Classifications

• • 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
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
• • 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 elastic materials having the rubber elasticity property. More specifically, these materials consist of molecules united by non-covalent or physical bonds, for example hydrogen bonds. These materials have properties reminiscent of those of a rubber. Unlike conventional elastomers, the materials according to the invention can become fluid above a certain temperature, which is an advantage in the stages of implementation and recycling of these materials. By definition, an elastomer must both have dimensional stability over very long times and be capable of recovering its initial shape after very large deformations (elongation of 100 to 600%). The rubber elasticity property is also appreciated by the remanent deformation after relaxation of the stress causing the deformation.
• seals thermal, acoustic, pneumatic, cable, sheath, shoe soles, packaging, coatings (paints, cosmetics, films), elastic hose clamps, vacuum tubes, transport tubes and hoses, rheological additives (eg cosmetics) fluids or additives in adhesives and hot melt glues (called hot-melt in English terminology) .
• rubber elasticity it is meant that the material undergoing a uniaxial deformation of 20% for a period of 15 minutes at the use temperature returns to its original size with a remanent deformation of less than 5% of the initial dimension, that is to say the material of initial length L 0 before deformation has been deformed under uniaxial stress at a length L d for 15 minutes still at the use temperature such that (L d -L 0 ) / L 0 is greater than or equal to 0, 2 and finds a length L ⁇ , final length of the material after release of the stress such that (L f -L 0 ) / L 0 is less than 0.05, advantageously (L d - L 0 ) / L 0 is greater or equal to 0.8, preferably (L d -L 0 ) / L 0 is greater than or equal to 1.
• Rubber elasticity is in principle a property characteristic of polymer systems. Usually, it does not occur in inorganic materials (glasses, metals, oxides, ionic solids ...) or in molecular materials, whether crystalline or amorphous.
• Traditional elastomers such as SBR rubber (abbreviation for Styrene Butadiene Rubber) or NBR (abbreviation for Nitrile Butadiene Rubber) are polymers resulting from the linking of molecules (monomers) attached to each other. to others by covalent bonds. These polymers can in addition be crosslinked.
• SBR rubber abbreviation for Styrene Butadiene Rubber
• NBR abbreviation for Nitrile Butadiene Rubber
• polyamide 6 objects thermoplastic polymer
• PA 6 polyamide 6 objects
• PA 6 thermoplastic polymer
• PA 6 polyetherblocamides
• EPR abbreviation for Ethylene Propylene Rubber
• thermoplastic elastomers and thermoplastic polymers all result from the sequence of molecules (monomers) attached to each other by covalent bonds that are called macromolecules, these macromolecules have molecular weights of at least 10000 g / mole.
• A is oxygen, sulfur or NH and X is any moiety; the hydrogen bonds in the supramolecular polymer being between two identical or different functions chosen from the functions (1) to (5).
• the polymers of the invention can be used alone, that is to say in the form of a composition consisting essentially of these polymers and optionally stabilizers, antioxidants or in the form of a mixture with other polymers or other products.
• the elastomers are not described or suggested.
• starting from Crayamid 115® is a polyamidoamine (MW -2000-4000 g / mol), a condensation product of a TOFA type of acid dimer (abbreviation Anglo-Swedish TaII OiI
• the subject of the invention is a material comprising at least one molecule with a molecular mass ranging from 9 to 9000 g / mol, said molecule comprising at least three associative functional groups, each associative functional group comprising at least one function capable of forming a physical link.
• said material having a rubber elasticity measured at the temperature of use, said rubber elasticity being defined by the fact that after uniaxial strain deformation for 15 minutes of said material of an initial length L 0 to a length L d such that (L d -L 0 ) / L 0 is greater than or equal to 0.2, the material is found after relaxation of the uniaxial stress with a length L f such that (L f -L 0 ) / L 0 is less than or equal to 0.05, since L 0 is the initial length of the material, L d is the length of the uniaxially stressed deformed material and L f is the final length of the material after loosening of the uniaxial stress.
• a physical link mention may be made, for example, of ⁇ bonds, ionic bonds, van der Waals bonds, metal-ligand coordination bonds and hydrogen bonds.
• the material comprises at least one molecule of molecular weight ranging from 9 to 9000 g / mol, said molecule comprising at least three associative functional groups, each associative functional group comprising at least one function capable of forming two physical bonds .
• the material comprises at least one molecule of molecular weight ranging from 9 to 9000 g / mol, said molecule comprising at least three associative functional groups, each associative functional group comprising at least one function capable of forming three physical bonds .
• the material comprises at least one molecule of molecular mass ranging from 9 to 9000 g / mol, said molecule comprising at least three associative functional groups, each associative functional group comprising at least one function capable of forming four physical bonds.
• the material is characterized in that (L d -L 0 ) / L 0 is greater than or equal to 0.8.
• the material is characterized in that (L d -L 0 ) / L 0 is greater than or equal to 1.
• the material is characterized in that the molecules capable of forming physical bonds are derived from triacids or from a mixture comprising diacids and triacids, these diacids or triacids comprising at least 5 carbon atoms.
• the material is characterized in that the molecules capable of forming physical bonds are of plant origin.
• the material is characterized in that the molecules capable of forming physical bonds are molecules having from 12 to 100 carbon atoms.
• the material is characterized in that the molecules capable of forming physical bonds are molecules having from 24 to 90 carbon atoms. According to one embodiment, the material is characterized in that the molecules capable of forming physical bonds are dimers or trimers.
• the material is characterized in that the molecules united by non-covalent bonds carry associative groups of formula (1) below:
• A is oxygen, sulfur or NH
• the carbon atoms in formula (1) may be substituted.
• A denotes oxygen.
• the material comprises (i) molecules having at least 3 associative groups and (ii) molecules having a single associative group.
• the difference between the number of associative groups belonging to molecules that have at least three associative groups per molecule and twice the total number of molecules comprising at least three associative groups is greater than 80% of the number of molecules comprising a single associative group where associative means able to associate by physical links.
• this difference is greater than 100%, advantageously greater than 150%.
• the molecular weight of the molecules constituting the material is between 17 and 5000 g / mol, advantageously between 500 and 1500 g / mol.
• R is chosen from the group -CH 2 -CH 2 - and the grouping -CH 2 -CH 2 -NH-CH 2 -CH 2 -.
• all the associative groups of the molecules having at least 3 associative groups are of formula (4 ').
• the molecules united by non-covalent bonds are chosen from:
• (A 1 B) (R 21 R 3 ) or (R 31 R 2 ) in which R 1 , R 2 are saturated or unsaturated hydrocarbon chains terminated by a secondary amide group carrying a 2-imidazolidone and R-terminus 3 , R 4 saturated or unsaturated hydrocarbon chains.
• the molecules united by non-covalent bonds are chosen from:
• the invention also relates to objects made partly or wholly of the material according to any one of the preceding claims.
• the present invention relates to a material having the rubber elasticity property.
• Said material consists of molecules with a mass of between 9 and 9000 g / mol, all or some of the molecules having at least three groups, also designated by "associative groups", said associative groups being themselves constituted of one or more functions able to associate by physical bonds.
• this material has rubber elasticity properties which are the prerogative of macromolecules.
• this material has rubbery elasticity at room temperature. Above a certain temperature the material flows as a simple liquid. The material is thermoreversible, that is to say that by cooling there is a material having the rubber elasticity property. This material is self-repairing and potentially recyclable which is never the case of a chemically crosslinked elastomer.
• the elastic properties in particular the relaxation time at various temperatures, the creep properties, the glass transition temperature T 9 , the temperature at which the material becomes fluid T ⁇ , solubility in different media, chemical resistance.
• the properties of the material mentioned above can also be modulated by addition of adjuvants such as plasticizers, antioxidant additives, etc.
• the material of the invention can be dissolved in certain solvents, which is an advantage over conventional crosslinked elastomers.
• the molecules constituting the material of the invention carry associative groups of formula (1) below:
• A is oxygen, sulfur or NH
• the carbon atoms in formula (1) may be substituted.
• A is oxygen.
• the group of formula (1) preferably imidazolidone, it is possible to produce elastic materials having unique properties. While consisting of small unpolymerized and non-chemically cross-linked molecules, this material has rubber elasticity properties that are unique to macromolecules. At high temperature (> 180 ° C) the material flows as a simple liquid.
• the material according to the invention is capable of swelling in the presence of water or moisture.
• the addition of water is also a means of varying the properties mentioned above.
• the invention also relates to objects made in part or in whole of this material.
• Rubber elasticity can be appreciated by observing the behavior of the material during elongation or compression.
• a test piece of the tensile material is subjected to an elongation of 20% for 15 minutes at the temperature under consideration and the residual strain is then measured, when the tension is released, as compared with the specimen before traction.
• the residual deformation is less than 5%.
• the residual strain is also measured after 20% compression for 15 minutes, the residual strain is also less than 5%.
• Rubber elasticity in the sense of the invention is defined by the equation (L (-L 0 ) / L 0 less than or equal to 0.05 after deformation of the material for 15 minutes at the temperature of use and (L d - L 0 ) / L 0 is greater than or equal to 0.2, advantageously 0.8, preferably 1.
• L 0 initial length of the material
• L d length of deformed material under uniaxial stress
• L f final length of the material after release of the stress.
• the molecules constituting the material it is necessary that at least some of them have at least three groups capable of associating through non-covalent interactions.
• the associative groupings must be well chosen but the environment also has its importance. In a non-polar environment, if the associative groups are surrounded for example by hydrocarbon chains, the electrostatic interactions are strong, in a polar medium on the contrary if the associative groups are surrounded for example by polyoxyethylene chains, the electrostatic interactions are weakened.
• the molecules must have an association constant in the medium of greater than 1000 Lmol -1 and advantageously greater than 10000 Lmol -1 .
• the material consists for example of (i) molecules having at least 3 associative groups (ii) molecules having two associative groups and (iii) molecules having a single associative group.
• the difference between the number of associative groups belonging to the molecules which have at least three associative groups per molecule and twice the total number of molecules comprising at least three associative groups is greater than 80% of the number of molecules comprising a single associative group ( where associative means able to associate by non-covalent interactions).
• this difference is greater than 100% and more preferably greater than 150%.
• the molecular weight of the molecules constituting the material is between 17 and 5000 g / mol and preferably between 500 and 1500 g / mol.
• the associative groups of the molecules constituting the material are of formula (1) as described above. Either this group is present on the molecule or it is attached to a molecule or else it is obtained by reaction of a product of formula (2 '):
• the associative groups of formula (1) can also be attached to molecules in order to obtain the constituent molecules of the material of the invention.
• the product of formula (3 ') below can be fixed:
• the product of formula (3 ') can be obtained by reacting the product of formula (2') with diethylenetriamine of formula:
• each of the molecules having at least 3 associative groups capable of associating, by non-covalent interactions at least one of the following formula:
• R is selected from the group -CH 2 -CH 2 - and the group -CH 2 -CH 2 -NH-CH 2 -CH 2 -
• all the associative groups of the molecules having at least 3 associative groups are of formula (4 ').
• a molecule having associative groups of formula (4 ') in which A denotes oxygen can be obtained by reacting a product of formula (3') with the carboxylic acid groups of an optionally hydrogenated polyacid which is itself obtained from from fatty acids.
• This molecule having associative groups of formula (4 1 ) in which A denotes oxygen can also be obtained by reaction of an acid with a diethylenetriamine (DETA) or triethylenetetramine (TETA) amine and then reaction with a product. of formula (2 ') such as urea.
• DETA diethylenetriamine
• TETA triethylenetetramine
• ni 5 to 8
• X 1 0 or 1
• V 1 0 or 1
• Z 1 0 or 1
• R 2
• the groups R 1 to R 6 may be in axial or equatorial position. According to a particular form, when the products are obtained from dimer of non-hydrogenated fatty acids rich in linolenic acid, the majority products according to formulas I and II may have the following structure, (VI, VII).
• the molecules capable of forming physical bonds may be derived from fatty acids, ie saturated or unsaturated carboxylic acids containing at least 5 carbon atoms, such as linear diacids such as glutaric acid, adipic acid, lactic acid, and the like. pimelic acid, suberic acid, azelaic acid, sebacic acid, or branched as 3,3-dimethyl glutaric acid, dimers and trimers of fatty acids of plant origin such as lauric acid , myristic, palmitic, oleic, linoleic, stearic, linoleic that are found especially in pine oil, rapeseed, corn, sunflower, soybean, grape seed.
• fatty acids ie saturated or unsaturated carboxylic acids containing at least 5 carbon atoms, such as linear diacids such as glutaric acid, adipic acid, lactic acid, and the like.
• Dimers or trimers of fatty acids are understood to mean oligomers of 1, 2 or 3 monomers, which are identical or different.
• these saturated or unsaturated carboxylic acids contain from 12 to 100 carbon atoms and even more advantageously from 24 to 90 carbon atoms.
• the acid dimer used contains a certain proportion of acid trimer
• the material obtained by this method of synthesis will also comprise a certain proportion of the molecule VII, characterized by the presence of more than two groups. imidazolidone.
• the acid dimer used contains a certain proportion of tetramers, pentamers or other molecules carrying more than two acid functions
• the material obtained by this method of synthesis will comprise molecules characterized by the presence of more than two groups 2 -imidazolidone.
• the temperature above which the material becomes fluid depends on the nature of the molecules. It is usually between 180 and 270 ° C. It increases with X 1 and increases when the polarity of the medium decreases.
• elongation at break there is a temperature range in which it can be between 50 and 700%. This elongation at break is measured using tensile test pieces according to the ISO 527 standard.
• the material As regards the properties of the material, it is soluble in benzyl alcohol at 60 ° C.
• the water intake is 17% by mass after immersion in water for 5 days at room temperature.
• the material swells in the presence of saturated or unsaturated hydrocarbons such as dodecane, this makes it possible to lower the glass transition temperature.
• a nonvolatile swelling agent will be selected.
• the materials according to the invention flow as molecular liquids at high temperature. This is an advantage in the case of an implementation by injection and molding: on the one hand the fluidity makes it possible to accelerate the rates in this type of process, on the other hand to replicate more faithfully the details of the mold.
• the materials of the invention are soluble in benzyl alcohol but resistant to most solvents.
• the materials of the invention may contain additives including water, plasticizers.
• Tg and Tf can be set by the composition. Relaxation times can also be adjusted by the plasticizers.
• the mixture is heated to 130 ° C. 11.65 g (0.194 mol) of urea are then added. After about 5 minutes, a gas evolution of ammonia (verified by pH paper) is observed, which is accompanied by foaming of the reaction medium. When the evolution of ammonia decreases, the temperature is raised from 5 ° C. to 5 ° C. and so on up to 150 ° C. The reaction mixture becomes difficult to stir. The heating is stopped and the product UD 1018 is recovered by detaching it from the stirring anchor. It is then placed in a vacuum oven for one week at 70 0 C (5mmHg vacuum) to evacuate the ammonia. After each step, gel permeation chromatography (GPC) analyzes are carried out in benzyl alcohol at 130 ° C. to verify that there is no polymerization and that the masses of the compounds remain low (Mn ⁇ 1500g.mol-1)
• FIGS. 3a and b represent the isotherms of the storage modules, G '(v) FIG. 3a and losses, G "(v) FIG. 3b of the compound UT1008 as a function of the biasing frequency.
• FIG. ⁇ a and b represent the creep tests FIG. ⁇ a and recovery FIG. ⁇ b. Constraints of increasing intensity ( ⁇ ) are applied to the sample during 1000 s and then relaxed.
• the mechanical admittance (compliance) J strain / strain is represented as a function of time. The deformations are 1.47%, 7.43%, 15.1%, 30.7% and 36.5% respectively.
• FIG. 6 represents a uniaxial tensile experiment at 90 ° C. of compound UT1008 until rupture.
• the elongation rate is 100% .min -1 .
• the final deformation is 240%.
• the compound UD1018 gives similar results.
• FIGS. 7a and b show the sigma stress during the tensile cycles
• FIG. 8 represents creep experiments for UT1008. The deformation is 100% and maintained for 24 hours. Deformation rates are 50% min -1 and temperature 70 ° C.
• FIG. 9 shows UT1008B swelling experiments with water at room temperature.
• dumbbell-shaped tensile test pieces (25mm inter-dumbbell spacing) were placed in the presence of dodecane for 96 hours at room temperature so as to swell the samples with about 10% dodecane (test tube 1) and about 15% of dodecane (test tube 2).
• the samples are kept at 60 ° C. for 12 hours in a closed container.
• Test tube 1 8.6% of dodecane Cycle 1. Elongation at 100% (speed 100% / min) then return to 0% (speed 40% / min). The loss of recovery is 5.9% after 200 min. Cycle 2. Elongation at 100% (speed 100% / min) then return to 0% (speed 40% / min). The recovery loss is 0.3% after 70 min. Cycle 3. Elongation at 400% (speed 40% / min). The loss of recovery is 7.6% after
• FIGS. 10a and b represent the preceding uniaxial traction tests at 25 ° C. of the compound UD1018 supplemented with 8.6% of dodecane, ⁇ before rupture (cycles 1-3), b) until failure (cycle 4), c) after breaks and successive gluing (cycles 5,6).
• the stress is represented as a function of the deformation defined above.
• the elongation rate is +100% .min -1 (cycles 1, 2), +40% min -1 (cycles 3-6), and the breaking strain is 570%.
• Test tube 2 12.8% of dodecane
• Cycle 5 After rupture, the two ends of the test piece are brought into contact. This is conserved vertically, the loss of recovery is 10% after 36 hours Cycle 6 Elongation until rupture (speed 40% / min). Rupture 240%.
• FIG. 11 represents the preceding uniaxial traction tests at 25 ° C. of the compound
• FIG. 12 represents the evolution of the dimensions of a rectangular zone of dimensions L 0 Xe 0 marked on one face of the test piece during a uniaxial tensile test.
• LYL 0 is the deformation along the axis of traction
• e / e 0 is the deformation in the direction perpendicular to the axis of traction.

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• 2005
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