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Definitions

• the invention relates to a self-healing composition based on at least one elastomer matrix comprising a segment chosen from polysiloxanes, polyesters, polyethers, polycarbonates, and polyolefins and a polyurea or polyurethane segment, and at least a polymeric material as a healing additive, its preparation process, its uses, an electric and / or optical cable comprising a layer obtained from said composition, and a particular healing additive.
• Polymeric materials during their service life, generally undergo many stresses which can be mechanical, thermal or even chemical. These stresses damage the materials, weaken them and sometimes make them unusable. It is known to use polymeric materials which self-heal or self-repair when they have undergone external degradations, such as cuts, lesions and / or cracks.
• the two most well-known strategies include the inclusion of reactive compounds (exogenous agents) which are released at the time of injury and react to repair the properties of the material (assisted scarring); and the incorporation of reversible bonds, such as those based on multiple hydrogen bonds, the material then has the intrinsic ability to heal.
• this process generally requires an external stimulus, an element which triggers the repair: an additive such as water or a solvent, an input voltage, heat, light, external pressure, or else specific environmental conditions such as a particular pH level.
• EP2785765B1 describes a silicone or polyurethane elastomer having self-healing properties.
• the elastomer described comprises a polymer chain functionalized with at least two sulfur atoms in the form of thiol, thiolate or forming part of a disulfide.
• these elastomers have insufficient mechanical properties, in particular in terms of stress and elongation at break, for many applications using rubbers.
• supramolecular silicone elastomeric materials have known in recent years a particular attention for their elastomeric properties, their good electrical resistance at high temperature, while guaranteeing good mechanical properties, in particular in terms of Young's modulus, and stress. and elongation at break.
• So-called supramolecular materials have the advantage of comprising so-called “reversible” (non-permanent) intermolecular bonds, unlike polymers from traditional chemistry which rely on so-called “irreversible” (permanent) bonds.
• the so-called “reversible” bonds can be hydrogen, ionic and / or hydrophobic bonds.
• these supramolecular silicone elastomeric materials thus have the advantage of being able to fluidize above a certain temperature, which facilitates their use, as well as their recycling.
• Such supramolecular silicone elastomers are described for example by Yilgor et al., Polymer, 2001, 42, 7953-7959. However, such elastomers do not have self-healing properties at room temperature.
• the object of the invention is therefore to overcome all or part of the drawbacks of the prior art and to provide a self-healing material, in particular at room temperature, easily recyclable, and having good mechanical properties, in particular in terms of module d 'Young, elongation and breaking stress.
• Another object of the invention is to provide a simple process, easily industrializable, economical and environmentally friendly for the preparation of said material.
• the first object of the invention is therefore a self-healing composition comprising at least one elastomer matrix corresponding to the following formula (I):
• SMi is a segment chosen from polysiloxanes, polyesters, polyethers, polycarbonates, and polyolefins,
• said SMi segment being associated with a polyurea or polyurethane SDi segment, in which:
• Ri is a divalent alkylene, arylene, or aralkylene group, comprising from 3 to 20 carbon atoms,
• R 2 is a divalent alkylene, arylene, or aralkylene group, comprising from 1 to 30 carbon atoms, said group optionally comprising one or more heteroatoms chosen from an oxygen atom, a sulfur atom and a halogen atom,
• Xi and X 2 are oxygen atoms -O- or amine groups -NH-, and
• X'i is an oxygen atom -O-, an amine group -NH- or an amine group -NR 4 -, R 4 being an alkyl group comprising from 1 to 12 carbon atoms, a benzyl group, a group allyl, or an alkylene group such as X'i and the group X 3 as defined below together form a ring, and
• o SM 2 is a segment chosen from polysiloxanes, polyesters, polyethers, polycarbonates, and polyolefins, said segment SM 2 being associated with a segment SD 2 , in which:
• R'i is a divalent alkylene, arylene, or aralkylene group, comprising from 3 to 20 carbon atoms,
• R ' 2 is a divalent alkylene, arylene, or aralkylene group, comprising from 1 to 30 carbon atoms, said group optionally comprising one or more heteroatoms chosen from an oxygen atom, a sulfur atom and a halogen atom ,
• X ' 2 is an oxygen atom -O-, an amine group -NH- or an amine group -NR 5 -, R 5 being an alkyl group comprising from 1 to 12 carbon atoms, a benzyl group, or a allyle group,
• o X 3 is an amine group -NH- or an amine group -NR 6 -, R 6 being an alkyl group comprising from 1 to 12 carbon atoms, a benzyl group, or an allyl group,
• o X 4 is an oxygen atom or a sulfur atom
• o p, q, r and s are such that the molar mass of the polymer material of formula (II) is between 1 and 200 kg / mol approximately,
• said elastomeric matrix (I) and said polymeric material (II) being such that:
• Xi is an amine group -NH-
• X is different from an oxygen atom -O-
• X ' 2 is different from an oxygen atom -O- when p 1 0, and at least l' one of the following definitions applies:
• * X ' 2 is an amine group -NR 5 - and p 1 0, * X 3 is an amine group -NR 6 -,
• X 3 is an amine group -NR 6 -.
• a second object of the invention is also a self-healing composition
• a self-healing composition comprising at least one elastomer matrix corresponding to formula (I) as defined in the first object of the invention, and a polymer material corresponding to the following formula (IIa) :
• segment SM 2 being associated with a segment SD 2 , in which: o R'i is as defined for formula (II), o R ' 2 is as defined for formula (II),
• o X'i is an oxygen atom -O-, an amine group -N H-, an amine group -NR 4 -, or a mixture of an amine group -N H- and an amine group -NR 4 -, R 4 being as defined for formula (II), where X ' 2 is an oxygen atom -O-, an amine group -N H-, an amine group -NR 5 -, or a mixture of an amine group -N H- and an amine group -NR 5 -, R 5 being as defined for formula (II), o X 3 is an amine group -NH-, an amine group -NR 6 -, or a mixture of an amine group -NH- and an amine group -NR 6 -, R 6 being as defined for the formula (II)
• o X 4 is an oxygen atom or a sulfur atom, and preferably an oxygen atom
• o p and r are such that the molar mass of the polymer material of formula (Ha) is between 1 and 200 kg / mol approximately,
• said elastomer matrix (I) and said polymer material (lia) being such that:
• Xi is an amine group -NH-
• X is different from an oxygen atom -O-
• X ' 2 is different from an oxygen atom -O- when p 1 0, and at least l' one of the following definitions applies:
• X'i is a mixture of an amine group -NH- and an amine group -
• X ' 2 is a mixture of an amine group -NH- and an amine group - NR 5 -, and p 1 0,
• X 3 is a mixture of an amine group -NH- and an amine group -
• Xi is an oxygen atom -O-
• X'i is an oxygen atom -O-
• X ' 2 is an oxygen atom -O- when p 1 0, and
• X 3 is a mixture d 'an amine group -NH- and an amine group -NR 6 -.
• the composition of the invention exhibits self-healing properties at room temperature: a (micro-) crack or break occurring in this composition can be repaired at room temperature, in particular using a simple contact of the two fracture surfaces, under slight pressure, without it being necessary to stick or heat. Furthermore, the self-healing composition of the invention is easily recyclable, and has good mechanical properties, in particular in terms of Young's modulus, elongation and tensile strength.
• the molar mass of the polymeric or elastomeric compounds as described below is preferably determined by the method of size exclusion chromatography (well known according to Anglicism "Size exclusion chromatography” or SEC).
• the elastomer matrix (I) preferably has a molar mass of between 20 and 100 kg / mol approximately.
• the SMi segment is generally called soft segment or block, said to be flexible or flexible, because it brings the elastomeric properties to the matrix.
• the SDi segment of the elastomer matrix of formula (I) is a hard segment or block, said to be rigid, and it provides the thermoplastic properties. The association of the SMi and SDi segments within the elastomer matrix (I) makes it possible to obtain good mechanical properties.
• the SMi segment is chosen from polysiloxanes, polyesters, polyethers, polycarbonates, and polyolefins.
• polyesters mention may be made of a polycaprolactone, or a poly (butanediol succinate).
• polyethers examples include poly (ethylene oxide), poly (propylene oxide), and poly (butylene oxide).
• polycarbonates mention may be made of a poly (trimethylene carbonate).
• polysiloxanes examples of polysiloxanes, mention may be made of a methylated, fluorinated, phenylated, vinylated polysiloxane, or one of their copolymers.
• the SMi segment is preferably chosen from polysiloxanes and polyethers.
• the SMi segment is chosen from polysiloxanes, and more preferably polydimethylsiloxanes.
• the SMi segment is chosen from polyethers.
• the alkylene group within the meaning of the present invention, can be linear (i.e. unsubstituted) or branched (i.e. substituted), cyclic (i.e. comprising at least one ring) or non-cyclic (i.e. comprising no ring).
• the alkyl group within the meaning of the present invention, can be linear (i.e. unsubstituted) or branched (i.e. substituted), cyclic (i.e. comprising at least one ring) or non-cyclic (i.e. comprising no ring).
• the arylene group within the meaning of the present invention, can be mono or polysubstituted.
• the aralkylene group within the meaning of the present invention, can be a group comprising at least one alkylene radical and at least one arylene radical, said alkylene and arylene radicals being linked by a carbon-carbon, carbon-nitrogen, carbon-oxygen bond or carbon-sulfur.
• the Ri alkylene group preferably contains from 3 to 16 carbon atoms, and more preferably from 5 to 15 carbon atoms. Linear alkylene groups having 3 to 10 carbon atoms and cyclic groups having 5 to 15 carbon atoms are preferred.
• the Ri arylene group preferably contains from 4 to 16 carbon atoms, and more preferably from 5 to 12 carbon atoms.
• the Ri aralkylene group preferably contains from 3 to 16 carbon atoms, and more preferably from 5 to 15 carbon atoms.
• the arylene radical can comprise from 4 to 20 carbon atoms, and preferably from 5 to 15 carbon atoms
• the alkylene group can comprise from 1 to 10 carbon atoms, and preferably from 1 to 6 carbon atoms.
• Aralkylene groups comprising two phenylene groups linked by an alkylene group or comprising two alkylene groups linked by a phenylene group are preferred.
• the group Ri is chosen from the following formulas:
• the group Ri is chosen from the following formulas:
• the R 2 alkylene group preferably contains from 1 to 20 carbon atoms, and more preferably from 2 to 12 carbon atoms. Cyclic or linear alkylene groups, optionally comprising one or more oxygen atoms, are preferred.
• the R 2 arylene group preferably contains from 4 to 16 carbon atoms, and more preferably from 5 to 12 carbon atoms.
• the phenylene group optionally substituted by one or more halogen atoms such as chlorine atoms, or by one or more alkyl groups having from 1 to 5 carbon atoms, said alkyl groups possibly comprising one or more sulfur atoms or d oxygen is preferred.
• the R 2 aralkylene group preferably contains from 5 to 30 carbon atoms, and more preferably from 8 to 25 carbon atoms.
• the arylene radical can comprise from 4 to 20 carbon atoms, and preferably from 5 to 15 carbon atoms, and the alkylene group can comprise from 1 to 10 carbon atoms, and preferably from 1 to 6 carbon atoms.
• Aralkylene groups comprising two phenylene groups linked by an alkylene group or comprising two alkylene groups linked by a phenylene group are preferred.
• the phenylene group can be substituted by one or more halogen atoms such as chlorine atoms.
• the alkylene group can include one or more sulfur or oxygen atoms.
• R 2 is chosen from an alkylene group comprising from 2 to 12 carbon atoms and the groups having the following formulas:
• R 2 is chosen from an alkylene group comprising from 2 to 12 carbon atoms and the groups having the following formulas:
• n can be equal to zero (absence of a chain extender) or greater than zero (presence of a chain extender).
• the presence of a chain extender makes it possible to increase the proportion of SDi segments, and thus to advantageously modulate the mechanical properties of the composition, in particular to improve its Young's modulus.
• the polymer material (II) or the polymer material (IIa) are the polymer material (IIa)
• the polymeric material (II) [respectively the polymeric material (IIa)] preferably has a molar mass of between 10 and 50 kg / mol approximately. With this molar mass, a good compromise is obtained in terms of self-healing and mechanical properties.
• the segment SM 2 is generally called soft segment or block, called flexible or flexible and it brings the elastomeric properties to the material.
• the segment SD 2 of the polymer material of formula (II) [respectively of the polymer material (lia)] is a hard segment or block, said to be rigid and it provides the thermoplastic properties.
• the SM 2 segment is chosen from polysiloxanes, polyesters, polyethers, polycarbonates, and polyolefins.
• polyesters mention may be made of a polycaprolactone, or a poly (butanediol succinate).
• polyethers examples include a poly (ethylene oxide), a poly (propylene oxide), or a poly (butylene oxide).
• polycarbonates mention may be made of a poly (trimethylene carbonate).
• polystyrene resin examples include polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene resin, polystyrene resin, polystyrene resin, polysty
• polysiloxanes examples include a methylated, fluorinated, phenylated, vinylated polysiloxane, or one of their copolymers.
• the SM 2 segment is preferably chosen from polysiloxanes and polyethers.
• the SM 2 segment is chosen from polysiloxanes, and more preferably polydimethylsiloxanes.
• the SM 2 segment is chosen from polyethers.
• alkyl group R 4 for the amine group -NR 4 - of X′i an alkyl group comprising from 1 to 6 carbon atoms such as a methyl, ethyl or propyl group is preferred, and more preferably a ethyl group.
• the alkylene group R'i preferably contains from 3 to 16 carbon atoms, and more preferably from 5 to 15 carbon atoms. Linear alkylene groups having 3 to 10 carbon atoms and cyclic groups having 5 to 15 carbon atoms are preferred.
• the R′i arylene group preferably contains from 4 to 16 carbon atoms, and more preferably from 5 to 12 carbon atoms.
• the R′i aralkylene group preferably contains from 3 to 16 carbon atoms, and more preferably from 5 to 15 carbon atoms.
• the arylene radical can comprise from 4 to 20 carbon atoms, and preferably from 5 to 15 carbon atoms
• the alkylene group can comprise from 1 to 10 carbon atoms, and preferably from 1 to 6 carbon atoms.
• Aralkylene groups comprising two phenylene groups linked by an alkylene group or comprising two alkylene groups linked by a phenylene group are preferred.
• the group R'i is chosen from the following formulas:
• the group R'i is chosen from the following formulas:
• the groups Ri and R'i may be identical or different, and preferably identical.
• the R ′ 2 alkylene group preferably contains from 1 to 20 carbon atoms, and more preferably from 2 to 12 carbon atoms. Cyclic or linear alkylene groups, optionally comprising one or more oxygen atoms, are preferred.
• the group R ′ 2 arylene preferably contains from 4 to 16 carbon atoms, and more preferably from 5 to 12 carbon atoms.
• the phenylene group optionally substituted by one or more halogen atoms such as chlorine atoms, or by one or more alkyl groups having from 1 to 5 carbon atoms, said alkyl groups possibly comprising one or more sulfur atoms or d oxygen is preferred.
• the R ′ 2 aralkylene group preferably contains from 5 to 30 carbon atoms, and more preferably from 8 to 25 carbon atoms.
• the arylene radical can comprise from 4 to 20 carbon atoms, and preferably from 5 to 15 carbon atoms, and the alkylene group can comprise from 1 to 10 carbon atoms, and preferably from 1 to 6 carbon atoms.
• Aralkylene groups comprising two phenylene groups linked by an alkylene group or comprising two alkylene groups linked by a phenylene group are preferred.
• the phenylene group can be substituted by one or more halogen atoms such as chlorine atoms.
• the alkylene group can include one or more sulfur or oxygen atoms.
• R' 2 is chosen from an alkylene group comprising from 2 to 12 carbon atoms and groups having the following formulas:
• R ′ 2 is chosen from an alkylene group comprising from 2 to 12 carbon atoms and the groups having the following formulas:
• p can be equal to zero (absence of a chain extender) or greater than zero (presence of a chain extender).
• the presence of a chain extender makes it possible to increase the proportion of SD 2 segments, and thus to advantageously modulate the mechanical properties of the composition, in particular to improve its Young's modulus.
• the groups R 2 and R ′ 2 can be identical or different, and preferably identical.
• alkyl group R 5 for the amine group -NR 5 - of X ′ 2 an alkyl group comprising from 1 to 6 carbon atoms such as a methyl, ethyl or propyl group is preferred, and more preferably a methyl group.
• alkyl group R 6 for the amine group -NR 6 - of X 3 an alkyl group comprising from 1 to 6 carbon atoms such as a methyl, ethyl or propyl group is preferred, and more preferably a group methyl.
• s is such that 0 ⁇ s ⁇ 10, and s is preferably equal to zero.
• the group R 3 optionally comprises one or more heteroatoms chosen from an oxygen atom, a nitrogen atom, and one of their mixtures, in particular in the form of one or more amide, ester, urethane or urea functions.
• the R 3 alkylene group preferably contains from 3 to 24 carbon atoms, and more preferably from 6 to 24 carbon atoms.
• Branched alkylene groups in particular those comprising at least one amide or ester function capable of linking the trivalent R 3 group to the —NH— radicals of formula (II), are preferred.
• the R 3 arylene group preferably contains from 4 to 16 carbon atoms, and more preferably from 5 to 12 carbon atoms.
• the phenylene group optionally substituted by one or more alkyl groups having from 1 to 5 carbon atoms, the alkyl groups possibly being substituted by one or more nitrogen, oxygen atoms or a mixture thereof, is preferred.
• the R 3 aralkylene group preferably contains from 5 to 30 carbon atoms, and more preferably from 8 to 25 carbon atoms.
• the arylene radical can comprise from 4 to 20 carbon atoms, and preferably from 5 to 15 carbon atoms
• the alkylene group can comprise from 1 to 10 carbon atoms, and preferably from 1 to 6 carbon atoms.
• Aralkylene groups comprising three phenylene groups linked by an alkylene group or comprising three alkylene groups linked by a phenylene group are preferred.
• the alkylene and phenylene groups can be, independently of one another, substituted by one or more atoms of nitrogen, oxygen or one of their mixtures.
• R 3 is chosen from an alkylene group comprising from 3 to 24 carbon atoms and the groups having the following formulas:
• R 4 is an alkylene group such that X′i and X 3 together form a ring
• R 4 is preferably a linear alkylene group comprising 2 or 3 carbon atoms.
• the group R 5 for the amine group -NR 5 - of X ′ 2 / is an alkyl group as defined in the invention.
• the group R 5 for the amine group -NR 5 - of X ′ 2 is a benzyl or allyl group.
• the group R 6 for the amine group -NR 6 - of X 3 is an alkyl group as defined in the invention.
• the group R 6 for the amine group -NR 6 - of X 3 is a benzyl or allyl group.
• the material of formula (II) is such that Xi is an amine group -NH-, X is different from an oxygen atom -O-, X ' 2 is different of an oxygen atom -O- when p 1 0, and X 4 is a sulfur atom and / or X'i is an amine group -NR 4 -.
• the elastomer matrix (I) and the polymer material (II) can advantageously be such that:
• Xi is an amine group -NH-
• X is an amine group -NH- or -NFLr, and preferably an amine group -NH-
• X 3 is an amine group -NH- or -NR 6 -, and preferably an amine group -NH-
• X 4 is a sulfur atom, or
• Xi is an amine group -NH-
• X is an amine group -NR 4 -
• X 3 is an amine group -NH- or -NR 6 -, and preferably an amine group -NH-
• X is an atom oxygen.
• p 0, or p 1 0 and X ′ 2 is an amine group -NH- or -NR 5 -, and preferably an amine group -NH-.
• SMi and SM 2 are preferably chosen from polysiloxanes and polyethers.
• the material of formula (II) is such that Xi is an oxygen atom -O-, X'i is an oxygen atom -O-, X ' 2 is an oxygen atom -O- when p 1 0, and X 3 is an amine group -NR 6 -.
• the elastomer matrix (I) and the polymer material (II) can advantageously be such that Xi is an oxygen atom -O-, X is an oxygen atom -O- , X 3 is an amine group -NR 6 -, and X 4 is an oxygen atom.
• SMi and SM 2 are preferably chosen from polyesters, polyethers, and polyolefins.
• Such a compound of formula (IIa) has, like the compound of formula (II), healing properties.
• the expression “mixture of an amine group -NH- and of an amine group -NR 4 -, -NR 5 -, or -NR 6 - means the presence on certain parts or units of the polymer material ( lia) of an amine group -NH-, and the presence on other units or parts of the same polymeric material (Ha) of an amine group -NR 4 -, -NR 5 -, or -NR 6 -.
• at least one of the groups R 4 , R 5 , or R 6 is distributed statistically in the chain of the polymer material (Ha). This is called the substitution rate.
• the substitution rate T 4 relating to the group R 4 , the substitution rate T 5 relating to the group R 5 and the substitution rate T 6 relating to the group R 6 are such that 0% ⁇ T 4 ⁇ 100%, 0% ⁇ T 5 ⁇ 100%, and 0% ⁇ T 6 ⁇ 100%, it being understood that at least one of said rates T 4 , T 5 , or T 6 is strictly greater than 0% and strictly less than 100%.
• a substitution rate T x of 100% means that all the amine groups are substituted in the polymer material (IIa) and that there is therefore no mixture of amine groups -NH- and -NR 4 -, or mixture of amine groups -NH- and -NR 5 -, or mixture of amine groups -NH- and - NR 6 -.
• the substitution rate T 4 , T 5 , or T 6 ranges from approximately 30 to 70%.
• substitution rate can be determined by NMR analysis, in particular by the presence of the peaks of the groups R, R 5 , or R 6 in the polymer material of formula (IIa).
• X'i is an oxygen atom -O-
• X ' 2 is an oxygen atom -O- when p 1 0, and
• X 3 is a mixture of an amine group - NH- and an amino group -NR 6 -.
• the polymer material (II) [respectively the polymer material (lia)] preferably represents from 0.1 to 100% by mass approximately, preferably from 0.5 to 50% by mass approximately, and more preferably from 1 to 20% by mass approximately, relative to the total mass of the elastomer matrix (I). With these proportions a good compromise is obtained in terms of self-healing and mechanical properties.
• the composition may also comprise at least one inorganic filler, in particular chosen from silica, preferably in the form of quartz, talc, calcium carbonate, carbon black, and one of their mixtures.
• the inorganic filler can make it possible to reinforce the mechanical properties of the composition.
• Silica, and in particular quartz, as the inorganic filler is preferred.
• the inorganic filler can represent from 1 to 70% by mass approximately, relative to the total mass of the elastomer matrix (I), and preferably from 5 to 30% by mass approximately, relative to the total mass of the elastomer matrix (I).
• the SMi and SM 2 segments in the composition are of the same chemical nature.
• they can be together polysiloxanes, polyesters, polyethers, polycarbonates, or polyolefins, and preferably polysiloxanes or polyethers.
• the composition of the invention preferably has a Young's modulus varying from 0.5 to 50 MPa approximately, and more preferably from 0.5 to 20 MPa approximately.
• the composition of the invention preferably has a breaking stress varying from 0.1 to 20 MPa approximately, and more preferably from 0.2 to 5 MPa approximately.
• the composition of the invention preferably has an elongation at break varying from 50 to 2000% approximately, and more preferably from 60 to 1200% approximately.
• the third object of the invention is also a method of preparing a composition in accordance with the first or second object of the invention, characterized in that it comprises at least one step of mixing the elastomer (I) with the polymer material (II) or polymer material (Ha), solvent or melt.
• the mixing step comprises the following substeps:
• the solvent Si can be chosen from tetrahydrofuran, acetone, diacetone alcohol, dichloromethane, toluene, and one of their mixtures.
• the solvent S 2 can be chosen from tetrahydrofuran, acetone, diacetone alcohol, dichloromethane, toluene, and one of their mixtures.
• the solvents Si and S 2 are preferably identical.
• the resulting mixture obtained can be shaped, in particular by spraying the above-mentioned resulting solution onto said support, or by stretching with a film applicator.
• the mixing step comprises the following substeps:
• the elastomer (I) can be prepared by polyaddition of at least one diisocyanate with at least one polymer chosen from polysiloxanes, polyesters, polyethers, polycarbonates, and polyolefins, optionally in the presence of a catalyst.
• the polymer has in particular terminal functions allowing polyaddition with the diisocyanate, such as amine functions, or alcohol functions.
• the diisocyanate can be chosen from 2,4 toluene diisocyanate, 4,4 'diphenylmethane diisocyanate, 1,6 hexamethylene diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-bis (1-isocyanato-1-methylethyl) benzene and 1,1'-methylenebis (4-isocyanatocyclohexane).
• the polymeric material (II) or (IIa) can be prepared according to the same methods as those as defined above for the preparation of the elastomer (I).
• a fourth object of the invention is the use of a polymer material corresponding to formula (II) or (IIa) as defined in the first or second subject of the invention, as a healing additive for a elastomer corresponding to formula (I) as defined in the first subject of the invention.
• the composition acquires self-healing properties, in particular at room temperature, without degrading the mechanical properties of the elastomer matrix (I).
• the composition according to the invention exhibits self-healing characteristics without any external stimuli (temperature, pressure, etc.). .) is required.
• the fifth object of the invention is the use of a composition in accordance with the first or second object of the invention, as a self-healing material, in particular at room temperature.
• the sixth object of the invention is the use of a composition in accordance with the first or second object of the invention, for the manufacture of seals, in particular seals, coatings, vibration damping materials, or insulating materials for electrical and / or optical cables.
• compositions of the invention can also be used for the manufacture of conveyor belts, impact protection, professional gloves, coatings, in particular anti-corrosion coatings, metals, or additives in the field of adhesives, bitumens, organic binders, paints, varnishes, pastes and sealants.
• the seventh subject of the invention is an electrical and / or optical cable comprising at least one electrical and / or optical conductive element, and at least one polymer layer surrounding the electrical and / or optical conductive element, characterized in that that the polymer layer is obtained from a composition in accordance with the first or second object of the invention.
• the eighth object of the invention is a healing additive, characterized in that it is a polymer material corresponding to formula (II) as defined in the first subject of the invention, and in which X'i is a group amine -N-ethyl, N-benzyl, or N-allyl, and preferably an N-ethyl group, X 3 is an amine group -NH-, SM 2 is a polydimethylsiloxane segment, and X 4 is an oxygen atom .
• the molecular weight of the polymers was measured by the method known as SEC for “Size exclusion chromatography”.
• Size exclusion chromatography (SEC) measurements were carried out with three PL Mixed Gel C using columns of 5 ⁇ m (commercial products of the company Agilent) (7.5 ⁇ 300 mm; having separation limits: 0.2 to 2000 kg. Mol 1 ) maintained at 40 ° C, coupled to a solvent distribution module and to a Viscoteck 3580 sample detector with differential refractive index (IR).
• the mobile phase used is composed of THF, at a flow rate of 1 ml. min 1 , and toluene was used as the flow marker. All the polymers according to the invention were injected (100 ⁇ L) at a concentration of 5 mg.ml 1 after filtration through a 0.45 ⁇ m membrane.
• An OMNISEC data analysis device was used for data acquisition and analysis.
• Example 1 Preparation of a self-healing composition C1 in accordance with the invention
• IPDI isophorone diisocyanate
• THF anhydrous tetrahydrofuran
• DMS-A214 N-ethylaminoisobutyl
• Example 2 Preparation of a self-healing composition C2 in accordance with the invention
• toluene-2,4-diisothiocyanate (0.57 mmol) was dissolved at room temperature under an inert atmosphere (N 2 ), in 20 ml of anhydrous THF. Then, a polydimethylsiloxane substituted in the terminal positions with 3-aminopropyl (FluidNH40d; 0.60 mmol) was dissolved in 18 ml of anhydrous THF and the resulting solution was added to the flask using a syringe pump ( with a flow rate of 1.3 ml / h). The resulting solution was stirred for 17 hours.
• toluene-2,4-diisocyanate (11.85 mmol) was dissolved at room temperature under an inert atmosphere (N 2 ), in 200 ml of anhydrous THF, then a polydimethylsiloxane substituted in the terminal positions with 3 -aminopropyl (FluidNH40d; 8.98 mmol) was added to the flask. The resulting solution was stirred for 3 hours. An additional quantity of the substituted polydimethylsiloxane (2.99 mmol) dissolved in 10 ml of anhydrous THF was added using a syringe pump (with a flow rate of 1.4 ml / h).
• toluene-2,4-diisocyanate (1 mmol) was dissolved at room temperature under an inert atmosphere (N 2 ), in 20 ml of anhydrous THF. Then, a polydimethylsiloxane substituted in the terminal positions with N-ethylaminoisobutyl (DMS-A214; 1.1 mmol) was added to the flask. The resulting solution was stirred for 24 hours. The completion of the reaction was checked by infrared spectroscopy by the disappearance of the absorption peak of the isocyanate. Once the reaction was complete, the solvent was evaporated and the product obtained dried under vacuum (10 3 mbar) at 70 ° C for 2 days. 2.6 g of product were obtained (98% yield).
• toluene-2,4-diisocyanate (TDI; 7.39 mmol) was dissolved at room temperature under an inert atmosphere (N 2 ), in 200 ml of anhydrous THF, then a polydimethylsiloxane substituted as terminal positions with 3-aminopropyl (FluidNH40d; 4.49 mmol) was added to the flask. The resulting solution was stirred for 4 hours.
• Example 4 physico-chemical characterizations of the self-healing compositions C1, C2 and C3 according to the invention
• Young's modulus (in MPa), stress at break (in MPa) and elongation at break (in%) were determined using a device sold under the trade name Instron 5565 by the company Instron in the following way: the values of the stress at break as well as the elongation at break were measured directly during the break of the material. Regarding Young's modulus, the value has been determined by analysis of the slope of the traction curve over the first 5 percent of deformation.
• the self-healing character has been demonstrated as follows: either by visual monitoring of the closure of a notch (example 1), or by recovery of the tensile strength at a given time from a sample previously notched on half of its width (examples 2 and 3).
• Table 1 illustrated below lists the values of Young's modulus, breaking stress and elongation at break, before notching of compositions C1, C2 and C3, and for comparison of the elastomeric matrices (1-1), ( 1-2) and (1-3) as prepared in Examples 1 to 3 above, as well as the self-healing times (in hours) and self-healing percentages (in%) of the compositions C1 , C2 and C3 after notching.
• compositions have a breaking stress which can be lowered compared to the elastomers of formula (I).
• the recovery from the breaking stress of the compositions is greater than for the elastomers (eg from 17% to 85% for the compositions and from 0% for the elastomers).
• the addition of a polymer material of formula (II) therefore accelerates the kinetics of self-repair of the composition, while guaranteeing good mechanical properties.
• Figure 1 attached shows the self-healing properties of composition C1 and for comparison of elastomer 1-1 when they were subjected to the following protocol: cuts with a cutter were made in layers obtained at starting from composition C1 (Figure IA) and elastomer 1-1 (Figure IB), then the self-repair was visually followed at room temperature as a function of time. It is observed after 6 days at room temperature that the notch has strongly resorbed only in the case of composition C1 (FIG. IA). The black line represents the original size of the notch (2.5 cm).
• Example 5 Preparation of a C4 self-healing composition in accordance with the invention
• the reaction medium was cooled using an ice water bath (5 ° C), stirred and under an inert atmosphere.
• the solution containing the elastomeric matrix (1-4) was transferred by cannula in 40 minutes into the flask containing sodium hydride in THF.
• the ice-water bath was removed and three cycles of vacuum-argon were carried out in the reaction medium.
• iodomethane CH3I; 4, llmL; 66.08 mmol
• the reaction medium was cooled using an ice water bath (5 ° C), stirred and under an inert atmosphere.
• the solution containing the elastomeric matrix (1-4) was transferred by cannula in 40 minutes into the flask containing sodium hydride in THF.
• the ice-water bath was removed and three cycles of vacuum-argon were carried out in the reaction medium.
• benzyl bromide (BnBr; 4.96 ml; 41.86 mmol) was added dropwise to the reaction medium.
• the product obtained was purified by precipitation in pentane (500 ml), followed by filtration and drying under vacuum (10 3 mbar) at 40 ° C for 1 day. 6.50 g of product were obtained (84% yield).
• the number-average molar mass (Mn) of the polymer (II-5), measured by SEC, is 68501 g / mol.
• Example 7 Preparation of a C6 self-healing composition in accordance with the invention
• the reaction medium was cooled using an ice water bath (5 ° C), stirred and under an inert atmosphere.
• the solution containing the elastomeric matrix (1-5) was transferred by cannula in 40 minutes into the flask containing sodium hydride in THF.
• the ice-water bath was removed and three cycles of vacuum-argon were carried out in the reaction medium.
• iodomethane CH 3 I; 2.61 ml; 41.85 mmol
• Example 8 Preparation of a C7 self-healing composition in accordance with the invention
• the elastomeric matrix (1-5) as defined above (6.72 g; 13.44 mmol of urethane function) was dissolved in 250 ml of anhydrous tetrahydrofuran (THF) at room temperature under inert atmosphere (Ar).
• anhydrous tetrahydrofuran (THF) at room temperature under inert atmosphere (Ar).
• sodium hydride NaH; 0.9845 g; 41.02 mmol; 60% in mineral oil
• 10 ml of tetrahydrofuran (THF) were introduced.
• the reaction medium was cooled using an ice water bath (5 ° C), stirred and under an inert atmosphere.
• the solution containing the elastomeric matrix (1-5) was transferred by cannula in 40 minutes into the flask containing sodium hydride in THF.
• the ice-water bath was removed and three cycles of vacuum-argon were carried out in the reaction medium.
• benzyl bromide (BnBr; 4.96 ml; 41.02 mmol) was added dropwise to the reaction medium.
• the product obtained was purified by precipitation in pentane (450 ml), followed by filtration and drying under vacuum (10 3 mbar) at 40 ° C for 1 day. 5.52 g of product were obtained (70% yield).
• the number-average molar mass (Mn) of the polymer (II-7), measured by SEC, is 41,966 g / mol.
• Example 9 physico-chemical characterizations of the self-healing compositions C4, C5, C6 and C7 in accordance with the invention
• the Young's modulus (in MPa), the breaking stress (in MPa), and the elongation at break (in%) were determined by a tensile test carried out at a displacement speed of 30 mm / min on dumbbell type geometry specimens 5a (ISO 527) obtained by injection molding process, using a device sold under the trade name INSTRON 5565 by the company Instron.
• the values of the breaking stress as well as the elongation at break were measured directly during the rupture of the material. With regard to the Young's modulus, the value was determined by analysis of the slope of the traction curve between 1 and 1.5 percent of deformation.
• the self-healing character has been demonstrated as follows: either by visual monitoring of the closure of a notch,
• Table 2 illustrated below lists the values of Young's modulus, breaking stress and elongation at break, before cutting and after cutting of compositions C4, C5, C6 and C7, and for comparison of the elastomeric matrices (1 -4) and (1-5).
• the self-healing time (in hours) and the percentage of self-healing (in%) are mentioned for each composition.
• Example 1 0 preparation of a self-healing position C8 including taking a polymeric material of form u (I I I)
• the elastomeric matrix (1-4) as defined above (6.12 g; 12.48 mmol of urethane function) was dissolved in 250 ml of anhydrous tetrahydrofuran (THF) at room temperature under atmosphere inert (Ar).
• anhydrous tetrahydrofuran (THF) at room temperature under atmosphere inert (Ar).
• sodium hydride NaH; 0.6023 g; 25.10 mmol; 60% in mineral oil
• 10 ml of tetrahydrofuran (THF) were introduced.
• the reaction medium was cooled using a bath ice water (5 ° C), stirred and under an inert atmosphere.
• the solution containing the elastomeric matrix (1-4) was transferred by cannula in 40 minutes into the flask containing sodium hydride in THF.
• the ice-water bath was removed and three cycles of vacuum-argon were carried out in the reaction medium.
• iodomethane CH 3 I; 0.51 ml; 8.24 mmol
• compositions in accordance with the invention have shown their self- healing using similar proportions of compounds of formula (I) and (II) as described in the previous examples.
• composition C9 comprising a compound of the following formula (I):
• composition C1 0 comprising a compound of formula (I) below:
• composition C1 1 comprising a compound of formula (I) below:
• Figure 2 attached shows one of the self-healing compositions as defined above, which heals dramatically after 24 hours, without external stimuli (temperature, pressure %)

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• 2018
  • 2018-08-01 FR FR1857196A patent/FR3084669B1/fr active Active
• 2019
  • 2019-07-30 US US17/264,781 patent/US20210292464A1/en not_active Abandoned
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