Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D233/30—Oxygen or sulfur atoms
  • C07D233/32—One oxygen atom
  • C07D233/36—One oxygen atom with hydrocarbon radicals, substituted by nitrogen atoms, attached to ring nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
  • C08G83/008—Supramolecular polymers

Definitions

• the present invention relates to novel supramolecular materials based on linear or branched oligomers terminated at each of their ends by an associative group comprising a nitrogen heterocycle carried by a particular sequence. It also relates to the method of preparation of these materials, as well as their uses.
• supramolecular materials are materials consisting of molecules 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.
• these materials also have elastomeric 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. Although they are not composed of crosslinked polymers but small molecules, these materials, like elastomers, are capable of exhibiting dimensional stability over very long times and recovering their initial shape after large deformations. They can be used to make thermal or acoustic insulators, cables, sheaths, shoe soles, packaging, necklaces, resilient clamping, vacuum tubes, or fluid transport tubes.
• the document WO 2006/016041 describes an AEIO (or UDETA) graft-modified polymer or a UDETA derivative.
• the polymer is a polyamide, in particular a copolyamide of the Platamid ® type
• UDETA is grafted onto its acidic ends (which are of different types in the case of Platamid ® ).
• the product of this reaction is therefore composed of a mixture of compounds having different ends of chain.
• This grafting also has the effect of increasing the viscosity of the polyamide, until a value of G "corresponding to a viscosity of 17 Pa.s is reached.
• Example 1 discloses a material formed by reacting adipic acid on a PA-11 type polyamide, followed by the functionalization of the product obtained with UDETA. Again, this compound has a viscosity too high.
• thermoplastic materials such as a high stress and elongation at break, and more particularly a tensile strength greater than 3 MPa, preferably 4 MPa, or even 10 MPa, over a wide temperature range, while maintaining a low viscosity at molten state, similar to that of oils (typically less than 10 Pa.s or even 1 Pa.s). It would thus be possible to improve the processability of these materials, in particular their fiber wetting capacity making it possible to use them in the manufacture of fibrous composites, as well as their recycling capacity and their durability.
• a supramolecular material which differs from those known in that it is semi-crystalline, with a melting point greater than or equal to 120 ° C. and preferably greater than or equal to 140 ° C.
• this material comprises an associative UDETA type group known to increase the viscosity of the polymers on which it is grafted.
• the crystallites present below the melting temperature of the material act as crosslinking points and make it possible to confer on it the desired thermal and mechanical properties.
• This material can be obtained by an easily industrializable process, by polycondensing a diacid, a diamine and a modifier compound carrying an associative group located at the end of a particular sequence, these reagents being used in given stoichiometric ratios. It has been shown that the terminal associative groups, provided they are grafted via this particular sequence, give the material the required melting point and crystallinity, while the central oligo-amide chain has sufficient flexibility to contribute to obtaining the desired mechanical properties.
• the latter is more particularly constituted by an alternation of rigid blocks (formed by the diacid units) and flexible blocks (formed by the diamine units).
• the modifier compound makes it possible to reduce the size of the chains of molecules constituting the material and thus to give it a low melt viscosity.
• the subject of the present invention is therefore a material comprising linear or branched XY oligomers which are more than 90% terminated in number of their ends by the same group -M-L 2 -CO-L 1 -A
• A is a an associative group comprising a nitrogen heterocycle
• Li is a chemical bond or a spacer arm consisting of a saturated or unsaturated hydrocarbon chain, cyclic or not, optionally interrupted by one or more oxygen and / or nitrogen atoms
• L 2 is a saturated or unsaturated hydrocarbon chain, cyclic or not, containing at least 4 carbon atoms, optionally interrupted by one or more oxo groups and optionally substituted by one or more -OH groups and / or one or more chlorine atoms
• M is selected from CO, NH and O (where CO is carbonyl).
• the subject of the invention is also a process for preparing this material, comprising a polycondensation step:
• A is an associative group comprising a nitrogen heterocycle
• Li is a chemical bond or a spacer arm consisting of a saturated or unsaturated hydrocarbon chain, cyclic or not, optionally interrupted by one or more oxygen and / or nitrogen atoms
• L 2 is a saturated or unsaturated hydrocarbon chain, cyclic or not, containing at least 4 carbon atoms, optionally interrupted by one or more oxo groups and optionally substituted by one or more -OH groups and / or one or more chlorine atoms
• W is a reactive group capable of reacting:
• the molar ratio of the acid functions of the diacid to the reactive functions of the modifier compound in this case from 1 to 8, it being understood that the number of moles of amine functions of the diamine is equal to sum of number of moles of the aforementioned acidic and reactive functions,
• the molar ratio of the amine functions of the diamine to the reactive functions of the modifier compound ranging in this case from 1 to 8, it being understood that the number of moles of acid functions of the diacid is equal to the sum the number of moles of the amine and reactive functions mentioned above.
• the present invention further relates to the uses of this material as an additive in bitumens, as a matrix of composite materials, as hot melt adhesive or as an additive in hot melt adhesives.
• n ranges from 4 to 14, as well as its use as a modifying compound in the process according to the invention.
• the supramolecular material according to the invention comprises linear or branched X.Y oligo- amides ending more than 90% in number of their ends with the same particular pattern, and preferably at 100%.
• oligo-amides polycondensates having a low average molecular weight in number, Mn.
• Mn can be predicted according to the molar ratios of the reactants involved in the polycondensation and the degree of progress of the reaction, using conventional formulas, known to those skilled in the art.
• the molar ratios will be chosen such that the Mn predicted by the Stockmayer formula, WH (Journal of Polymer Science 1952, 9, 67-71), and assuming a total conversion, is less than 10,000 g / mol and preferably less than 4500g / mol.
• oligo-amides XY is meant homopolyamides or low-mass copolyamides obtained from at least one diacid and at least one diamine, as opposed to the oligoamides containing units obtained by condensation of amino- acids.
• linear oligo-amide refers to oligomers containing only diacid and diamine units in the chain
• branched oligo-amides refers to oligoamides comprising in the chain one or more polyacid or polyamine units of functionality greater than 2.
• this material comprises oligomers corresponding to formula (Ia) below: X-NH-Ra-NH- [CO-Rb-CO-NH-Ra-NH-] a -X
• Ra denotes a saturated or unsaturated hydrocarbon chain, optionally interrupted by one or more oxygen and / or nitrogen atoms,
• Rb denotes a saturated or unsaturated hydrocarbon chain
• a denotes the average number of units per chain and is greater than 0 and less than or equal to 20, preferably less than or equal to 9, and even more preferably between 1 and 3,
• X denotes a group AL 1 -CO-L 2 -CO- where:
• A is an associative group comprising a nitrogen heterocycle
• Li is a chemical bond or a spacer arm consisting of a saturated or unsaturated hydrocarbon chain, cyclic or not, optionally interrupted by one or more nitrogen and / or oxygen atoms,
• L.2 is a saturated or unsaturated hydrocarbon chain, cyclic or not, containing at least 4 carbon atoms, optionally interrupted by one or more oxo groups and optionally substituted by one or more -OH groups and / or one or more chlorine atoms .
• the group X contains a sequence L 1 -CO-L 2 -CO- where L12 denotes a linear alkylene chain and Li 'denotes a -NH-CH2-CH2- chain.
• the material according to the invention comprises oligomers corresponding to formula (Ib) below:
• Ra, Rb and a have the definitions indicated above, X 'denotes a group AL 1 -CO-L 2 -M 1 - where:
• A, Li and L 2 are as defined above,
• Mi is an oxygen atom or an NH group.
• At least one of the Ra and Rb chains is not a linear alkylene chain.
• the dicarboxylic acid used in the first step of the process according to the invention advantageously comprises from 4 to 100 carbon atoms. It can be a linear and saturated dicarboxylic acid containing from 4 to 22 carbon atoms, such as succinic acid, 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 acid and mixtures thereof.
• the dicarboxylic acid used in this invention may be a branched and saturated dicarboxylic acid, for example containing from 6 to 10 carbon atoms, such as 3,3-dimethylglutaric acid.
• the diacid may be an aromatic diacid such as terephthalic acid, isophthalic acid, naphthalenic diacids and mixtures thereof.
• the diacid may be cycloaliphatic. In the latter case, it may comprise the following carbon skeletons: norbornyl methane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropan, di (methylcyclohexyl), di (methylcyclohexyl) propane.
• Can also be used according to the invention dimer carboxylic acid of vegetable origin, consisting of two identical or different fatty acid monomers, optionally mixed with monomers and / or trimers of fatty acids, these mixtures being chosen so that the polycondensate obtained remains below the point of chemical freezing.
• These plant-based compounds may or may not be unsaturated. They result from the oligomerization (especially dimerization) of unsaturated fatty acids such as undecylenic, myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic and docosenoic acids, which are usually found in oils.
• a mixture of oligomers of fatty acids containing at least 30% by weight, or even at least 50% by weight and preferably at least 70% by weight, of linear C55 fatty acid dimers or cyclic, optionally partially or fully hydrogenated, said mixture containing a small percentage of fatty acid monomers (typically less than 5%, preferably less than 2% and more preferably less than 1% by weight in total) and preferably containing different isomers of the same dimer of fatty acid.
• dimer fatty acids those sold by the company Croda under the trade name Pripol ® 1006, 1009, 1012, 1013, 1017, 1022, 1025 and 1027, by Arizona Chemicals under the trade name Unidyme ® 14, by the company BASF under the trade name Empol ® 1008, 1016 or 1018, or by the company OLEON under the trade name Radiacid ® 0980.
• diacids and polyacids derived from fatty substances as described in document FR2962131 A1 and represented in FIGS. (IIa) (IIb) and (IIc) of said document.
• diacids are obtained by modifying fatty acids or mixtures of fatty acids of natural origin (rapeseed oil, oleic acid for example) with the aid of thiols carrying an acid function, by thiol-ene chemistry.
• An aromatic diacid such as terephthalic acid, or a linear and saturated dicarboxylic acid containing from 4 to 12 carbon atoms, such as adipic acid or sebacic acid, is preferably used in the present invention.
• the diamine may be chosen from any linear, branched or cyclic, saturated or unsaturated compound bearing two primary amine functions.
• the term "diamine” thus encompasses polyamines comprising only two primary amine functions and at least one other secondary or tertiary amine function.
• the diamine may thus be a compound of formula (II):
• p is an integer from 3 to 20, such as cadaverine, putrescine, hexamethylenediamine or 1,12-diaminododecane.
• cycloaliphatic diamines and branched chain diamines such as isophorone diamine or bis (3-methyl-4-aminocycloxyl) methane (BMACM) or diamine dimers derived from vegetable fatty acids can be used, in particular of C 18 fatty acids, which may be partially or fully hydrogenated, such as those mentioned above.
• BMACM 3-methyl-4-aminocycloxyl methane
• diamine dimers derived from vegetable fatty acids
• diamines are the linear diamines containing heteroatoms (N) in their chain, in particular the compounds of formula (III):
• R 1 and R 2 independently denote a hydrogen atom or a C 1 -C 6 alkyl group such as a methyl group
• n and n 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.
• Ri and R 2 denote a hydrogen atom
• M + n 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 (III) are DETA (diethylene triamine), TETA (triethylene tetramine), TEPA (tetraethylene pentamine), spermine and dihexylene triamine.
• Still another type of diamines comprising hetero atoms (0) in their chain and usable according to the invention, consists of polyetheramines in particular consisting of a linear or branched polyether chain, such as a polypropylene glycol chain, polyethylene glycol, or polytetramethylene glycol, and copolymers thereof, each end of which carries a primary amino group.
• polyetheramines in particular consisting of a linear or branched polyether chain, such as a polypropylene glycol chain, polyethylene glycol, or polytetramethylene glycol, and copolymers thereof, each end of which carries a primary amino group.
• Such compounds are especially available from the company HUNTSMAN under the trade names Jeffamine ® Series D, ED or EDR.
• diamines and polyamines both branched and bearing a heteroatom (S) in their chain, such as those described in document FR2962131 A1 and represented in FIGS. (Ha) (IIb) and (Ile) of said document.
• S heteroatom
• diamines are obtained in particular by modification of unsaturated triglycerides of natural origin (rapeseed oil for example) using thiols carrying an amine function (such as cysteamine) by thiolene chemistry.
• the linear diamines, the linear diamines containing heteroatoms (O, S or N) in their chain, the branched chain diamines and the cycloaliphatic diamines may be used in mixtures in which, preferably, the molar fraction of diamines Linear substances not containing hetero atoms in their chain do not exceed 50% of the total number of moles of diamine involved.
• the diamine according to the invention may optionally be used in admixture with monoamines or polyamines, these mixtures being chosen so that the polycondensate obtained remains below the chemical gel point.
• diamines comprising a flexible block which is deemed to be difficult to crystallize.
• These amines can be selected from the following list: polyetheramines comprising a linear or branched polyether chain (in particular of poly (ethylene glycol) structure, poly (propylene glycol), poly (tetramethylene glycol) and their copolymers), each end of which carries a primary amine group, diamines and branched polyamines whose chain comprises a sulfur atom, and diamine dimers from vegetable fatty acids optionally partially or totally hydrogenated, as described above.
• polyetheramines comprising a linear or branched polyether chain (in particular of poly (ethylene glycol) structure, poly (propylene glycol), poly (tetramethylene glycol) and their copolymers), each end of which carries a primary amine group, diamines and branched polyamines whose chain comprises a sulfur atom, and diamine dimers from vegetable fatty acids optionally partially or totally hydrogenated, as described above.
• the diamine dimers derived from vegetable fatty acids, which may be partially or completely hydrogenated, are the preferred diamines.
• Modifier compound derived from vegetable fatty acids, which may be partially or completely hydrogenated, are the preferred diamines.
• the diamine or the dicarboxylic acid reacts with a modifying compound carrying, on the one hand, an associative group comprising a nitrogen heterocycle and, on the other hand, a reactive function capable of reacting with the diamine or the diacid, respectively.
• This modifier compound has the general formula: AL ! -CO-L 2 -W wherein: A is an associative group comprising a nitrogen heterocycle; Li is a chemical bond or a spacer arm consisting of a saturated or unsaturated hydrocarbon chain, cyclic or not, optionally interrupted by one or more oxygen and / or nitrogen atoms; L 2 is a saturated or unsaturated hydrocarbon chain, cyclic or not, containing at least 4 carbon atoms, optionally interrupted by one or more oxo groups and optionally substituted by one or more -OH groups and / or one or more chlorine atoms; and W is a reactive group capable of reacting with amino or acid functions of the diamine or diacid, respectively.
• Y is selected from oxygen, sulfur or NH
• associative groups include imidazolidonyl, triazolyl, triazinyl, bis-ureyl and ureido-pyrimidyl groups.
• a preferred associative group for use in the present invention is the imidazolidonyl group.
• the modifier compound reacts with the amine functions of the diamine.
• the molar ratio of the acid functions of the diacid to the reactive functions of the modifying compound is between 1 and 8, for example between 1 and 3, it being understood that the number of moles of amine functions of the diamine is equal to the sum the number of moles of the aforementioned acidic and reactive functions.
• Li and L 2 have the meanings indicated above, and
• Wi is a carboxylic acid, ester, anhydride or acyl chloride function.
• the modifying compound corresponds to formula (IV):
• R 1, R 2 and each R 1 independently denotes a hydrogen atom, an -OH group or a -CH 3 group, preferably a hydrogen atom; n is from 2 to 12 and is preferably 2, 4 or 6, more preferably 2; and R 3 is -OH, -OCH 3 or chlorine, preferably -OCH 3 .
• the above modifying compounds can be obtained by reacting UDETA (or 2-aminoethyl) imidazolidin-2-one) on:
• an alicyclic anhydride such as glutaric anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, diglycolic anhydride or itaconic anhydride, or
• aromatic anhydride such as 1,8-naphthalic, phthalic and isatoic anhydrides, or
• a dicarboxylic acid such as adipic acid, or
• a carboxylic acid diester such as dimethyl adipate or dimethyl terephthalate, or
• UDETA can itself be prepared by reacting urea with diethylene triamine (DETA).
• DETA diethylene triamine
• Other similar modifying compounds can be obtained by replacing UDETA with UTETA or UTEPA, which can be respectively prepared by reacting urea with triethylene tetramine (TETA) and tetraethylene pentamine (TEPA).
• TETA triethylene tetramine
• TEPA tetraethylene pentamine
• the modifying compound is chosen from the compounds corresponding to formula (VI):
• R 1, R 2 , R 3 and R 4 independently denote a hydrogen atom, a hydroxy group, an amino group, a nitro group or an alkyl group, as well as their positional isomers and their esters, acyl chlorides and anhydrides.
• the modifying compound may alternatively react with the acid functions of the dicarboxylic acid used in the process according to the invention.
• the molar ratio of the amine functions of the diamine to the reactive functions of the modifying compound is between 1 and 8, it being understood that the number of moles of acid functions of the diacid is equal to the sum of the number of moles of the amine functions and reagents mentioned above.
• the modifier compound generally has the formula: AL 1 -CO-L 2 -W 2
• Li and L 2 have the meanings indicated above, and
• W 2 is an OH or NH 2 group .
• UPy ureido-pyrimidyl derivative
• the diacid when the modifier compound reacts with the amino functions of the diamine and (ii) when the modifier compound reacts with the acidic functions of the diacid, the diacid may be replaced by a mixture of monoacid Bl, diacid B2, triacid B3 etc ..., and / or the diamine may be replaced by a mixture of monoamine Al, diamine A2, triamine A3 ..
• the quantities of polyacids and polyamines of functionality greater than or equal to 3 must be limited so as not to reach the chemical freezing point.
• A1 denotes, in the case (i) the number of moles of monoamine and in the case (ii) the sum of the numbers of moles of monoamine and of modifying compound,
• n B1 denotes, in the case (i) the sum of the numbers of moles of monoacid and of modifying compound and in the case (ii) the number of moles of monoacid,
• n A2 denotes the number of moles of diamine
• n B2 denotes the number of moles of diacid
• n A3 denotes the number of moles of triamine
• n B3 denotes the number of moles of triacid
• n Ai (i> 3) denotes the number of moles of polyamine containing amine functions
• Bj (j> 3) denotes the number of moles of polyacid with acidic functions.
• a modifier compound which has been previously synthesized, isolated and optionally purified so as to have a purity of at least 90%.
• the synthesis of this compound may optionally constitute a preliminary stage of the process according to the invention. However, it is excluded that this compound is synthesized in situ, to avoid the formation of undesirable products such as the one illustrated below, obtained from UDETA and a diacid
• the dicarboxylic acid, the diamine and the modifying compound are introduced, in the molar ratios indicated above, either simultaneously, or successively in any order, into a reactor.
• the polycondensate reaction is carried out at a temperature of 50 to 200 ° C, for example 160 to 200 ° C, for a period ranging from 1 to 24 hours, in particular from 4 to 6 hours.
• the reaction is usually carried out with stirring, for example at a rate of
• the evolution of the reaction can be followed by infrared spectroscopy.
• the disappearance of the characteristic bands of the diacid or the diamine in favor of the amide makes it possible to determine the moment when the reaction is completed.
• This reaction produces oligo-amides of variable chain lengths, functionalized at each of their ends by associative units and thus capable of associating with each other by reversible hydrogen bonds as a function of temperature. It has been observed that the length of the chains obtained, as well as their crystallizable fraction, were directly related to the aforementioned stoichiometric ratios. The latter are therefore adjusted to obtain a material having the required crystallinity to confer good mechanical properties and a molecular weight sufficiently low to have a low viscosity in the molten state.
• the polycondensate obtained at the end of this process is semi-crystalline, for example characterized by a melting enthalpy greater than 10 J / g, and it has generally a melting temperature (T f ) of between 120 and 260 ° C, preferably between 130 and 180 ° C, and more preferably between 140 and 170 ° C, and a glass transition temperature (T g ) generally between - 25 ° C and 100 ° C and preferably between -25 ° C and 10 ° C.
• T f melting temperature
• T g glass transition temperature
• Its number-average molecular weight, as measured by GPC, is generally less than 4,500 g / mol, for example between 1,000 and 3,000 g / mol, but may alternatively go up to 10,000 g / mol.
• This material has a low melt viscosity, generally less than 10 Pa.s, preferably less than 1 Pa.s and typically between 0.1 and 0.5 Pa.s at 30 ° C above its melting point, and good mechanical properties at ambient temperature and over a wide temperature range above ambient, which result in a breaking stress greater than 1 MPa, especially greater than 3 MPa, preferably greater than 4 MPa, or even greater than 10 MPa, and possibly a ductile behavior in tension.
• the aforementioned properties are measured according to the techniques given in the Examples section of this description.
• the material according to the invention has at least one, and preferably all, these properties.
• the material according to the invention can in particular be used to manufacture gaskets, thermal or acoustic insulators, shoe soles, packaging, coatings (paints, films, cosmetic products), trapping and release systems.
• active ingredients vacuum tubes, and generally parts having good resistance to tearing and / or fatigue, additives rheological, additives for bitumen or additives for hot melt adhesives, or even matrices of composites.
• Thermal analysis The samples were characterized by differential scanning calorimetry (DSC). The following protocol was applied: first heating at 10 ° C / min from -100 ° C to 250 ° C, isothermal 5 min at 250 ° C, cooling at -10 ° C / min to -100 ° C, isothermal at -100 ° C for 5 min then second heating up to 250 ° C at 10 ° C / min.
• the fusion enthalpies were measured using the TA Universal Analysis software in "Sigmoidal tangent" mode. Melting temperatures were determined at the peak apex and glass transition temperatures at the point of inflection.
• Rheology the viscosity of the samples was measured with a shear rate of 100s -1 , using a rheometer equipped with a 50 mm diameter cone-plane geometry. The sample was placed under the geometry preheated to 180 ° C.
• This example illustrates the synthesis of various modifying compounds used according to the invention.
• glutaric anhydride (7.95 g, 0.07 mol) was introduced into an addition funnel.
• Acetonitrile (15ml) was added to the anhydride and solubilized at 60 ° C with stirring (the solubilization was not complete).
• the reaction mixture was stirred for 20h at room temperature and then at 40 ° C for 4 hours.
• the product, which precipitated as it formed as a white powder was recovered by filtration (vacuum pump), washed twice with acetonitrile and dried under a bell at room temperature.
• the product obtained was a chemically characterized white powder: the purity of the final product could easily be determined by proton NMR.
• This method can be applied to the synthesis of similar modifying compounds having different chain sizes.
• UDETA (30 g or 0.232 mol) and dimethyl adipate (364.13 g or 2.090 mol) in large excess (9 equivalents).
• the transparent starting mixture was stirred and a nitrogen flow was set up in order to evacuate the methanol that formed in the reaction medium.
• the flask was placed in a bath of silicone oil heated at 140 ° C for a period of 6 hours.
• the excess diester was removed by distillation at 160 ° C. under static vacuum initially, at 180 ° C. under static vacuum when the distillation slowed down, then under dynamic vacuum at 160 ° C. to recover the largest possible amount of diester.
• the product formed was washed five times with pentane and dried under a bell at room temperature. during 24 hours.
• the final product (UDETA-C6) could be characterized by NMR and showed good purity.
• a similar process can be implemented by substituting a dicarboxylic acid or a dicarboxylic acid chloride for the diester used above.
• the UDETA (20 g, 0.155 mol) was solubilized in 30 ml of acetonitrile in a two-necked flask equipped with a bar magnetized at room temperature.
• the flask was surmounted by an addition funnel in which was introduced a solution of 18.3 ml (0.17 mol) of caprolactone in 15 ml of acetonitrile.
• This solution was added dropwise to the reaction mixture over a period of 30 minutes at room temperature.
• the mixture was then stirred for 12 hours and then 4 hours more at 40 ° C.
• the solution was concentrated in a rotary evaporator and allowed to freeze for 12 hours to crystallize the reaction product, which was then recovered by filtration, washed
• n ranged from 0 to 3.
• the reaction was carried out in a double wall reactor with a diameter of 60 mm and a nominal volume of IL, regulated using a circulating bath with silicone oil circulation, the pipes of which were reinforced by a metal sheath.
• This reactor was surmounted by a mechanical stirrer and was provided with a bottom valve, a gas inlet and a bubbler.
• the reaction was monitored by infrared and the reaction products were analyzed by NMR and GPC.
• Pripol ® 1009 52.5 g (0.18 mol) of Pripol ® 1009 were weighed and introduced into the reactor. was then introduced into the reactor 101.01 g (0.37 mol) of Priamine ® 1074 and then 50 g (0.18 mol) of UDETA C6. The reactor was then closed and heated to 180 ° C. with stirring at 280 rpm. A nitrogen flow of 300 ml / min was set up using a pipe that could withstand high temperatures. This pipe was introduced closer to the mixture with stirring. A gas outlet connected to a bubbler made it possible to check the tightness of the reactor and to retain the methanol formed during the reaction. Infrared (IR) monitoring was put in place to determine when the heating was to be shut down.
• IR Infrared
• the reaction was complete after 6 hours and the oligomer obtained was recovered at the bottom valve in a teflon beaker. The product obtained crystallized rather quickly in the beaker and did not adhere to it. It could easily be retrieved and analyzed.
• n 0 M n (mol) m (g) Mn
• UDETA-C6 271.26 0.184325 50 n 2 M n (mol) m (g) Mn
• n ranged from 0 to 3.
• Example 2 a comparative sample was also prepared by replacing UDETA-C6 with a modifying compound not falling within the scope of the invention.
• UDETA-C6 271.26 n 1 M n (mol) m (g) Mn
• n 3 M n (mol) m (g) Mn
• Example 2 The materials prepared in Examples 2 and 3 were subjected to the various tests presented above, in order to evaluate their physicochemical and mechanical properties.
• the materials synthesized according to Example 3 were annealed for 1 h at 100 ° C before measuring their enthalpy of fusion.
• modifier compound according to the invention by another compound having no nitrogen heterocycle results in a material having a melting point below 120 ° C, which is insufficient for many applications, or even a material that is not solid but is in the form of a viscous liquid at room temperature.
• Example 5 Materials obtained by replacing the modifier compound with UDETA
• Comparative oligo-amide was prepared using UDETA instead of the UDETA-C6 modifier group according to the invention.
• This material was prepared according to a method similar to that described in Example 2, from 50 g of Pripol ® 1009 (0.175 mol), 24 g of Priamine ® 1074 (0.088 mol) and 11.32 g of UDETA (0.088 mol ) except that the Priamine ® and UDETA were introduced into the reactor heated to 180 ° C before adding the Pripol ® 1009.
• the product obtained was present, in the ambient, in the form of a very viscous liquid having no significant mechanical properties. Its viscosity was below 0.3 Pa.s at 180 ° C.

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• 2013
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• 2014
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  • 2014-02-25 EP EP14713178.3A patent/EP2958953B1/fr not_active Not-in-force
  • 2014-02-25 CN CN201480010219.8A patent/CN105143308A/zh active Pending
  • 2014-02-25 US US14/770,282 patent/US20160009656A1/en not_active Abandoned
  • 2014-02-25 WO PCT/FR2014/050398 patent/WO2014128426A1/fr not_active Ceased

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