative to the total weight of the supramolecular polymer. The compound (A) used in the first step of the synthesis process of the supramolecular polymer may in particular carry at least three identical or different functions chosen from acid, ester or acyl chloride functions. It advantageously comprises from 5 to 100, preferably from 12 to 100 and more preferably from 24 to 90 carbon atoms. The compound (A) may, when reacted with the compound (B) and / or the compound (C), be in admixture with mono- and bifunctional compounds, such as mono- and diacids, in particular mono- and dimers of fatty acids. It is preferred to use according to the invention as compound (A) mixtures of dimers (oligomers of 2 identical or different monomers) and trimers of fatty acids of vegetable origin. The compound (A) may thus be a trimer of at least one of the following acids, undecylenic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, eicosenoic acid and docosenoic acid, which are commonly found in tall oil fatty acids, rapeseed, corn, sunflower, soybean, grapeseed, linseed, jojoba, eicosapentaenoic acid and docosahexaenoic acid found in fish oils.

The compound (A) may be a mixture of fatty acid trimer and diacids chosen from a linear alkyl dicarboxylic acid such as glutaric acid, adipic acid, pimelic acid, suberic acid and azelaic acid. , sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, thapsic acid, octadecanedioic acid or branched acid such as 3,3- glutaric dimethyl.

Examples of fatty acid trimers are the compounds of the following formulas which illustrate the cyclic trimers derived from 18-carbon fatty acids, in the light of the fact that the commercially available compounds are mixtures of steric isomers and isomers of position of these structures, possibly partially or totally hydrogenated. H3C- (CH2) 4-CH2 CH2- (CH2) 5-CH2-COOH H3C- (CH2) 4-CH2 CH2- (CH2) 5-CH2-COOH H3C- (CH2) 3-CH2-CH = CH-CH2 CH2- (CH2) 5-CH2-COOH

C18 acid trimer

It is thus possible to use a mixture of oligomers of fatty acids containing dimers, trimers and monomers of linear or cyclic Cu fatty acids, said mixture being predominant in dimers and trimers and containing a small percentage (usually less than 5% ) of monomers. Preferably, said mixture comprises: 0 to 40% by weight, preferably 0.1 to 5% by weight of identical or different fatty acid monomers, 0.1 to 99% by weight, preferably 18 to 85% by weight of identical or different fatty acid dimers, and - 0.1 to 90% by weight, preferably 5 to 85% by weight, identical or different fatty acid trimers.

Even more preferably, said mixture of molecules derived from fatty acids has an average molecular weight greater than 400 g / mol. Examples of dimeric / trimeric mixtures of fatty acids (% by weight). Croda's Pripol® 1017, a mixture of 75-80% of dimers and 18-22% of trimers with on the order of 1-3% of monomeric fatty acids, Croda's Pripol® 1048, a mixture of 50/50% dimers / trimers, - Pripol® 1013 from Croda, a mixture of 95-98% dimers and 2-4% trimers with 0.2% maximum fatty acid monomers, - Pripol® 1006 of Croda, a blend of 92-98% dimers and up to 4% trimers with up to 0.4% monomeric fatty acids, - Croda Pripol® 1040, a mixture of dimers and acid trimers with at least 75% trimers and less than 1% monomeric fatty acids, - Arizona Chemicals Unidyme® 60, a blend of 33% dimers and 67% trimers with less than 1% monomeric fatty acids, - Unidyme® 40 from Arizona Chemicals, a mixture of 65% dimers and 35% trimers with less than 1% monomeric fatty acids, - Unidyme® 14 from Arizona Chemicals, mixture of 94% dimers and less than 5% trimers and at very high oligomers with about 1% of monomeric fatty acids, Empal® 1008 from Cognis, a mixture of 92% dimers and 3% higher oligomers, essentially trimers, with 5% of monomeric fatty acids, Empal® 1018 from Cognis, a mixture of 81% of dimer and 14% of higher oligomers, essentially of which trimers, with the order of% acids Fatty monomers, Oleon's Radiacid® 0980, a mixture of dimers and trimers with at least 70% trimers. Radiacid® 0950 from Oleon, a mixture of 79-85% of dimers and 13-19% of fatty acid trimers with about 1 -3% of monomeric fatty acids. Pripol®, Unidyme®, Empal®, and Radiacid® products include Cu fatty acid monomers and fatty acid oligomers corresponding to C18 multiples. According to a particular embodiment, the mixture of diacid and triacid carboxylic acid may be partially or completely replaced by a diacid (s) and triacid (s) derivative, this derivative being chosen from an acid salt, an acid ester and an acid chloride. As an example of an ester, mention may be made of a methyl, ethyl or isopropyl ester of a fatty acid as defined above. A preferred fatty acid ester is a fatty acid methyl ester, and particularly a fatty acid dimer methyl ester or a mixture of fatty acid oligomers as defined above. As an example of a fatty acid chloride, mention may be made of sebacoyl chloride.

For its part, the compound (B) carries at least one reactive group which may in particular be chosen from primary or secondary amine groups or alcohol. Alternatively, the compound (B) can carry at least two such identical or different groups. It is preferred according to the invention that the compound (B) carries at least one primary amine function. In the case in particular where the reactive group of the compound (B) is capable of reacting with both the first and second functions of the compound (A), it is preferred that, in the first step of the process, the ratio of the number of the reactive groups of the compound (B) to the sum of the functions of the compound (A) ranges from 0.05 to 0.8 and preferably from 0.15 to 0.7. Compound (B) can thus meet any one of formulas (B1) to (B5). R ~ N, N ~ R 'A

(B1) / N R-N, N

(B2) R "(B4)

O O R, R 1, R NH NH NH NH (B 5)

or .

R denotes a unit containing at least one reactive function,

R 'denotes a hydrogen atom,

R ", R 1 and R 2 denote any group, A denotes an oxygen or sulfur atom or a group -NH, preferably an oxygen atom.Preferred examples of compounds (B) are 2-aminoethylimidazolidone ( UDETA), 1- (2 - [(2-aminoethyl) amino] ethyl) imidazolidone (UTETA), 1- (2- {2 - [(2-aminoethylamino] ethyl} amino) ethyl] imidazolidone (UTEPA), N- (6-aminohexyl) -N '- (6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl) urea (UPy), 3-amino-1,2,4-triazole and 4-Amino-1,2,4-triazole UDETA is preferred for use in the present invention Some of these compounds can be obtained by reacting urea with a polyamine, for example, UDETA, UTETA and UTEPA can be respectively prepared by reacting urea with diethylenetriamine (DETA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA) .The reaction of compound (B) with the compound ( A) can for example be performed at a rature between 20 and 200 ° C, preferably between 130 and 170 ° C, for a time ranging from 1 to 15 h, for example from 3 to 9 am, preferably with stirring under inert atmosphere. This compound is then reacted with at least one bifunctional compound (C) in such a way that the functions of (C) react with the second functions, i.e. the remaining reactive functions, of the compound (A). ). It will be avoided in this step to be placed under catalytic conditions likely to lead to homopolymerization of the compound (C).

The compound (C) carries at least two functions, identical or different, chosen in particular from the epoxy, alcohol and amine functions. Compound (C) can be a diepoxide. It can thus be chosen from: bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromo bisphenol A diglycidyl ether, or hydroquinone diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether bisphenol A polypropylene glycol diglycidyl ether, diglycidyl ester of terephthalic acid, epoxidized polyunsaturated fatty acids, and epoxidized limonene; and their mixtures. Alternatively, the compound (C) may be a polyepoxide containing at least three epoxide functions, chosen for example from: castor oil triglycidyl ether, 1,1,1-tris (hydroxymethyl) propane triglycidyl ether, trisphenol triglycidyl ether, glycerol tridlycidyl ether, glycerol propoxylate triglycidyl ether, glycerol ethoxylate triglycidyl ether, trimethylol propane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritolpolyglycidyl ether, poly (glycidyl acrylate), polyglycidyl methacrylate epoxidized polyunsaturated fatty acids, epoxidized vegetable oils, epoxidized fish oils and epoxidized limonene. In another variant, the compound (C) may be a diol. In this case, the compound (C) may be chosen from: ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, octanediol, nonanediol, decanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyesters with hydroxy ends, polybutadienes with hydroxy ends, polydimethylsiloxanes with hydroxy ends, polyisobutylenes with hydroxy ends, polybutadiene-co-acrylonitrile copolymers with ends hydroxy, diol dimers derived from fatty acids and mixtures thereof. According to another possibility, the compound (C) may be a polyol containing at least three alcohol functions. Examples of such compounds include. sugars such as sorbitol, pentaerythritol, trimethylolpropane, as well as glycerol and its ethoxylated and propoxylated derivatives, castor oil (castor garlic) and diol dimers derived from fatty acids such as Pripol® 2033 from Croda.

Alternatively, the compound (C) may be a polyamine. The polyamine may be any compound carrying at least two amine functions, preferably primary amine, and preferably a compound of formula (I). H2N- (CHR1) m- (CHR2) n- [NH- (CH2) x] y -NH- (CHR3) p- (CHR4) qNH2 (I) wherein: R1, R2, R3 and R4 are independently a hydrogen atom or a C 1 -C 6 alkyl group such as a methyl group, m, n, p and q independently denote an integer ranging from 1 to 3.25 x x denotes an integer ranging from 1 to 6 y denotes an integer ranging from 0 to 2. In formula (I) above, at least one, and preferably all, of the conditions below are satisfied. - R1, R2, R3 and R4 denote a hydrogen atom, - m + n is equal to 2, 3 or 6, preferably 2, - p + q is equal to 2, 3 or 6, preferably 2 X represents an integer ranging from 2 to 4; y is equal to 0 or 1, preferably 0. Preferred examples of polyamines of formula (I) are DETA (diethylenetriamine), TETA (triethylenetetramine). ), TEPA (tetraethylene pentamine) and dihexylene triamine.

Alternatively, the polyamine may be a linear alkylene diamine containing 3 to 40 carbon atoms such as cadaverine, putrescine, hexamethylenediamine or 1,12-diaminododecane or a cyclic alkylene diamine such as isophorone diamine, or the diamine dimer named Priamine of Croda. The reaction of the polyamine (compound (C)) with the mixture of diacid / triacid carboxylic acid or their derivatives salt, ester or acid chloride used (compound (A)), may, for example, be carried out at a temperature between 20 and 200 ° C, preferably between 140 and 180 ° C, for a period ranging from 1 to 24 hours, for example from 6 to 8 hours, advantageously with stirring and under an inert atmosphere. In a preferred embodiment, the compound (A) is a mixture of polycarboxylic acids or its salt, ester or acid chloride derivative reacted with at least one compound (C) which is a polyamine in a molar ratio. amine functions at the acid functions 17 of the dicarboxylic acid of between 0.95 and 0.0.2 and preferably between 0.85 and 0.3. The supramolecular polymer used in the present invention is derived from the reaction of the compound (A) with the compound (B) and with the compound (C). These reactions can be performed simultaneously or successively. In the case where these reactions are conducted successively, the reaction of the compound (A) with the compound (B) will preferably be carried out first but the reverse order is also possible. They may also be carried out either in separate reactors or in the same reactor, without it being necessary to provide a washing or purification step after the first of these reactions.

It is preferred that the supramolecular polymer also contains intermolecular hydrophobic bonds, advantageously due to interactions between alkyl groups carried by each of the trifunctional molecules described above. By "alkyl" is meant in the sense of the invention side groups (CnH2n + 1) and not alkylene chains (CnH2n), for example. In a particularly preferred manner, each of these molecules comprises C6-C24 alkyl chains, advantageously in greater number than said terminal associative groups. They may in particular be provided by the compounds (A), in particular when they are trimers of fatty acids. In a particular embodiment, the supramolecular polymer defined above is reacted with urea. Thus, preferably, the product resulting from the reaction of at least one compound (A) with at least one compound (B) and at least one compound (C) is reacted with urea to form junctions di (amidoethyl) urea, diamidotetraethyl triurea and / or urea. The reaction can for example be carried out at a temperature of 110 to 180 ° C, preferably 120 to 160 ° C by carrying out a temperature ramp, for a period ranging from 30 minutes to 24 hours, preferably for a period of 1 hour. at 6 hours, under an inert atmosphere and, advantageously, with stirring. Again, this reaction can be carried out in a reactor separate from that or those used in the preceding step or steps, or in the same reactor. It is thus clear that all the steps of the process for obtaining the supramolecular polymer can be carried out in the same reactor, by successive addition of the reagents, which makes the process particularly simple and economical. The function of the urea in this step is to create additional associative groups, for example according to the following reaction schemes: ## STR2 ## The compounds (A), (B) and (C) previously described can be introduced, in the state of the invention. melted, in the solid state powdery or non-pulverulent, or liquid, for example in solution or aqueous dispersion. However, it is preferred that they be introduced in the pulverulent solid state or in the molten state in order to avoid the use of solvents which need to be subsequently removed. When the process for obtaining the supramolecular polymer has a final reaction step with urea, therefore, in addition to the reactions of (A) with (B) and (C), it is preferred that the compound (C) is a polyamine as described above, and it is particularly preferred that the compound (C) is diethylene triamine or DETA.

The proportions of (A), (B) and (C) used in the method of synthesis of the supramolecular polymer, as well as their nature, and the choice of whether or not to perform an additional reaction step with urea, determine the characteristics mechanical means of said polymer. Thus, it is possible to obtain mechanical properties ranging from those of an elastomer to those of a plastomer. These parameters also determine the solubility properties of said polymer. Thus, it is possible that the supramolecular polymer is completely or partially soluble in polar solvents such as alcohols. According to one embodiment of the invention, the average number of associative groups per molecule is at least 1.2, preferably at least 2 or even at least 2.2. The supramolecular polymers used in the invention advantageously have elastomeric properties such as that of rubber elasticity or hyperelasticity, that is to say the property of being able to undergo uniaxial deformation at its operating temperature. at room temperature for example, for at least 20%, for example for 15 minutes, and recovering, once this stress is relaxed, most of its initial dimension, for example, with a remanent deformation of less than 5%. of its initial dimension. These supramolecular polymers may, moreover, be capable of self-healing after cutting and, after contacting the edges of the cut, have still elastomeric properties enabling them to undergo, for example, tensile deformation of at least 20%, or even at least 100% before breaking and recover most of their initial dimensions once the stress is relaxed, with, for example, a remanent deformation less than 10% of their initial dimension.

The supramolecular polymers defined above are materials in the form of soft solids, which it is necessary to extract from the reactor used for their synthesis. According to one preferred variant, the product can be extracted from the reactor in the liquid state and "finished" by a heat treatment in an oven, oven, heating strips or any other suitable equipment until it is converted into a soft solid. The supramolecular polymer may be cut or ground, in particular cold, for example in a hammer mill, ball mill, balls, grinders or knives and then washed, for example with water, and optionally shaped, in particular by hot pressing, calendering, thermoforming or any other method. Preferably, the supramolecular polymer, optionally washed with water, is roughly cut into strips or pieces.

Elastomers

In a preferred embodiment of the invention, the material made from supramolecular polymer further comprises at least one elastomer. Among the elastomers, we can cite as non-exclusive examples, natural rubber, polybutadiene, synthetic polyisoprene, polychloroprene and their hydrogenated versions, polyisobutylene, block copolymers of polybutadiene and isoprene with styrene as well as their hydrogenated versions such as poly styrene-b-butadiene (SB), poly styrene-b-butadiene-b-styrene (SBS), poly styrene-b-isoprene-b-styrene (SIS), poly styrene-b- (isoprene-stat-butadiene) -b-styrene or poly styrene-b-isoprene-b-butadiene-b-styrene (SIBS), hydrogenated SBS (SEBS), poly styrene-b-butadiene-b methyl methacrylate (SBM), as well as its hydrogenated version (SEBM), poly (methyl methacrylate) -b-butyl acrylate-methyl methacrylate (MAM), poly styrene-b-butyl acrylate-b-styrene (SAS), random copolymers of butadiene with styrene (SBR) and acrylonitrile (NBR) and their hydrogenated versions, the caoutc butyl or halogenated houcs, polyethylenes, polypropylenes, silicone elastomers of general formula - (Si (R) (CH 3) - O) n - with CH 3 and R bonded to the silicon atom and this bonded to the oxygen atom, and R may be a methyl, phenyl, vinyl, trifluoropropyl or 2-cyanoethyl, ethylene-vinyl alcohol copolymers, ethylene-propylene and ethylene-propylene-diene copolymers, copolymers of ethylene with acrylic and vinyl monomers such as copolymers of ethylene and vinyl acetate, copolymers of ethylene, vinyl acetate, and maleic anhydride, available from the company Arkema under the trade name Orevac®, copolymers of ethylene, acrylic ester, copolymers of ethylene, acrylic ester, maleic anhydride, copolymers of ethylene, acrylic ester, functional acrylic ester such as acrylate or glycidyl methacrylate, available from from ARKEMA under the trade name LOTADER®, flexible acrylic polymers or copolymers such as resins based on methacrylic esters such as butyl polyacrylate and its copolymers with styrene, or other acrylic or vinyl monomers, multiblock polyamide / polyether copolymers, such as those available from the company ARKEMA under the name PEBAX®, elastomer based on polyesters and polyurethane (PUR), recycled rubbers based on thermoplastic elastomers or based on recycled cross-linked rubber such as that from the recycling of tires, as well as their mixtures. As a preferred elastomer, one or more elastomers selected from the list below are advantageously used for the manufacture of rubber articles. Preferably, the elastomer according to the invention may comprise one or more diene elastomers crosslinked or otherwise, virgin or derived from one or more recycling. The term "diene elastomers" is more specifically understood to mean (1) homopolymers obtained by polymerization of a conjugated diene monomer having from 4 to 22 carbon atoms, for example 1,3-butadiene or 2-methylbutadiene-1, 3, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene; (2) copolymers obtained by copolymerization of at least two of the abovementioned conjugated dienes with one another or by copolymerization of one or more of the abovementioned conjugated dienes with one or more ethylenically unsaturated monomers chosen from: vinyl aromatic monomers having from 8 to 20 carbon atoms, for example: styrene, ortho-, meta- or para-methylstyrene, the commercial mixture "vinyl-toluene", paratertiobutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene; vinyl nitrile monomers having 3 to 12 carbon atoms, such as, for example, acrylonitrile, methacrylonitrile; acrylic ester monomers derived from acrylic acid or methacrylic acid with alkanols having from 1 to 12 carbon atoms, for example methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinyl aromatic units, vinyl nitriles and / or acrylic esters; (3) ternary copolymers obtained by copolymerization of ethylene, of an α-olefin having 3 to 24 carbon atoms with a non-conjugated diene monomer having from 6 to 12 carbon atoms, for example elastomers obtained from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type such as in particular 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene (EPDM elastomer); (4) copolymers obtained by copolymerization of isobutene and isoprene (butyl rubber), as well as the halogenated, in particular chlorinated or brominated, versions of these copolymers; (5) a mixture of several of the aforementioned elastomers (1) to (4) between them. The polymers that can be used according to the invention can be obtained according to conventional polymerization techniques well known to those skilled in the art.

Additives

The material made from supramolecular polymer according to the invention can be used as such or in single or multiphase mixtures with one or more compounds such as petroleum cuts, solvents, mineral and organic fillers, plasticizers, tackifying resins, processing aids, lubricants, anti-oxidants, anti-radiation additives, (anti-UV), pigments and / or dyes. In particular, additives that may be added include: - lubricants, such as stearic acid and its esters, waxy esters, polyethylene waxes, paraffin or acrylic lubricants - dyes 25 - mineral pigments or organic, such as those described in Plastics Additives and Modifiers Handbook, Section VIII, Dyes ", J. Edenbaum, Ed., Van Nostrand, pp. 884-954. Examples of useful pigments include carbon black, titanium dioxide, clay, metallic particles or treated mica particles of the brand IRIODIN® marketed by MERCK, - plasticizers such as esters, such as phthalates or adipates, ethers, such as di-methyl iso-sorbide, amides - thermal stabilizers and / or UV, such as stearates of tin, lead, zinc, cadmium, barium or sodium, including the Thermolite® ARKEMA, the ceramic powder, hydroxide magnesium, hydrotalcites, magnesium carbonates and other alkaline earth carbonates, zinc oxide, zinc stannate, zinc hydroxystannate, zinc phosphate, zinc borate, zinc sulphide, aluminum hydroxide, aluminum phosphate and red phosphorus, nitrogen-containing organic compounds belonging to the class of triazines such as melamine and / or its derivatives such as melamine cyanurate. The zinc-based compounds, such as zinc borate, may be present in proportions of between 0.01 and 5% by weight, preferably between 0.1 and 5% by weight, relative to the total weight of the material. epoxides, sulphides or laco-stabilizers, such as natural oils

antioxidants, for example phenolic, phosphitic, UV stabilizers, fillers, antistatic agents, fungicides and biocides, blowing agents for the production of expanded parts, such as azodicarbonamides, azobisobutyronitrile, diethyl azobisobutyrate, flame retardants, including antimony trioxide, tin, molybdenum and / or bismuth derivatives, as well as boron and zinc oxides, calcium borates, calcium and / or zinc stannate, zinc borate, aluminum trihydroxide, magnesium dihydroxide, brominated flame retardants such as poly (pentabromobenzyl (meth) acrylate), and brominated or chlorinated phosphate esters, ammonium phosphates, phosphinates, pyrophosphates and polyphosphates, melamine cyanurates, metal salts of phosphonic or phosphinic acid, red phosphorus, decabromodiphenyl ether, and pentaerythritol; solvents, and - their mixtures. The use of a filler is particularly preferred. The strength, heat resistance and dimensional stability of the materials made according to the present invention can be improved by a load. In the present invention, there is no particular limitation on the material of which the charge is made and, as specific examples, mention may be made of silica gel, alumina, carbon black, copper, iron, nickel, zinc, tin, stainless steel, aluminum, gold, silver and other metal powders, silica, fumed silica , aluminum silicate, calcium silicate, silicic acid, hydrated calcium silicate, hydrated aluminum silicate, carbon nanotubes, glass, for example in the form of solid or hollow glass beads , quartz powder, mica, talc, clay, titanium oxide, iron oxide, zinc oxide, calcium carbonate, magnesium carbonate, magnesium oxide, calcium oxide, magnesium sulfate, potassium titanate and diatomaceous earth. When a filler is present, its content is preferably between 1 and 50% by weight and better still between 1 and 25% by weight relative to the total weight of the material. If this content is less than 1% by weight, the reinforcing effects of the filler are not obtained sufficiently, while if the content exceeds 50% by weight, the material obtained can become fragile. The material manufactured according to the invention from supramolecular polymer has excellent fireproofing properties. Thus, this material can be used in electrical or electronic components requiring high levels of fireproofing and in automotive components for example elements for contact support of electromagnetic switches and circuit breakers, platelets, such as platelets. printed circuit boards, integrated circuit packages and electrical component packages. Specific examples of electrical or electronic components include current receiving panels, power distribution panels, electromagnetic switches, circuit breakers, transformers, electromagnetic contacts, circuit protectors, relays, transformers, various types of sensors, various types of motors, diodes, transistors and integrated circuits and other semiconductor devices.

In addition, it is also possible to use preferably the materials manufactured according to the invention as an alternative or combination (in the form of alloys, multilayer materials, assembled materials) to materials made from traditional elastomers, or semi-rigid thermoplastics. Without pretending to axhaustivity, the following fields of application can be cited. Building or construction industry: gaskets or insulation, insulating underlayment for tiles, parquet, soundproofing material, tubes, ducts, pipe or duct coverings, small profiles. Transportation industry: assembly and sealing joints, bellows, tubes, sheaths or coverings of such tubes and sheaths, casings and tanks, silent blocks and other parts having damping functions, anti-vibration device, upholstery or interior lining, tarpaulins, bumper, leisure industry: games, toys, sporting goods, coated textiles. In addition to being used in the form of molded articles, the materials according to the invention made from supramolecular polymer can also be used as a flame retardant film or coating for molded or extruded articles, as mentioned above. above, or for covering cables, or for fibers. Thus, preferably the material made from supramolecular polymer is included in an automobile component, an electrical component, an insulating device, a coating, a game, a toy, or a sporting article. The objects described above can be obtained for example by using a single-screw or twin-screw extruder, a mixer, a kneader, a mixing roll or other usual melting and kneading machines, and then forming into a prescribed shape by injection molding, extrusion molding, vacuum molding by calendering, rotational molding, thermoforming, or blowing and the like.

The invention will be better understood in the light of the following examples, given for purposes of illustration only, and which are not intended to limit the scope of the invention, defined by the appended claims.

EXAMPLES

EXAMPLE 1 Preparation of a Supramolecular Polymer (A) First Step: Sub-step a: In a reactor of diameter 60 mm and nominal volume 500 ml equipped with a bottom valve, a temperature regulation by fluid coolant, mechanical agitation, a dropping funnel, a Dean-Stark and a gas inlet, preheated to 40 ° C, 76 g of Empol® 1016 [acid number 194, monomer level (4%), dimer (80%), trimer (16%) and 6.7 g of purified UDETA (52 mmol), a [NH 2] / [COOH] ratio of 0.2. The bath temperature is raised to 150 ° C for 8 hours under a flow of nitrogen of 500 ml / minute and stirring of 280 rpm. During this step, the reduction of the 8NH2 signal (1505 cm-1), the increase of the signal vC = 0 (1648 cm-1) and the evolution of water vapor are observed by infrared spectroscopy. Stopping the reaction is decided when the release of steam ceases (8 hours in the present example).

After this substep, the product of the reaction is stored at 50 ° C in the reactor.

- Sub-step b: We use the same assembly and the same conditions (nitrogen, stirring) as before. 10.7 g (104 mmol) of diethylene triamine (purity 98%) are placed in the dropping funnel. The reactor body is heated to 160 ° C and the amine is slowly added dropwise intermittently over a total of 3 hours. The reaction is allowed to continue for another 4 hours at 160.degree. During this second step infrared spectroscopy shows the same type of evolution as before. The end of the release of water vapor, again noted, is used as a criterion for stopping the reaction. After this step, the product is collected by the bottom valve (86 g are collected) and stored at room temperature. It is a highly adhesive viscoelastic liquid on many substrates including glass, metal and paper. The glass transition temperature measured by DSC (Differential Scanning Calorimetry) is -11 ° C. Rheological measurements made in plane parallel geometry with an imposed deformation of 1% provided, at the loading frequency of 1 rad / s, the following results: T (° C) 25 35 50 70 90 G '(Pa) 33078 9812 1884 234 34 G "Pa) 49311 17568 4695 947 225 Second stage: In a large reactor (diameter 100 mm) of nominal volume 500 ml equipped with a thermal fluid temperature regulation, a mechanical stirrer and an inlet of gas preheated to 80 ° C., 67 g of the above product and 6.1 g of urea are introduced, the stirring is adjusted to 50 revolutions / min and the temperature is raised to 135 ° C. After one half At this temperature and throughout the process, a significant amount of ammonia is detected using a pH indicator paper.Throughout this step, monitoring the reaction by infrared spectroscopy reveals the decrease in Urea signal vC = O 1675 cm-1 The temperature is maintained in total two hours at 135 ° C, then 1 hour at 140 ° C, then one hour at 145 ° C. At this stage, it is found that the initially turbid reaction mixture tends to become transparent. One gram of water is added and the solution becomes cloudy again. The mixture is heated to 150 ° C. for a further period of approximately 1 hour, during which a decrease in the evolution of ammonia is observed.

The stopping criterion is this time that the product is solid and clings to the axis of the agitator. As soon as it is the case, the product is collected on the stirring rod.

Formatting: The pieces obtained are placed in a plastic bag and cold ground with a hammer. Fragments of size 1 to 2 mm are washed by immersion in water for 72 hours. In the water, the washed fragments tend to stick to each other. The sample, previously drained, is redrawn into pieces of approximately 5 mm in size and placed in a mold made of a 1.6 mm thick brass plate pierced with a rectangular hole, placed between two sheets of paper. anti adhesive. After a first pressing at 120 ° C. for 10 minutes (applied pressure 10 MPa), the film obtained has thickness irregularities which are corrected by addition of material and repressing until a satisfactory appearance is obtained.

EXAMPLE 2 Preparation of a Supramolecular Polymer (B) In a Schott reactor with a useful volume of 4000 ml, placed on an electric balloon heater and equipped with a temperature probe, mechanical stirring with a poly-anchor type mobile ethylene tetrafluoro, a dropping funnel, a condenser condenser, a Dean-Stark and a nitrogen inlet terminating in a polytetrafluoroethylene dipping rod, 1000 g of PripolTM 1040 from Croda are introduced (acid number 186), ie 3.32 moles of carboxylic acid and 245 g of UDETA at 87.6% purity by weight, ie 1.66 moles of amine). It is assumed that the impurities of the UDETA can provide the equivalent of 0.13 mol extra. The mixture is heated to 170 ° C to remove the condensation water. When the condensation water is removed and trapped in the Dean-stark, the medium is cooled to 80 ° C. At 80 ° C., 294 g of a DGEBA type epoxy resin, EpikoteTM 828 EL from Resolution (epoxide level of 5.2 mol / kg), or 1.53 mol, are added and the mixture is left stirring at 80 ° C for 15 minutes. The product thus obtained is emptied from the reactor and can be stored without cooking in polypropylene pots. To obtain the final hybrid elastomeric material, an oven baking at 120 ° C. for 24 hours is carried out, preferably in a 5 mm thick layer in a non-adherent support, such as trays coated with poly tetrafluoroethylene.

EXAMPLE 3 Preparation of a Supramolecular Polymer (C) In a Schott reactor of useful volume 4000 ml, placed on an electric balloon heater and equipped with a temperature probe, a mechanical stirring with a mobile anchor type poly ethylene tetrafluoro, a dropping funnel, a condenser condenser, a Dean-Stark and a nitrogen inlet terminating in a polytetrafluoroethylene dipping rod, 1000 g of PripolTM 1040 from Croda are introduced (acid number 186), ie 3.32 moles of carboxylic acid and 245 g of UDETA at 87.6% purity by weight, ie 1.66 moles of amine). It is assumed that the impurities of the UDETA can provide the equivalent of 0.13 mol extra. The mixture is heated to 170 ° C to remove the condensation water. When the condensation water is removed and trapped in the Dean-stark, the medium is cooled to 120 ° C. At 120 ° C., 414 g of Arkema EcepoxTM PB 3 epoxidized soybean oil (epoxide level of 3.7 mol / kg), ie 1.53 mol, are added and the mixture is stirred at 120 ° C. for 15 minutes. The product thus obtained is emptied from the reactor and can be stored without cooking in polypropylene pots. To obtain the final hybrid elastomeric material, baking in an oven at 120 ° C. for 48 hours is carried out, preferably in a 5 mm thick layer in a non-adherent support, such as trays covered with poly tetrafluoroethylene. The product is sticky and may be talcated on the surface to facilitate its handling and in particular the measurement of mechanical properties.

Example 4: Fire resistance tests The properties are determined on test pieces, according to the following methods: - The flame resistance is measured according to standard IEC 60695-11-10, edition 1.1, 08-2003 method B. Specimens 2-3 mm thick, 80 mm long and 10 mm wide were used. The test pieces are conditioned at room temperature. The result is coded as follows: V-2: the average burning time is less than 25 seconds, the maximum burning time is less than 30 seconds (self-extinguishing); drop of polymer igniting the cotton; no residual flame or incandescence of the sample up to the collet V-1: average combustion time is less than 25 seconds, the maximum combustion time is less than 30 seconds (self-extinguishing); no inflammation of the cotton. V-0: average combustion time is less than 5 seconds, the maximum burning time is less than 10 seconds (self-extinguishing); no inflammation of the cotton. The test results are as follows: The test piece made from the supramolecular polymer (A) of Example 1 was classified VO; The test piece made from the supramolecular polymer (B) of Example 2 was classified as V2. Example 5: Measurement of the limit oxygen index (ILO)

The purpose of this test is to determine the minimum oxygen concentration, in an oxygen / nitrogen mixture, which can sustain the combustion of a vertical test specimen under test conditions specified in ISO 4589-2. July 1996. The results are defined as values of the oxygen index at the test temperature, which is characteristic of the temperature at which a plastic material is likely to be subjected to conditions of use with overheated

With supramolecular polymer (A) of Example 1, the value of ILO is greater than 40%. With the supramolecular polymer (B) of Example 2, it is 23%. 10

Claims (12)

REVENDICATIONS1. Use, for the manufacture of a fire-resistant material, of at least one supramolecular polymer obtainable by the reaction of at least one at least trifunctional compound (A) carrying first and second functions with: at least one compound (B) bearing, on the one hand, at least one reactive group capable of reacting with the first functions of (A) and, on the other hand, at least one associative group; and at least one at least one bifunctional compound (C) whose functions are capable of reacting with the second functions of the compound (A) to form ester, thioester or amide bridges. 2. Use according to claim 1, characterized in that the compound (A) is a trimer of at least one of the following acids, undecylenic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, eicosenoic acid, docosenoic acid, eicosapentaenoic acid and docosahexaenoic acid. 3. Use according to claim 1 or 2, characterized in that the compound (A) is a mixture of fatty acid trimer and dicarboxylic acid selected from: a linear alkyl dicarboxylic acid including glutaric acid, adipic acid, pithelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, thapsic acid, octoctadecanedioic or branched acid including 3,3-dimethylglutaric acid. 4. Use according to any one of claims 1 to 3, characterized in that the compound (B) corresponds to one of the formulas (B1) to (B5). Wherein R denotes a unit containing at least one reactive function, R 'denotes a hydrogen atom, R ", R1 and R2 denote any group A denotes an oxygen or sulfur atom or an -NH group, preferably an oxygen atom. 5. Use according to claim 4, characterized in that the compound (B) is chosen from 2-aminoethylimidazolidone, 1- (2 - [(2-aminoethyl) amino] ethyl) imidazolidone, 1- (2- {2 [(2-aminoethylamino] ethyl] amino) ethyl] imidazolidone, N- (6-aminohexyl) -N '- (6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl) urea, 3 -amino-1,2,4-triazole and 4-amino-1,2,4-triazole. 6. Use according to any one of claims 1 to 5, characterized in that the compound (C) carries at least two functions, identical or different, selected from epoxy functions, alcohol and amine. 7. Use according to claim 6, characterized in that the compound (C) corresponds to the formula (I): H2N- (CHR1) rr, - (CHR2) n- [NH- (CH2), Jy NH- (CHR3) p- (CHR4) q -NH2 (I) wherein: R1, R2, R3 and R4 independently denote a hydrogen atom or a C1-C6 alkyl group such as a methyl group, m, n, p and q independently denote an integer from 1 to 3, wherein x is an integer from 1 to 6, y is an integer from 0 to 2. 8. Use according to claim 7, characterized in that, in the formula (I), at least one, and preferably all, the following conditions are satisfied: - R1r R2, R3 and R4 denote an atom of hydrogen, - m + n is equal to 2, 3 or 6, preferably 2, - p + q is equal to 2, 3, or 6, preferably 2, - x denotes an integer ranging from 2 to 4, y is 0 or 1, preferably 0. 9. Use according to claim 8, characterized in that the compound (C) is chosen from: diethylene triamine, triethylene tetramine, tetraethylene pentamine, dihexylene triamine. 10. Use according to any one of claims 1 to 9, characterized in that the supramolecular polymer as defined above in claims 1 to 9 is reacted with urea. 11. Use according to any one of claims 1 to 10 characterized in that the material further comprises an elastomer and / or an additive selected from a filler, a thermal stabilizer and a flame retardant. 12. Use according to any one of the preceding claims characterized in that the material is included in an automotive component, an electrical component, an insulating device, a coating, a game, a toy, or a sport article.