Classifications

• • 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
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/28—Preparatory processes
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article

Definitions

• the present invention relates to a new method of synthesis of supramolecular materials, as well as the materials obtained and their applications.
• the so-called supramolecular materials are materials consisting of 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. It is thus possible to envisage using them in fields of application such as coatings (paints, cosmetics, etc.), adhesives, hot melt adhesives and powder coatings or as an additive in thermoplastics or in bitumens. .
• 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 seals, thermal or acoustic insulators, tires, cables, sheaths, shoes, packaging, patches (cosmetics or dermo-pharmaceuticals), dressings, elastic hose clamps, vacuum tubes, or tubes and hoses for transporting fluids.
• polyamines in particular diethylene triamine, DETA, triethylene tetramine, TETA or tetraethylene pentamine, TEPA
• polyamines in particular diethylene triamine, DETA, triethylene tetramine, TETA or tetraethylene pentamine, TEPA
• associative groups for example imidazolidone functional groups
• DETA or TETA DETA or TETA with a polyacid such as dimers and trimers of fatty acids or polyacrylic acid.
• This material does not have elastomeric properties.
• a self-healing elastomeric supramolecular material is further 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. It is stated that this Alternatively, the product can be obtained by reaction of the triacids with the condensation product of urea with a polyamine such as diethyl triamine (DETA).
• DETA diethyl triamine
• This method also makes it possible to easily adjust the architecture of the materials obtained, and consequently their properties, by modifying the quantity and the nature of the reagents involved. It is thus possible in particular to obtain a material having the properties of a thermoplastic elastomer, or even such an elastomer self-healing, that is to say capable, once cut, torn or scratched, to repair by simply bringing the fractured surfaces into contact without the need to heat up or apply significant pressure or to carry out any reaction chemical, the repaired material retaining elastomeric properties.
• the subject of the present invention is a process for synthesizing a supramolecular material comprising:
• the subject of the invention is also the material that can be obtained by this method.
• the dicarboxylic acid used in the first step of the process according to the invention advantageously comprises from 5 to 100, preferably from 12 to 100 and more preferably from 24 to 90 carbon atoms. It can be a linear alkyldicarboxylic 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 alkyldicarboxylic acid such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid,
• the diacid may also be mixed with other compounds such as mono- or tri-carboxylic acids. It is thus possible to use a mixture of mono-, di- and trimeric fatty acids.
• dimers oligomers of 2 identical or different monomers
• mixtures of dimers and trimers of fatty acids of vegetable origin are preferred.
• Oligomerization of unsaturated fatty acids such as undecylenic, myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic and docosenoic acids, which are commonly found in pine oils (TaIl oil fatty acids), rapeseed, corn, sunflower, soy, grape seeds, linseed, jojoba, 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 pine oils (TaIl oil fatty acids), rapeseed, corn, sunflower, soy, grape seeds, lins
• fatty acid oligomers containing dimers, trimers 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 monomers.
• said mixture comprises:
• 0.1 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 dimers of the same or different fatty acids, and
• 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
• Arizona Chemical Unidyme® 14 a mixture of 94% of dimers and less than 5% of trimers and other higher oligomers with about 1% of monomeric fatty acids
• Empol® 1008 from Cognis, a mixture of 92% of dimers and 3% of higher oligomers, essentially trimers, with about 5% of monomeric fatty acids,
• Empol® 1016 from Cognis, a mixture of 80% dimers, 4% monomers and 16% fatty acid trimers
• Empol® 1018 from Cognis, a mixture of 81% dimer and 14% d higher oligomers, including essentially trimers, with about 5% of monomeric fatty acids.
• Pripol® products, Unidyme®, Empol® and Radiacid® comprise fatty acid monomers Cis and oligomers of fatty acids corresponding to multiples of C 8.
• the dicarboxylic acid may be partially or completely replaced by a diacid derivative (s), this diacid derivative being chosen from an acid ester and an acid chloride.
• an 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 dicarboxylic acid or the ester derivative or acid chloride is reacted with a modifying compound bearing both associative groups and reactive functions capable of reacting with the carboxylic acid functions.
• the acid ester or acid chloride of the dicarboxylic acid or derivative used in a molar ratio of reactive functions to carboxylic acid functions (respectively ester or acid chloride) of between 0.10 and 0.50, preferably between 0.10 and 0.30.
• associative groups groups capable of associating with each other by hydrogen bonds, advantageously by 1 to 6 hydrogen bonds.
• examples of associative groups that can be used according to the invention are the imidazolidonyl, triazolyl, triazinyl, bis-ureyl and ureido-pyrimidyl groups.
• the imidazolidonyl group is preferred.
• the reactive functions can in particular be chosen from primary or secondary amine functions or alcohol.
• the modifying compound carries at least one primary amine function.
• the modifying compound can thus satisfy any one of the formulas (B1) to (B5):
• R denotes a unit containing at least one reactive function
• R 'de notes a hydrogen atom
• R ", Ri and R2 denote any groups
• A denotes an oxygen or sulfur atom or an -NH group, preferably an oxygen atom.
• Preferred examples of modifying compounds are 2-aminoethylimidazolidone (UDETA), 1- (2 - [(2-aminoethyl) amino] ethyl) imidazolidone (UTETA), 1- (2-
• UDETA [(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.
• 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 reaction of the modifying compound with the dicarboxylic acid 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 hours. h, advantageously with stirring and under an inert atmosphere.
• the dicarboxylic acid or its ester derivative or acid chloride is also reacted, in the first step of the process according to the invention, with at least one polyamine, for example in a molar ratio of the amine functions to the acid functions of the dicarboxylic acid of between 0.90 and 0.50, in particular between 0, 90 and 0.70.
• the polyamine may be any compound carrying at least two amine functions, preferably primary amine, and preferably a compound of formula (I):
• Ri, R 2, R 3 and R 4 independently denote a hydrogen atom or an alkyl group C x -C 6 such as methyl group, m, 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.
• 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 according to the invention may be a linear alkylene diamine containing 3 to 20 carbon atoms such as cadaverine, putrescine, Hexamethylene diamine or 1,12-diaminododecane or a cyclic alkylene diamine such as isophorone diamine.
• reaction of the polyamine with the dicarboxylic acid or the ester or acid chloride derivative used may, for example, be carried out at a temperature of between 20 and 200 ° C., preferably between 140 and
• the first step of the process according to the invention comprises the reaction of the dicarboxylic acid or its ester derivative or acid chloride, both with the modifying compound and with the polyamine described above. These two reactions can be performed simultaneously or successively. In the case where these reactions are conducted successively, the reaction with the modifier compound 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 polycondensate obtained at the end of the first step can be semi-crystalline with a melting temperature (Tf) most often between 30 and 150 ° C. and it has a glass transition temperature (T g ) most often between -50 0 C and 20 0 C.
• Tf melting temperature
• T g glass transition temperature
• the product resulting from this first stage is then reacted, in a second stage, with urea, without it being necessary to carry out a washing or a prior purification thereof.
• the reaction may for example be carried out at a temperature of 130 to 170 ° C., preferably 130 to 160 ° C., by carrying out a temperature ramp, for a period ranging from 30 minutes to 8 hours, preferably for a period of 1 hour. at 6 hours, under an inert atmosphere and, advantageously, with stirring.
• this reaction can be carried out in a reactor separate from that or those used in the first stage, or in the same reactor. It is therefore understood that all the steps of the process according to the invention can be implemented in the same reactor, by successive addition of reagents, which makes the process particularly simple and economical.
• the function of urea is to create additional associative groups, for example according to the following reaction schemes:
• the reagents (dicarboxylic acid or derivative, modifying compound, polyamine and urea) described above can be introduced, in the process according to the invention, in the molten state, in the pulverulent state, or by solvent, for example in aqueous solution. However, it is preferred that they be introduced in powder form or in the molten state to avoid the use of solvents which need to be subsequently removed.
• This material consists of a set of molecules of different lengths, containing a portion soluble in an alcohol and optionally an insoluble part, ie a fraction representing from 0.1 to 90% of the weight of the material and which is not soluble in any solvent.
• the number-average molecular weight of the soluble fraction is preferably from 300 to 300,000 g / mol, as measured by GPC.
• the average number of associative groups per molecule is at least 1.2, preferably at least 2 or even at least 2.2.
• this material comprises molecules containing binding bridges, preferably amide, formed in the first step of its synthesis process, by reaction of the reactive groups (advantageously primary amine) of the modifying compound with a part of the dicarboxylic acid and by reacting the amine functions of the polyamine with another part (preferably the remainder) of the dicarboxylic acid.
• This material also contains hydrogen bonds between the associative groups carried by the molecules which constitute it, and which are provided by the modifier compound and by the reaction of urea on the polyamine.
• this material also contains intermolecular hydrophobic bonds, advantageously due to interactions between pendant alkyl groups provided by the dicarboxylic acid. Such groups are especially present in fatty acid dimers.
• thermoplastic elastomer properties that is to say the property of being able to be subjected to uniaxial deformation at ambient temperature, possibly at least 20% for 15 minutes, and to recover, once this stress released, its initial dimension, with a remanent deformation less than 5% of its initial dimension, and which can be put and reformed at high temperature.
• It can also be capable of self-healing after a cut and present, after contacting the edges of the cut, elastomeric properties allowing it to undergo, for example, a tensile deformation of at least 100% or at least 200% before breaking and recovering its initial dimensions once the stress is released, with a remanent deformation of less than 10% of its initial dimension.
• a material is generally obtained in the form of a soft solid, which can be extruded or cold ground, for example in a hammer mill, ball mill, ball mill or grinding mill. or knives and then washed, for example with water, and finally shaped, in particular by hot pressing, calendering, thermoforming or any other method.
• the material according to the invention can in particular be used to manufacture gaskets, thermal or acoustic insulators, tires, cables, sheaths, shoe soles, packaging, coatings (paints, films, cosmetic products ), patches (cosmetics or dermopharmaceuticals) or other asset trapping and release systems, dressings, elastic hose clamps, vacuum tubes, fluid tubes and hoses, and in a manner general parts having good resistance to tearing and / or fatigue, rheological additives, additives for bitumen or additives for hot melt adhesives and adhesives.
• the invention therefore also relates to the use of the material according to the invention for the aforementioned purposes.
• the material according to the invention can be used as such or in single-phase or multiphase mixtures with one or more compounds such as petroleum fractions, solvents, mineral and organic fillers, plasticizers, resins and the like.
• tackifiers, antioxidants, pigments and / or dyes for example, in emulsions, suspensions or solutions.
• this material can be used for the manufacture of a cosmetic composition usually comprising a physiologically acceptable medium, that is to say compatible with keratin materials, containing for example at least one oil and / or water and / or an alcohol.
• This cosmetic composition can be used for the care and / or makeup of the skin and / or its integuments (such as eyelashes and nails) and / or lips or for washing, conditioning and / or putting in the form of hair.
• integuments such as eyelashes and nails
• Sub-step a In a reactor with a diameter of 60 mm and a nominal volume of 500 ml equipped with a bottom valve, a thermal fluid temperature regulation, a mechanical stirrer, a dropping funnel, a Dean-Stark and a gas inlet, preheated to 40 0 C, is introduced 76 g of Empol ® 1016 [acid number 194, monomer level (4%), dimer (80%), trimer (16%)] and 6.7g of purified UDETA (52 mmol), which is a ratio [HN 2 ] / [COOH] of 0.2. The bath temperature is brought to 150 ° C. for 8 hours under a flow of nitrogen of 500 ml / minute and stirring of 280 rpm.
• the product of the reaction is stored at 50 ° C. in the reactor.
• the reactor body is heated to 160 ° C. and the amine is slowly added dropwise intermittently over a total period of 3 hours.
• the reaction is allowed to continue for another 4 hours at 160 ° C.
• the same type of evolution is observed by infrared spectroscopy as previously.
• the end of The release of water vapor, again observed, is used as a criterion for stopping the reaction.
• 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:
• the stopping criterion is this time that the product is solid and clings to the axis of the agitator. As soon as this is the case, the product is collected on the stirring rod.
• the pieces obtained are placed in a plastic bag and cold-milled 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 redécoupe into pieces of approximately 5 mm in size which is placed in a mold consisting of a 1.6 mm thick brass plate pierced with a rectangular hole, placed between two sheets of release paper. After a first pressing at 120 ° C. for 10 minutes (applied pressure 10 MPa), the film obtained has irregularities in thickness which are corrected by adding material and repressing until a satisfactory appearance is obtained.
• Example 2 Traction test
• 60 mm is cut in half in the middle, left to rest for five minutes, repaired by contacting the rupture surfaces and then left to rest for two hours.
• a tensile test is carried out on the cicatrized ribbon after having drawn two marks 4 cm apart, on each side of the scar. The ribbon is stretched until it reaches 350% of deformation without breaking.
• the ribbon is then left standing at room temperature. After 40 minutes, we see that it has returned to its original size.
• This example shows that the process according to the invention makes it possible, under simple and economical conditions, to obtain materials having the rubber-elastic property and capable of self-repairing in the event of a break.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyamides (AREA)
• Paints Or Removers (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=40011199

Family Applications (1)

Country Status (7)

Families Citing this family (14)

Family Cites Families (11)

• 2008
  • 2008-05-05 FR FR0852981A patent/FR2930777B1/fr not_active Expired - Fee Related
• 2009
  • 2009-05-05 US US12/991,181 patent/US8536281B2/en not_active Expired - Fee Related
  • 2009-05-05 BR BRPI0910532A patent/BRPI0910532A2/pt not_active IP Right Cessation
  • 2009-05-05 JP JP2011507972A patent/JP5254431B2/ja not_active Expired - Fee Related
  • 2009-05-05 WO PCT/FR2009/050825 patent/WO2009141558A2/fr active Application Filing
  • 2009-05-05 EP EP09750039A patent/EP2276790A2/de not_active Withdrawn
  • 2009-05-05 CN CN200980116272.5A patent/CN102131846B/zh not_active Expired - Fee Related

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events