Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms

Definitions

• the present invention relates to the field of plasticizers, compounds used as additives in polymers to facilitate their transformation or to modify their mechanical properties, in particular their rigidity.
• the invention therefore relates to the use as a plasticizer in a plastic material of a molecule of average molecular mass greater than 500 g / mol, carrying at least one associative group comprising a nitrogenous heterocycle.
• plasticizer means a compound corresponding to one and preferably two, three or all the following definitions: (1) This is a product that meets the definition given in ASTM D883, "Plastics Nomenclature”. published by American Society for Testing Materials, Philadelphia, PA.
• It is a compound which, when added to a polymer, modifies the glass transition temperature and in particular lowers the glass transition temperature of a polymer by at least 2 ° C, at least 3 ° C or at least 4 ° C, preferably at least 5 ° C when added in sufficient amount.
• the lowering of the glass transition temperature is a function of the amount of plasticizer compound in the composition. This amount should be such that it is sufficient to cause a decrease, an effective lowering of the glass transition temperature of the polymer.
• plasticizer is understood to mean a compound corresponding to definition (4) above.
• the glass transition temperature, or Tg is a property associated with amorphous and semi-crystalline polymers. crystalline (because of the existence in them of an amorphous part).
• the Tg of a polymer can be measured by various techniques capable of detecting a significant change in property passing through the Tg, such as dilatometry or calorimetry, due to changes in specific volume or heat capacity associated with the passage of time.
• properties that make it possible to detect the Tg are also the refractive index, the rigidity (expressed in the form of hardness, mechanical modules, etc.). Since Tg is physically associated with molecular mobility, techniques capable of translating phenomena related to this mobility such as dielectric spectroscopy, nuclear magnetic resonance, dynamic mechanical analysis, etc. can also be used to detect Tg.
• the Tg is measured by applying to the sample (and possibly to the reference, as in the differential calorimetry) a ramp rising or falling temperature.
• the glass transition temperature of the polymer is measured either by calorimetry or by dynamic mechanical analysis.
• a compound is a plasticizer according to one of the preferred embodiments of the invention, provided that one or both measurement methods make it possible to observe a reduction in the Tg of the polymer by at least 2 ° C. at least 3 ° C or at least 4 ° C, preferably at least 5 ° C when added in sufficient amount.
• the measurement of calorimetry is carried out using a differential scanning calorimeter, for example the calorimeter sold under the name MDSC 2920 or also under the name Q2000, by the company TA Instruments, by the technique known as differential scanning calorimetry or DSC.
• the calorimeter is used to measure the difference in energy required to maintain a sample of the product and a reference cell containing only air at the same temperature during the test. Tests can be made with this equipment in isothermal or temperature ramp mode. For Tg measurements, a rise or fall temperature ramp, set at a rate of 10 or 20 ° C / min, is applied. The Tg is measured in the glass transition zone, either at the first point of inflection of the rising ramp DSC signal or at the central point of the transition.
• the glass transition temperature of the polymer is first measured by one of the methods described above, then a mixture of the polymer and the compound is prepared and the measurement is carried out by the same method and under the same conditions.
• Dynamic mechanical analysis is conducted according to the method detailed below.
• the sample which does not comprise a plasticizer compound and the sample comprising it are also compared by carrying out measurements under the same conditions.
• the signals given by the dynamic mechanical analysis are, the complex module, M *, the real and imaginary parts, M 'and M'', respectively of the complex module and the delta tangent, defined as the ratio M''/M' .
• Tg is taken, by convention, either at the maximum of the signal from M '' or at the maximum of the signal of delta tangent or at the first point of inflection of the signal of M 'or M *.
• the plasticizer decreases Young's elastic modulus, E, or shear modulus, G, at a given temperature or temperature range.
• the range of temperature at which this module decrease occurs relative to the unplasticized product module is a range of interest for material applications.
• the range of temperature at which the modulus of the modified material is decreased is -50 ° C to 250 ° C. Module measurements as a function of temperature can be carried out by different tests or measuring devices such as small or large deformation mechanical tests.
• the Young's elastic modulus measurements as a function of the temperature making it possible to determine whether a compound is a plasticizer according to the invention are carried out by mechanical small-strain tests, using a dynamic mechanical analysis apparatus or DMA, such as the DMA Q800 device from the company TA INSTRUMENTS.
• DMA dynamic mechanical analysis apparatus
• the dynamic mechanical analysis has as principle the periodic solicitation of the sample, whose response to this solicitation is also periodic and more or less offset in time. For essentially elastic materials, this shift is practically zero, whereas for materials with behavior viscoelastic (very characteristic of polymer systems), this shift is significant and proportional to the viscoelastic nature.
• the tests are carried out, in general, by applying a sinusoidal stress
• the two signals are, therefore, more or less offset (phase shift).
• the stress is chosen so as to cause a deformation sufficiently small to remain in the field of study of linear viscoelasticity where stress and strain are linked by a parameter independent of the applied stress, the dynamic modulus.
• the apparatus DMA Q800 (TA INSTRUMENTS) performs measurements with sinusoidal deformations in the linear domain at constant frequency, for example of 1.0 Hz.
• the measurements of E *, E ', E''and tan ⁇ are carried out temperature function to highlight the differences in modulus between a pure polymer without plasticizer and the additive polymer of the plasticizer. More precisely, the follow-up of the complex modulus, E *, or of the real part, ⁇ ', is used to highlight the plasticizing effect (modulus decrease with respect to the modulus of the unplasticized polymer) in the temperature range d 'interest.
• the ramp rate for the temperature change is controlled and is 1 ° C / min, 2 ° C / min or 3 ° C / min.
• carrier in the sense of the present invention means that the molecule and the associative group are linked by one or more covalent bonds.
• sociative groups groups capable of associating with each other by hydrogen, ionic and / or hydrophobic bonds. It is a preferred embodiment of the invention of groups capable of associating with one another. hydrogen bonds, comprising a di or tri-nitrogen heterocycle generally of 5 or 6 atoms, preferably diazotized, and comprising at least one carbonyl function.
• each associative group comprises at least one donor "site” and one acceptor site with respect to the hydrogen bonding, so that two identical associative groups are autonomous. and can associate with each other by forming at least two hydrogen bonds.
• the associative group-bearing molecule has an average molecular mass of greater than 600 g / mol, and preferably greater than 700 or 1000 g / mol.
• the molecule carrying at least one associative group is in the form of a supramolecular polymer comprising molecules linked in a network by reversible physical bonds and / or in the form of a hybrid network comprising molecules bound in network by both reversible physical bonds and covalent bonds.
• the molecule carrying at least one associative group is a supramolecular polymer that can be obtained by the reaction of at least one at least bifunctional compound (A) carrying first and second functions with:
• supramolecular materials 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.
• the inventors have shown in the examples of the present application that the molecules carrying associative groups according to the invention have a lower migration and lower volatility than conventional plasticizers, while having excellent efficiency with regard to plasticization.
• plastics that can be plasticized by the molecule carrying associative groups
• cellulose derivatives such as cellulose acetate, cellulose acetate butyrate, cellulose nitrate, ethyl cellulose
• polyamides such as homo- and copolymers obtained by polymerization of lactam monomers (in particular caprolactam or lauryl lactam) and / or ⁇ , ⁇ -amino carboxylic acid (such as 11-aminoundecanoic acid or 12-aminododecanoic acid), polymers consisting of monomers obtained by reaction of a C 6 -C 14 aliphatic, cycloaliphatic or aromatic dicarboxylic acid
• copolymers containing monomers of the two families of polyamides mentioned above acrylic homo- and copolymers such as polymethyl methacrylate and its copolymers, polycarbonate , styrenic polymers such as polystyrene, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), halogenated vinyl polymers such as polychloride of vinyl (PVC), polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride
• PVDF acrylonitrile copolymers
• polyethers and polymers of vegetable or bacterial origin such as poly (lactic acid) or polyhydroxyalkanoates, polyvinyl acetate, and polyvinyl butyral.
• the plastic material may also be an elastomer, and in particular an elastomer chosen from rubber (or elastomeric) polymers having one or more glass transition temperature (s) lower than their temperature of use, that is, materials relatively flexible at the temperature of use, having at least one characteristic property of the rubbery elasticity, such as springback after significant deformations
• Ladders, c. 2008 (for example in Chapters 1 and 13). Those skilled in the art know these properties under names such as hyperelasticity, rubber elasticity or entropic elasticity. Such materials preferably have a Young's modulus, measured at the temperature of use, of between 1000 Pa and 100,000,000 Pa, and preferably between 50,000 Pa and 50,000,000 Pa. deformations at break greater than 20% and preferably greater than 100%.
• the elastomers used in the present invention have the property of being able to undergo uniaxial deformation at the use temperature, for example at room temperature, of at least 20%, for example for 15 minutes, and recovering, once this constraint is released, most of their initial dimension, for example, with a remanent deformation less than 10% of its initial dimension.
• elastomers are either of natural origin, such as elastomeric polymer materials derived from the exploitation of natural latex, or of synthetic origin, such as polymers or copolymers obtained by chain polymerization, catalytic or in stages, involving a majority of mass monomers. low molecular weight, typically less than 400 g / mol, or even less than 300 g / mol.
• Both the elastomers derived from the natural latex and the synthetic elastomeric polymers can also be chemically modified by functionalization reactions on the previously formed polymer chains.
• the halogenated elastomers can be obtained by total or partial halogenation of the double bonds still present in the polymer chains.
• certain hydrogenated elastomers are obtained by reactions of partial or total hydrogenation of these remaining double bonds.
• elastomers mention may be made, as a non-limiting example, of natural rubber, polybutadiene, synthetic polyisoprene, polychloroprene and their hydrogenated versions, polyisobutylene, block copolymers of polybutadiene and isoprene with styrene.
• polystyrene-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
• SEBM hydrogenated version
• SEBM poly (methylmethacrylate) -b-butyl acrylate-b-methyl methacrylate
• MAM poly styrene-b-butyl acrylate-b-styrene
• the elastomer may comprise one or more crosslinked elastomers or not, virgin or derived from one or more recycling.
• the elastomer comprises or consists exclusively of recycled elastomeric polymers, either thermoplastic or recycled crosslinked rubber.
• the supramolecular polymer is capable of being obtained by the reaction of at least one at least bifunctional 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 and possibly with the second functions of (A) and, secondly, at least one associative group.
• sociative groups 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.
• 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.
• the associative group (s) of the compound (B) and the reactive groups or functions thereof may be connected to one another by a linear or branched C1-C24 or preferably C1-C10 alkylene chain optionally interrupted by one or more atoms of nitrogen, more preferably a C1-C6 linear alkylene chain.
• 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.
• the compound (A) represents more than 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 two identical functions or different selected 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.
• Compound (A) may be in the form of a mixture of bifunctional compounds and mono- and / or polyfunctional compounds, such as monoacids and polyacids, in particular tri-, tetra-, pentaacids, or the like.
• fatty acid monomers and oligomers of fatty acids derived from at least three monomeric units of fatty acids, for example tetramer, pentamer, etc. 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 may or may not contain minor amounts of monomers and higher oligomers d 'Fatty acids.
• Oligomerization of unsaturated fatty acids such as undecylenic, myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic and docosenoic acids, which are commonly found in tall oil fatty acids, rapeseed, corn, sunflower, soy, grape seed, linseed, jojoba, castor, as well as the eicosapentaenoic and docosahexaenoic acids found in fish oils.
• unsaturated fatty acids such as undecylenic, myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic and docosenoic acids, which are commonly found in tall oil fatty acids, rapeseed, corn, sunflower, soy, grape seed, linseed, jojoba, castor
• 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, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, thapsic acid, octadecanedioic or branched acid such as 3,3-dimethylglutaric acid.
• a linear alkyl dicarboxylic acid such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, t
• the compound (A) is a mixture comprising 15 to 100% of fatty acid dimers, the balance being composed of monomers and / or trimers and / or higher oligomers of fatty acids.
• dimers and trimers of fatty acids that may be mentioned are the compounds of the following formulas which illustrate the cyclic trimers and dimers derived from fatty acids containing 18 carbon atoms, given that the compounds available commercially are mixtures of steric isomers and positional isomers of these structures, possibly partially or fully hydrogenated.
• oligomers of fatty acids containing dimers, trimers, higher oligomers and monomers of linear or cyclic Cis fatty acids, said mixture being predominant in dimers and trimers and containing a small percentage (usually less than 5%) of higher monomers and oligomers.
• said mixture comprises:
• said mixture of molecules derived from fatty acids has an average molecular weight of greater than 500 g / mol.
• dimeric / trimeric mixtures of fatty acids are: Pripol® 1017 from Uniqema, a mixture of 75-80% of dimers and 18-22% of trimers with about 1-3% of monomeric fatty acids,
• Uniqema Pripol® 1006 a mixture of 92-98% dimers and up to 4% trimers with a maximum of 0.4% of monomeric fatty acids
• Uniqema Pripol® 1040 a blend of dimers and fatty acid trimers with at least 75% trimers and less than 1% monomeric fatty acids
• Arizona Chemicals Unidyme® 60 33% blend dimers and 67% trimers with less than 1% monomeric fatty acids
• Unidyme® 40 from Arizona Chemicals, a blend of 65% dimers and 35% trimers with less than 1% monomeric fatty acids,
• Unidyme® 14 from Arizona Chemicals, a blend of 94% dimers and less than 5% trimers and other higher oligomers with about 1% monomeric fatty acids,
• Empol® 1008 from Cognis, a mixture of 92% of dimers and 3% of higher oligomers, essentially of which trimers, with about 5% of monomeric fatty acids,
• Empol® 1018 from Cognis, a mixture of 81% of dimers and 14% of higher oligomers, essentially of which trimers, with about 5% of monomeric fatty acids, • Oleon's Radiacid® 0980, a mixture of dimers and trimers with at least 70% trimers.
• Radiacid® 0950 from Oleon a mixture of 79-85% dimers and 13-19% fatty acid trimers with 1-3% monomeric fatty acids.
• Pripol®, Unidyme®, Empol®, and Radiacid® products include Cis fatty acid monomers and oligomers of fatty acids corresponding to multiple amino acids.
• 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.
• ester 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.
• fatty acid chloride mention may be made of sebacoyl chloride.
• the compound (B) carries at least one reactive group which may in particular be selected 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.
• the ratio of the number reactive groups of the compound (B) to the sum of the functions of the compound (A) ranges from 0.05 to 1.10 and preferably from 0.15 to 1.
• the supramolecular polymer is capable of being obtained by further reaction with 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 bridges. ester, thioester, amide, when said second functions of the compound (A) have not reacted with the compound (B).
• the ratio of the number of reactive groups of the compound (B) to the sum of the functions of the compound (A) is from 0.05 to 0.8 and preferably from 0.15 to at 0.7.
• compound (B) can thus satisfy any one of formulas B1) to (B5)
• R denotes a unit containing at least one reactive function
• R 'de notes a hydrogen atom
• R ", R1 and R2 denote any groups, especially a C1-C50 alkyl group
• A denotes an oxygen or sulfur atom or an NH group, preferably an oxygen atom.
• Preferred examples of compounds (B) are 2-aminoethylimidazolidone (UDETA), 1- (2-hydroxyethyl) imidazolidone [HEIO], 1- (2 - [(2-aminoethyl) amino] ethyl) imidazolidone (UTETA) 1- [2- ⁇ 2 - [(2-aminoethylamino] ethyl ⁇ amino) ethyl] imidazolidone
• UDETA N- (6-aminohexyl) -N '- (6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl) urea (UPy), and N- (6-) aminobutyl) - '- (6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl) urea, 3-amino-1,2,4-triazole and 4-amino-1,2,4 triazole.
• UDETA is preferred for use in the present invention.
• UDETA, UTETA and UTEPA can be respectively prepared by reacting urea with diethylene triamine (DETA), triethylene tetramine (TETA) and tetraethylene pentamine (TEPA).
• DETA diethylene triamine
• TETA triethylene tetramine
• TEPA tetraethylene pentamine
• the HEIO compound can be obtained by reacting the urea with the corresponding diamino alcohol, namely 2 - [(2-aminoethyl) amino] ethanol.
• the reaction of the compound (B) with the compound (A) may for example be carried out at a temperature of between 20 and 200 ° C., preferably between 130 and 170 ° C., for a period ranging from 1 to 15 hours, for example from 3 to 9 h, advantageously with stirring and under an inert atmosphere.
• the product resulting from the reaction of the compounds (A) and (B) can be used directly as a plasticizer according to the invention.
• the compound (B) has reacted only with the first functions of (A)
• the compound resulting from the first reaction step (A) + (B) can be reacted with a compound ( C) in a second step involving the second functions of the compound (A).
• the compound resulting from the first reaction step, (A) + (B) can then be reacted with an at least bifunctional compound (C), so 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.
• the 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 diglycidy
• 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 and epoxidized limonen
• the compound (C) may be a diol.
• the compound (C) can be chosen from: ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol,
• the compound (C) may be a polyol containing at least three alcohol functions.
• examples of such compounds are in particular: sugars such as sorbitol, pentaerythritol, trimethylolpropane, as well as glycerol and its ethoxylated and propoxylated derivatives, castor oil and diol dimers derived from fatty acids such as Pripol®
• 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):
• R1, R2, R3 and R4 independently denote a hydrogen atom or a C1-C6 alkyl group such as a methyl group
• n, p and q independently denote an integer ranging from 1 to 3,
• x denotes an integer ranging from 1 to 6,
• y denotes an integer ranging from 0 to 2.
• R1, R2, R3 and R4 denote a hydrogen atom
• M + n is 2, 3 or 6, preferably 2,
• P + q is 2, 3 or 6, preferably 2,
• X denotes an integer ranging from 2 to 4,
• y is 0 or 1, preferably 0.
• polyamines of formula (I) are DETA (diethylene triamine), TETA (triethylene tetramine), TEPA (tetraethylene pentamine) and dihexylene triamine.
• 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.
• the polyamine may be a di or triamine derived from vegetable fatty acid dimers and trimers, such as Versamine® 551 from Cognis.
• reaction of the polyamine (compound (C)) with the second functions of the product resulting from a first reaction step (A) + (B), functions which correspond, as previously described, to carboxylic acids or their salt, ester or acid chloride, may, for example, be carried out at a temperature between 20 and 200 ° C, preferably between 140 and 180 ° C, for a period of from 1 to 24 hours, for example from 6 to 8 hours, advantageously with stirring and under an inert atmosphere.
• all the functions of the compound (A) remaining after the first reaction stage having engaged the first functions of (A) with reactive functions of the compound (B), are reacted in a stoichiometric proportion with the reactive functions of the compound (C).
• the supramolecular polymer used in the uses of the invention is derived from the reaction of the compound (A) with the compound (B) and optionally 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.
• the supramolecular polymer defined above is reacted with urea.
• 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.
• This reaction can also be carried out at a fixed temperature of between 110 and 160 ° C for a fixed time ranging from 10 minutes to 24 hours.
• 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 urea has the function, in this step, to create additional associative groups, for example according to the following reaction schemes:
• the compounds (A), (B) and (C) described above can be used, in the molten state, 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 solid state powder or in the molten state to avoid the use of solvents that need to be subsequently removed.
• 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 synthesis process of the supramolecular polymer, as well as that their nature, and the choice of whether or not to carry out an additional reaction step with urea determine the mechanical characteristics of said supramolecular 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.
• 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 defined above are materials in the form of soft solids, which must be extracted from the reactor used for their synthesis.
• the product can be extracted from the reactor in the liquid state and
• 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.
• the associative group-bearing molecule defined above can be used in combination with a customary plasticizer chosen from adipates, such as diethyl adipate, di (2-ethyl hexyl) adipate, dimethoxyethyl adipate, and azelates, such as dicyclohexyl azelate.
• adipates such as diethyl adipate, di (2-ethyl hexyl) adipate, dimethoxyethyl adipate, and azelates, such as dicyclohexyl azelate.
• the associative group-bearing molecule defined above can also be used in combination with other customary additives for polymer formulations such as thermal stabilizers and UV stabilizers, fillers, dyes, pigments, and optical modifiers such as the brighteners.
• other customary additives for polymer formulations such as thermal stabilizers and UV stabilizers, fillers, dyes, pigments, and optical modifiers such as the brighteners.
• a heat transfer fluid such as oil from a thermostatic bath, 145 g of Pripol® 1017 acid dimer / trimer acid (mg KOH / g of product necessary to neutralize the acid groups) 193.4, and heated to 60-80 ° C with stirring. 161 g of 2-aminoethylimidazolidinone (UDETA) are then slowly added to the mixture. 88 mol% purity preheated (ie 60 ° C.) and homogenized by stirring. The reaction medium is then brought to 160 ° C. so as to cause the amino reaction (
• UDETA UDETA
• dimer / trimer mixture of fatty acid by extracting the condensation water, in particular through a sweeping of the reactor sky with nitrogen. The The reaction is allowed to continue for 16 hours, after which the reaction medium is cooled. The supramolecular polymer "SC" is then obtained. The solidification point of the polymer SC is identified at 61 ° C. and the residual acid number obtained is 1.49.
• the polymer is also characterized by a Tg of -15 to -10 ° C. determined using a DSC Q10 apparatus marketed by TA INSTRUMENTS.
• SC polymer designates the product synthesized in Example 1.
• Example 3 Study of the plasticization of polyamides by the SC polymer.
• the mixtures defined in Table 1 below were made on a DSM® bi-screw micro-extrudese with a capacity of 15 cm 3 .
• the temperature is set at 210 ° C (the temperature measured in the extruder is about 200 ° C).
• the speed of the screws is 100 RPM and the mixture lasts 2 minutes under a nitrogen sweep.
• tensile specimens are molded with a mini DSM ® brand injection molding machine.
• the temperature of the sheath is set at 210 ° C, that of the mold at 50 ° C and the pressure is maintained for 15 seconds.
• the indicated rates are the rates introduced into the machine, it is possible that slight differences exist with the composition of the final product, these small differences do not affect the results.
• the polyamide used is a BMNO (Polyamide 11 marketed by Arkema under the name Rilsan® BMNO).
• the SC polymer product is that synthesized in Example 1.
• BBSA butylbenzenesulfonamide
• BBSA butylbenzenesulfonamide
• Assays were performed using TA Instruments DMA® 2980 on previously prepared test pieces, applying a heating rate of 3 ° C / min and a frequency of 1 Hz.
• SC plasticizes but less than 8% BBSA, the effect is rather similar to that obtained SVGC 4% BBSA. It is observed that the mixtures of BBSA and 8% of SC polymer have a behavior similar to a plasticized nylonamide 8 SVGC 8% BBSA.
• BMNO absorbs gasoline, which increases its mass.
• the product with BBSA swells 7% less, which is due to the departure of BBSA.
• the SC polymer blend swells 4% less than BMNO alone, which is further proof that the SC polymer is less extracted than BBSA, but this time in a gasoline.
• BMNO + Polymer SC blends in 70/30 mass proportions are made using a Brabender® brand internal mixer with a capacity of 50 cm 3 . This 30% blend of SC is called the "concentrate”.
• the stirring speed is set at 60 RPM for 4 minutes, the temperature is set at 240 ° C. the products are then milled to be introduced into an extruder.
• Blends with BBSA and SC polymer are made using a Haake® twin-screw extruder.
• the SC polymer is introduced via the previously prepared concentrate.
• the compositions of the mixtures and the conditions used are shown in Table 7 below.
• the temperature profile applied to mixtures BMNO, BMNO polymer + SC + BMNO Polymer SC / BBSA is 150 ° C-220 ° C-230 o C-230 o C-230 ° C.
• the temperature profile applied to the BMNO + BBSA mixture is 170 ° C-240 ° C-230 ° C-230 ° C-230 ° C. Dumbbells are then injected with these formulations according to ISO 527 1BA.
• polyisoprene-based formulations (Natsyn® commercial reference) 2200) are prepared according to the following composition tables 10 and 11.
• the antioxidant is a polymerized 1, 2-dihydro-2,2,4-trimethylquinoline.
• the antioxidant is a polymerized 1, 2-dihydro-2,2,4-trimethylquinoline
• the ingredients are added to the mixer in the following order:
• the mixer is allowed to rotate until the torque is stabilized after the introduction of all the components.
• the formulations obtained are passed through a calender until a slab is obtained and then they are cross-linked in a press at 175 ° C. for 8 minutes.
• Specimens are then cut from the plates and the mechanical properties are measured at using an Instron® tensile machine at 500 mm / min in a room with a temperature of 22-24 ° C and humidity 40 - 60% controlled.
• the SC polymer has a plasticizing effect resulting in an increase in elongation at break.

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