阅读说明：本技术 自修复组合物 (Self-healing composition ) 是由 劳伦特·布泰耶 莱奥·西莫南 桑德兰·庞塞克 弗朗索瓦·加纳绍 罗曼·布吕尼曼 劳拉·路易 于 2019-07-30 设计创作，主要内容包括：本发明涉及一种自修复组合物,其基于至少一种弹性体基质以及至少一种作为修复添加剂的聚合物材料,其中弹性体基质包含选自聚硅氧烷、聚酯、聚醚、聚碳酸酯和聚烯烃中的片段以及聚脲或聚氨酯片段。本发明还涉及该自修复组合物的制备方法、该自修复组合物的用途、包括由所述组合物获得的层的电缆和/或光缆、以及特定的修复添加剂。(The invention relates to a self-healing composition based on at least one elastomer matrix and at least one polymer material as healing additive, wherein the elastomer matrix comprises segments selected from the group consisting of polysiloxanes, polyesters, polyethers, polycarbonates and polyolefins and polyurea or polyurethane segments. The invention also relates to a process for the preparation of the self-healing composition, to the use of the self-healing composition, to an electrical and/or optical cable comprising a layer obtained from said composition, and to a specific healing additive.)

1. A self-healing composition comprising at least one elastomeric matrix corresponding to the following formula (I):

wherein:

m and n are such that the molar mass of the elastomeric matrix of formula (I) is from 2kg/mol to 200kg/mol,

*SM₁is a segment selected from the group consisting of polysiloxanes, polyesters, polyethers, polycarbonates and polyolefins,

the segment SM₁With polyurea or polyurethane segments SD₁In combination, wherein:

*R₁is a divalent alkylene, arylene or aralkylene group comprising 3 to 20 carbon atoms,

*R₂is a divalent alkylene, arylene or aralkylene group comprising from 1 to 30 carbon atoms, said group optionally containing one or more heteroatoms selected from oxygen atoms, sulfur atoms or halogen atoms,

*X₁and X₂Is the same as oxygen atom-O-or amino group-NH-, and

*n≥0，

the self-healing composition is characterized in that the self-healing composition further comprises a polymeric material corresponding to the following formula (II):

wherein:

*0≤s≤10，

*R₃is an at least trivalent alkylene, arylene or aralkylene group comprising from 3 to 30 carbon atoms, said R₃The group may optionally contain one or more heteroatoms selected from oxygen atoms, nitrogen atoms, and mixtures thereof, said R₃The radicals may be substituted by 1, 2 or 3 additional-NH-C (═ O) X'₁-a group of E is substituted,

*X'₁is oxygen atom-O-, amino-NH-or amino-NR₄-，R₄Is alkyl, benzyl, allyl or alkylene comprising from 1 to 12 carbon atoms, such that X'₁And X as defined below₃The radicals together form a ring, an

E corresponds to the following formula (II'):

wherein:

οSM₂is a segment selected from the group consisting of polysiloxanes, polyesters, polyethers, polycarbonates and polyolefins,

the segment SM₂And fragment SD₂In combination, wherein:

οR'₁is a divalent alkylene, arylene or aralkylene group comprising 3 to 20 carbon atoms,

οR'₂is a divalent alkylene, arylene or aralkylene group comprising from 1 to 30 carbon atoms, said group optionally containing one or more heteroatoms selected from oxygen atoms, sulfur atoms or halogen atoms,

οX₁as defined in formula (I) above,

οX'₁as defined in formula (II) above,

οX'₂is oxygen atom-O-, amino-NH-or amino-NR₅-，R₅Is an alkyl, benzyl or allyl group comprising from 1 to 12 carbon atoms,

οX₃is amino-NH-or amino-NR₆-，R₆Is an alkyl, benzyl or allyl group comprising from 1 to 12 carbon atoms,

οX₄is an oxygen atom or a sulfur atom,

οp≥0，

o 0< q ≦ 1, and

p, q, r and s are such that the molar mass of the polymeric material of formula (II) is from 1kg/mol to 200kg/mol,

the elastomeric matrix (I) and the polymeric material (II) are such that:

when X is₁Is amino-NH-, X'₁Not being an oxygen atom-O-, when p ≠ 0, X'₂Is not an oxygen atom-O-, and at least one of the following definitions applies:

*X₄is a sulfur atom, and is a hydrogen atom,

*X'₁is amino-NR₄-，

*X'₂Is amino-NR₅-, and p.noteq.0,

*X₃is amino-NR₆-，

When X is₁Is oxygen atom-O-, X'₁Is an oxygen atom-O-, when p ≠ 0, X'₂Is an oxygen atom-O-, and at least one of the following applies:

*X₄is a sulfur atom, and is a hydrogen atom,

*X₃is amino-NR₆-。

2. A self-healing composition comprising at least one elastomeric matrix corresponding to formula (I) as defined in claim 1 and a polymeric material corresponding to the following formula (IIa):

wherein:

οSM₂as defined in claim 1, the first and second,

the segment SM₂And fragment SD₂In combination, wherein:

οR'₁as defined in claim 1, the first and second,

οR'₂as defined in claim 1, the first and second,

οX'₁is oxygen atom-O-, amino-NH-, amino-NR₄-, or are amino-NH-and amino-NR₄A mixed group of (A) and (B), R₄As defined in claim 1, the first and second,

οX'₂is oxygen atom-O-, amino-NH-, amino-NR₅-, or are amino-NH-and amino-NR₅A mixed group of (A) and (B), R₅As defined in claim 1, the first and second,

οX₃is amino-NH-, amino-NR₆-, or are amino-NH-and amino-NR₆A mixed group of (A) and (B), R₆As defined in claim 1, the first and second,

οX₄is an oxygen atom or a sulfur atom,

p is as defined in claim 1,

o q is 1, and

p and r are such that the molar mass of the polymeric material of formula (IIa) is from about 1kg/mol to 200kg/mol,

the elastomeric matrix (I) and the polymeric material (IIa) are such that:

when X is₁Is amino-NH-, X'₁Not being an oxygen atom-O-, when p ≠ 0, X'₂Is not an oxygen atom-O-, and at least one of the following definitions applies:

*X'₁is amino-NH-and amino-NR₄-a mixed group of (a) and (b),

*X'₂is amino-NH-and amino-NR₅-and p ≠ 0,

*X₃is amino-NH-and amino-NR₆-a mixed group of (a) and (b),

when X is₁Is oxygen atom-O-, X'₁Is an oxygen atom-O-, when p ≠ 0, X'₂Is an oxygen atom-O-, and X₃Is amino-NH-and amino-NR₆-mixed groups of (a) and (b).

3. The composition of claim 1 or 2, wherein R is₁And R'₁Identical or different and selected from the following formulae:

wherein symbol # represents R₁Attachment of a group to an NH group、R'₁The point of attachment of a group to the NH group and R'₁Radical and X₃The point of attachment of the group.

4. Composition according to any one of the preceding claims, characterized in that R₁And R'₁Identical or different and selected from the following formulae:

wherein symbol # represents R₁Point of attachment of group to NH group, R'₁The point of attachment of a group to the NH group and R'₁Radical and X₃The point of attachment of the group.

5. Composition according to any one of the preceding claims,

-when X'₂Is amino-NH-and/or-NR₅-is, -R'₂Selected from the group consisting of alkylene groups comprising 2 to 12 carbon atoms and groups having the formula:

wherein symbol # represents R'₂Radical and X'₂The point of attachment of the group,

-when X'₂R 'when being an oxygen atom-O'₂Selected from the group consisting of alkylene groups comprising 2 to 12 carbon atoms and groups having the formula:

wherein symbol # represents R'₂Radical and X'₂The point of attachment of the group.

6. A composition according to any preceding claim, characterized in thatThe segment SM₁And SM₂Is polysiloxane or polyether.

7. The composition according to claim 1 and any one of claims 3 to 6, wherein X is₁Is amino-NH-, X'₁Is amino-NH-or-NR₄-，X₃Is amino-NH-or-NR₆-, and X₄Is a sulfur atom.

8. The composition according to claim 1 and any one of claims 3 to 6, wherein X is₁Is amino-NH-, X'₁Is amino-NR₄-，X₃Is amino-NH-or-NR₆-, and X₄Is an oxygen atom.

9. The composition according to claim 1 and any one of claims 3 to 6, wherein X is₁Is an oxygen atom-O-, X'₁Is an oxygen atom-O-, X₃Is amino-NR₆-, and X₄Is an oxygen atom.

10. The composition according to claim 1 and any one of claims 3 to 9, wherein R is₃Selected from alkylene groups comprising 3 to 24 carbon atoms and groups having the formula:

wherein symbol # represents R₃The point of attachment of the group to the-NH-group.

11. Composition according to any one of the preceding claims, characterized in that the ratio: segment SD₂Molar mass/(segment SD)₂Molar mass + fragment SM₂Molar mass) between 0.01 and 0.6.

12. The composition according to any one of the preceding claims, characterized in that:

when X is₂When it is amine-NH-, R₂Selected from the group consisting of alkylene groups comprising 2 to 12 carbon atoms and groups having the formula:

wherein symbol # represents R₂Radical and X₂The point of attachment of the group,

when X is₂When it is an oxygen atom-O-, R₂Selected from the group consisting of alkylene groups comprising 2 to 12 carbon atoms and groups having the formula:

wherein symbol # represents R₂Radical and X₂The point of attachment of the group.

13. Composition according to any one of the preceding claims, characterized in that the ratio in the elastomer (I): segment SD₁Molar mass/(segment SD)₁Molar mass + fragment SM₁Molar mass) between 0.01 and 0.6.

14. Composition according to any one of the preceding claims, characterized in that it further comprises at least one inorganic filler.

15. Composition according to any one of the preceding claims, characterized in that the polymeric material (II) or (IIa) ranges from 0.1% to 100% by weight relative to the total weight of the elastomeric matrix (I).

16. A process for preparing the composition according to any one of the preceding claims, characterized in that it comprises at least one stage of mixing the elastomer (I) with the polymeric material (II) or (IIa) by the solvent route or by the melt route.

17. Use of a polymeric material corresponding to formula (II) or (IIa) as a repair additive for elastomers corresponding to formula (I) as defined in any one of claims 1,3, 4, 6 to 9, 12 and 13, said formulae (II) and (IIa) being as defined in any one of claims 1 to 11.

18. Use of a composition as defined in any one of claims 1 to 15 as a self-healing material, in particular at ambient temperature.

19. Use of a composition as defined in any one of claims 1 to 15 for the manufacture of a seal, a cladding, a material for shock absorption, or an insulation material for electrical and/or optical cables.

20. An electrical and/or optical cable comprising at least one electrically and/or optically conductive element, and at least one polymer layer surrounding said electrically and/or optically conductive element, characterized in that said polymer layer is obtained from a composition as defined in any one of claims 1 to 15.

21. A repair additive, characterized in that the repair additive is a polymeric material corresponding to formula (II) as defined in claim 1, and wherein X'₁Is amino N-ethyl, N-benzyl or N-propenyl, X₃Is amino-NH-, SM₂Is a polydimethylsiloxane fragment, and X₄Is an oxygen atom.

Examples

In the examples, the molar mass of the polymers is determined by the "SEC" (size exclusion chromatography) method.

Size Exclusion Chromatography (SEC) assay by using three PL Gel mix C using 5 μm chromatographyColumn (commercial product of Agilent) (7.5X 300 mm; separation limit: 0.2kg. mol.)^-1To 2000kg.mol^-1) The column was connected to a solvent distribution block and a Viscotek 3580 differential Refractive Index (RI) detector of the sample, maintained at 40 ℃. The mobile phase used consisted of THF at a flow rate of 1ml.min^-1And toluene was used as a flow rate marker. All polymers according to the invention were filtered through a 0.45 μm membrane at 5mg.ml^-1Was injected (100. mu.l). Data were acquired and analyzed using an OmniSEC data analysis device. The molar mass (Mn, number average molar mass, Mw, weight average molar mass) and the dispersity (═ Mw/Mn) were obtained from calibration curves based on Polystyrene (PS) Standards (obtained from Polymer Standards Service).

Other techniques than SEC techniques are envisaged for determining the molar mass of the composition according to the invention and known to the person skilled in the art of polymers.

Example 1: preparation of self-healing composition C1 according to the invention

1.1 preparation of the polymeric Material corresponding to formula (II-1)

A polymeric material of the following formula (II-1) is prepared by:

in a round bottom reaction flask, at ambient temperature and inert atmosphere (N)₂) The isophorone diisocyanate (IPDI; 0,78mmol) was dissolved in 20ml of anhydrous Tetrahydrofuran (THF) and then the terminal position N-ethylaminoisobutyl substituted polydimethylsiloxane (DMS-a 214; 0.78mmol) and a catalytic amount of triethylamine were added to the round bottom flask. The solution was then stirred for 12 days. Completion of the reaction was confirmed by disappearance of the absorption peak of isocyanate by infrared spectroscopy. Once the reaction was complete, the solvent was evaporated. The product obtained is then dissolved in 20ml of dichloromethane and subsequently washed with 3X 10ml of distilled water. Under vacuum (10)^-3mbar) was dried at 70 ℃ for 2 days. 1.8g of product are obtained (yield)87% in this case).

1.2 preparation of self-healing composition C1

To prepare the self-healing composition, an elastomeric matrix sold under the trade name Geniomer 80 and corresponding to the following formula (I-1) is used:

for this purpose, 5g of the elastomer matrix of the formula (I-1) and 538mg of the polymer material of the formula (II-1) prepared as described above in example 1.1 were dissolved in 20ml of THF and 2ml of THF, respectively. After stirring for 1 hour, the solution comprising the polymeric material of formula (II-1) is added to the solution comprising the elastomeric matrix of formula (I-1), and the resulting mixture is stirred for 3 hours. After homogenization is complete, the resulting mixture is transferred to a mold so that the solvent can evaporate slowly. The mould was placed in a fume hood for 24 hours and then under vacuum (10)^-3mbar) was dried at 70 ℃ for 2 days to obtain restorative composition C1.

Example 2: preparation of self-healing composition C2 according to the invention

2.1 preparation of the Polymer Material corresponding to formula (II-2)

A polymeric material of the following formula (II-2) is prepared by:

in a round bottom reaction flask, at ambient temperature and inert atmosphere (N)₂) Next, toluene-2, 4-diisothiocyanate (0.57mmol) was dissolved in 20ml of anhydrous THF. Then, 3-aminopropyl-substituted polydimethylsiloxane (FluidNH40 d; 0.60mmol) was dissolved in 18ml of anhydrous THF, and the resulting solution was added to a round-bottomed flask using a syringe pump (flow rate 1.3 ml/h). The resulting solution was stirred for 17 hours. Completion of the reaction was confirmed by disappearance of the absorption peak of isothiocyanate by infrared spectroscopy. Once reactedBundle, purification of the product obtained by precipitation in methanol (300ml), followed by filtration and in vacuo (10)^-3mbar) at 70 ℃ for 2 days. 1.46g of product were obtained (75% yield).

2.2 preparation of the elastomer base corresponding to formula (I-2)

Preparing an elastomeric matrix of formula (I-2) below by:

in a round bottom reaction flask, at ambient temperature and inert atmosphere (N)₂) Next, toluene-2, 4-diisocyanate (11.85mmol) was dissolved in 200ml of anhydrous THF, and then 3-aminopropyl-substituted polydimethylsiloxane (FluidNH40 d; 8.98mmol) was added to a round bottom flask. The resulting solution was stirred for 3 hours. An additional amount of substituted polydimethylsiloxane (2.99mmol) dissolved in 10ml of anhydrous THF was added using a syringe pump (flow rate 1.4 ml/h). At the end of the addition, the completion of the reaction was confirmed by the disappearance of the absorption peak of the isocyanate by infrared spectroscopy. Once the reaction is complete, the product obtained is purified by precipitation in methanol (1.5l), followed by filtration and in vacuo (10)^-3mbar) at 70 ℃ for 2 days. 35.68g of product were obtained (88% yield).

2.3 preparation of self-healing composition C2

5g of the elastomeric matrix of formula (I-2) prepared according to the above example 2.2 and 520mg of the polymeric material of formula (II-2) prepared according to the above example 2.1 were dissolved in 20ml of THF and 2ml of THF, respectively. After stirring for 1 hour, the solution comprising the polymeric material was added to the solution comprising the elastomeric matrix and the resulting mixture was stirred for 3 hours. After homogenization is complete, the resulting mixture is transferred to a mold so that the solvent can evaporate slowly. The mould was placed in a fume hood for 24 hours and then under vacuum (10)^-3mbar) was dried at 70 ℃ for 2 days to obtain restorative composition C2.

Example 3: preparation of self-healing composition C3 according to the invention

3.1 preparation of the polymeric Material corresponding to formula (II-3)

A polymeric material of the following formula (II-3) is prepared by:

in a round bottom reaction flask, at ambient temperature and inert atmosphere (N)₂) Next, toluene-2, 4-diisocyanate (1mmol) was dissolved in 20ml of anhydrous THF. Polydimethylsiloxane terminally substituted with N-ethylaminoisobutyl (DMS-A214; 1.1mmol) was then added to the round-bottom flask. The resulting solution was stirred for 24 hours. Completion of the reaction was confirmed by disappearance of the absorption peak of isocyanate by infrared spectroscopy. Once the reaction is complete, the solvent is evaporated and the product obtained is put under vacuum (10)^-3mbar) at 70 ℃ for 2 days. 2.6g of product were obtained (yield 98%).

3.2 preparation of the elastomer base corresponding to formula (I-3)

Preparing an elastomeric matrix of formula (I-3) below by:

in a round bottom reaction flask, at ambient temperature and inert atmosphere (N)₂) Toluene-2, 4-diisocyanate (TDI; 7.39mmol) was dissolved in 200ml of anhydrous THF, and then 3-aminopropyl substituted polydimethylsiloxane (FluidNH40 d; 4.49mmol) was added to a round bottom flask. The resulting solution was stirred for 4 hours. 1, 3-diaminopentane (3.1mmol) sold under the name Dytek EP diamine dissolved in 20ml of Dimethylformamide (DMF) was added using a syringe pump (flow rate 1 ml/h). At the end of the addition, the completion of the reaction was confirmed by the disappearance of the absorption peak of the isocyanate by infrared spectroscopy. Once the reaction is over, byThe product obtained is purified by precipitation in methanol (1.5l), followed by filtration and filtration in vacuo (10)^-3mbar) at 70 ℃ for 2 days. 13.72g of product were obtained (yield 85%).

3.3 preparation of self-healing composition C3

4g of the elastomeric matrix of formula (I-3) prepared according to the above example 3.2 and 496mg of the polymeric material of formula (II-3) prepared according to the above example 3.1 were dissolved in 40ml of THF and 2ml of THF, respectively. After stirring for 1 hour, the solution comprising the polymeric material was added to the solution comprising the elastomeric matrix and the resulting mixture was stirred for 4 hours. After homogenization is complete, the resulting mixture is transferred to a mold so that the solvent can evaporate slowly. The mould is placed in a ventilated place for 24 hours and then under vacuum (10)^-3mbar) was dried at 70 ℃ for 2 days to obtain restorative composition C3.

Example 4: physicochemical characterization of self-healing compositions C1, C2 and C3 according to the invention

Young's modulus (MPa), stress at break (MPa) and elongation at break (%) -were determined using a device sold under the trade name Instron 5565 by Instron as follows: the values of the stress at break and of the elongation at break are determined directly during the breaking of the material. As for young's modulus, the value of young's modulus was determined by analyzing the stress/strain curve in the initial 5% strain range.

Self-repairability was confirmed by: closure of the cut was monitored visually (example 1); or as confirmed by the recovery of the breaking stress of the sample at the given time for a sample in which a cut was previously formed in the range of half width thereof (examples 2 and 3).

Table 1 below lists the Young's modulus, stress at break and elongation at break of compositions C1, C2 and C3 prior to the formation of the cut and compares them to the elastomeric substrates (I-1), (I-2) and (I-3) prepared according to examples 1 to 3 above, and also shows the self-healing time (hours) and the self-healing ratio (%) of compositions C1, C2 and C3 after the formation of the cut.

TABLE 1

The breaking stress of the composition can be reduced relative to the elastomer of formula (I). However, the recovery of the stress at break of the composition is greater than the recovery of the stress at break of the elastomer (e.g., 17% to 85% for the composition and 0% for the elastomer). Thus, the addition of the polymeric material of formula (II) accelerates the self-healing kinetics of the composition, while ensuring good mechanical properties.

FIG. 1 shows the self-healing properties of composition C1 when the following experimental protocol was carried out on composition C1 and elastomer I-1, and compared to elastomer I-1: the layer obtained from composition C1 (fig. 1A) and the layer obtained from elastomer I-1 (fig. 1B) were cut with a knife and then monitored visually for self-healing over time at ambient temperature. It was observed that after 6 days at ambient temperature, the cut marks clearly disappeared only in the case of composition C1 (fig. 1A). The black line indicates the initial size of the cut (2.5 cm).

Example 5: preparation of self-healing composition C4 according to the invention

5.1 preparation of the polymeric Material corresponding to formula (II-4)

A polymeric material of the following formula (II-4) is prepared as follows:

in a dry round-bottom reaction flask, a commercially available elastomer matrix corresponding to the following formula (I-4) is placed under an inert atmosphere (argon, hereinafter also denoted as Ar) at ambient temperature

(10 g; carbamate function 20.4mmol) are dissolved in 500ml of anhydrous tetrahydrofuran(THF). In a second dry round bottom reaction flask under inert atmosphere (Ar), sodium hydride (NaH; 1.47 g; 61.25 mmol; 60% dispersed in mineral oil) was washed twice with 30ml of anhydrous Tetrahydrofuran (THF) under inert atmosphere (Ar) to remove mineral oil. 50ml of Tetrahydrofuran (THF) were introduced into the round-bottom reaction flask. The reaction medium is cooled using an ice-water bath (5 ℃) and then stirred under an inert atmosphere. The solution containing the elastomer matrix (I-4) was transferred over 40 minutes through a hollow needle into a round-bottomed flask containing sodium hydride dispersed in THF. At the end of the addition, the ice-water bath was removed and three vacuum-argon cycles were performed in the reaction medium. After stirring for 1 hour, iodomethane (CH) is added dropwise to the reaction medium₃I; 4.11 ml; 66.08 mmol). By proton nuclear magnetic resonance (¹H NMR) disappearance of the peak from N-H bond (8.90 to 8.95ppm) and CH₃The presence of an N peak (3.17ppm) to confirm the completion of the reaction. After stirring for 3 hours at ambient temperature, the reaction was stopped by adding methanol (MeOH; 1.51 ml; 44 mmol). Once the reaction was complete, the product obtained was purified by precipitation in water (1000ml), followed by filtration, washing with water and application in vacuo (10)^-3mbar) at 40 ℃ for 1 day. 8.9g of product are obtained (yield 87%). The number-average molar mass (Mn) of the polymer (II-4) was 63249 g/mol as determined by SEC.

5.2 preparation of self-healing composition C4

15.57g of the commercially available elastomer base of formula (I-4) as defined above and 4.67g of the polymeric material of formula (II-4) prepared as described above in example 5.1 were dissolved in 150ml of THF and 50ml of THF, respectively. After completion of dissolution by stirring, the solution containing the polymer material (II-4) was added to the solution containing the elastomer matrix (I-4), and then the resultant mixture was stirred for 1 hour. After homogenization, the resulting mixture is transferred into several molds so that the solvent can evaporate slowly. The mould was placed in a fume hood for 24 hours and then under vacuum (10)^-3mbar) at 40 ℃ for 1 day to obtain a self-healing composition C4.

Example 6: preparation of self-healing composition C5 according to the invention

6.1 preparation of the polymeric Material corresponding to formula (II-5)

A polymeric material of the following formula (II-5) is prepared as follows:

the elastomer substrate (I-4) as defined above (6.5 g; carbamate functions 13.26mmol) was dissolved in 250ml of anhydrous Tetrahydrofuran (THF) at ambient temperature under an inert atmosphere (Ar) in a dry round-bottom reaction flask. In a second dry round bottom reaction flask under inert atmosphere (Ar), sodium hydride (NaH; 0.987 g; 41.13 mmol; 60% dispersed in mineral oil) was washed twice with 20ml of anhydrous Tetrahydrofuran (THF) under inert atmosphere (Ar) to remove mineral oil. 10ml of Tetrahydrofuran (THF) were introduced into the round-bottom reaction flask. The reaction medium is cooled using an ice-water bath (5 ℃) and then stirred under an inert atmosphere. The solution containing the elastomer matrix (I-4) was transferred over 40 minutes through a hollow needle into a round-bottomed flask containing sodium hydride dispersed in THF. At the end of the addition, the ice-water bath was removed and three vacuum-argon cycles were performed in the reaction medium. After stirring for 1 hour, benzyl bromide (BnBr; 4.96 ml; 41.86mmol) is added dropwise to the reaction medium. By proton nuclear magnetic resonance (¹H NMR), by disappearance of the peak of N-H bond (8.90 to 8.95ppm) and CH₂The presence of an N peak (4.72ppm) to confirm the completion of the reaction. After stirring for 40 h at ambient temperature, the reaction was stopped by adding methanol (MeOH; 12 ml; 26.5 mmol). Once the reaction is complete, the reaction medium is introduced into 300ml of water to remove the salts. The mixture of reaction medium and water was introduced into a separatory funnel, into which 400ml of dichloromethane were introduced to extract the organic phase. With MgSO₄The organic phase was dried and concentrated. The product obtained was purified by precipitation in pentane (500ml), followed by filtration and filtration in vacuo (10)^-3mbar) at 40 ℃ for 1 day. 6.50g of product are obtained (84% yield). The number-average molar mass (Mn) of the polymer (II-5) was 68501 g/mol as determined by SEC.

6.2 preparation of self-healing composition C5

15.00g of a commercially available elastomer base of formula (I-4) as defined above and 5.30g of the polymeric material of formula (II-5) prepared according to example 6.1 above were dissolved in 150ml of THF and 50ml of THF, respectively. After completion of dissolution by stirring, the solution containing the polymer material (II-5) was added to the solution containing the elastomer matrix (I-4), and then the resultant mixture was stirred for 1 hour. After homogenization, the resulting mixture is transferred into several molds so that the solvent can evaporate slowly. The mould was placed in a fume hood for 24 hours and then under vacuum (10)^-3mbar) at 40 ℃ for 1 day to obtain a self-healing composition C5.

Example 7: preparation of self-healing composition C6 according to the invention

7.1 preparation of the polymeric Material corresponding to formula (II-6)

A polymeric material of the following formula (II-6) was prepared as follows:

in a dry round-bottom reaction flask, at ambient temperature and under an inert atmosphere (Ar), a commercially available elastomer matrix corresponding to the following formula (I-5)

(6.02 g; carbamate functionality 12.04mmol) was dissolved in 300ml of anhydrous Tetrahydrofuran (THF). In a second dry round bottom reaction flask under inert atmosphere (Ar), sodium hydride (NaH; 0.8771 g; 36.55 mmol; 60% dispersed in mineral oil) was washed twice with 20ml of anhydrous Tetrahydrofuran (THF) under inert atmosphere (Ar) to remove mineral oil. 10ml of Tetrahydrofuran (THF) were introduced into the round-bottom reaction flask. The reaction medium is cooled using an ice-water bath (5 ℃) and then stirred under an inert atmosphere. Through a hollow needleThe solution containing the elastomer matrix (I-5) was transferred over 40 minutes into a round-bottomed flask containing sodium hydride dispersed in THF. At the end of the addition, the ice-water bath was removed and three vacuum-argon cycles were performed in the reaction medium. After stirring for 1 hour, iodomethane (CH) is added dropwise to the reaction medium₃I; 2.61 ml; 41.85 mmol). By proton nuclear magnetic resonance (¹H NMR) disappearance of the peak from N-H bond (8.96 to 9.01ppm) and CH₃The presence of an N peak (3.17ppm) to confirm the completion of the reaction. After stirring for 17 h at ambient temperature, the reaction was stopped by adding methanol (MeOH; 1.28 ml; 29.24 mmol). Once the reaction was complete, the tetrahydrofuran was evaporated. The product obtained is washed with a dichloromethane/water mixture. The organic phase is extracted with 120ml of dichloromethane and washed three times with 120ml of water. With MgSO₄It was dried, filtered and dried. The product is placed under vacuum (10)^-3mbar) at 40 ℃ for 1 day. 5g of product were obtained (yield 87%). The number-average molar mass (Mn) of the polymer (II-6) was 42095 g/mol as determined by SEC.

7.2 preparation of self-healing composition C6

15.56g of the commercially available elastomer base of formula (I-4) as defined above and 4.80g of the polymeric material of formula (II-6) prepared as described above in example 7.1 were dissolved in 150ml of THF and 50ml of THF, respectively. After completion of dissolution by stirring, the solution containing the polymer material (II-6) was added to the solution containing the elastomer matrix (I-4), and then the resultant mixture was stirred for 1 hour. After homogenization, the resulting mixture is transferred into several molds so that the solvent can evaporate slowly. The mould was placed in a fume hood for 24 hours and then under vacuum (10)^-3mbar) at 40 ℃ for 1 day to obtain a self-healing composition C6.

Example 8: preparation of self-healing composition C7 according to the invention

8.1 preparation of the Polymer Material corresponding to formula (II-7)

A polymeric material of the following formula (II-7) was prepared as follows:

in a dry round-bottom reaction flask, the elastomer substrate (I-5) as defined above (6.72 g; carbamate functions 13.44mmol) was dissolved in 250ml of anhydrous Tetrahydrofuran (THF) at ambient temperature under an inert atmosphere (Ar). In a second dry round bottom reaction flask under inert atmosphere (Ar), sodium hydride (NaH; 0.9845 g; 41.02 mmol;

60% dispersed in mineral oil) was washed twice to remove mineral oil. 10ml of Tetrahydrofuran (THF) were introduced into the round-bottom reaction flask. The reaction medium is cooled using an ice-water bath (5 ℃) and then stirred under an inert atmosphere. The solution containing the elastomer matrix (I-5) was transferred over 40 minutes through a hollow needle into a round-bottomed flask containing sodium hydride dispersed in THF. At the end of the addition, the ice-water bath was removed and three vacuum-argon cycles were performed in the reaction medium. After stirring for 1 hour, benzyl bromide (BnBr; 4.96 ml; 41.02mmol) is added dropwise to the reaction medium. By proton nuclear magnetic resonance (¹H NMR), by disappearance of the peak of N-H bond (8.96 to 9.01ppm) and CH₂The presence of an N peak (4.72ppm) to confirm the completion of the reaction. After stirring for 42 h at ambient temperature, the reaction was stopped by adding methanol (MeOH; 1.18 ml; 26.95 mmol). Once the reaction is complete, the reaction medium is introduced into 300ml of water to remove the salts. The mixture of reaction medium and water was introduced into a separatory funnel, into which 450ml of dichloromethane were introduced to extract the organic phase. With MgSO₄The organic phase was dried and concentrated. The product obtained was purified by precipitation in pentane (450ml), followed by filtration and filtration in vacuo (10)^-3mbar) at 40 ℃ for 1 day. 5.52g of product are obtained (yield 70%). The number-average molar mass (Mn) of the polymer (II-7) was 41966 g/mol as determined by SEC.

8.2 preparation of self-healing composition C7

14.79g of a commercially available elastomeric matrix of formula (I-4) as defined above and 5.11g of a polymeric material of formula (II-7) prepared according to example 8.1 aboveThe material was dissolved in 150ml THF and 50ml THF, respectively. After completion of dissolution by stirring, the solution containing the polymer material (II-7) was added to the solution containing the elastomer matrix (I-4), and then the resultant mixture was stirred for 1 hour. After homogenization, the resulting mixture is transferred into several molds so that the solvent can evaporate slowly. The mould was placed in a fume hood for 24 hours and then under vacuum (10)^-3mbar) at 40 ℃ for 1 day to obtain a self-healing composition C7.

Example 9: physicochemical characterization of self-healing compositions C4, C5, C6 and C7 according to the invention

For a 5A dumbbell specimen (ISO 527) obtained by an injection molding process, young's modulus (MPa), stress at break (MPa), and elongation at break (%) were determined by performing a tensile test at a displacement rate of 30mm/min using a device sold by Instron under the trade name Instron 5565. The values of the stress at break and of the elongation at break are determined directly during the breaking of the material. As for young's modulus, the value of young's modulus was determined by analyzing the slope of the stress/strain curve in the strain range of 1% to 1.5%.

Self-repairability was confirmed by:

-visually monitoring the closure of the cut,

or by the recovery of the breaking stress at a given time of a 5A standardized dumbbell specimen, in which the specimen is cut in the center of the processing zone of the specimen and then the two halves of the specimen are brought into direct (t < 20 seconds) contact again manually for 2 minutes.

Table 2 below sets forth the values of Young's modulus, stress at break and elongation at break for compositions C4, C5, C6 and C7 before and after cutting, and compares them with the elastomeric matrices (I-4) and (I-5). In addition, the self-healing time (hours) and the self-healing ratio (%) of each composition are listed.

TABLE 2

Example 10: preparation of self-healing composition C8 comprising a polymeric material of formula (III)

10.1 preparation of the Polymer Material corresponding to formula (IIa-8)

A polymeric material of the formula (IIa-8):

the elastomer substrate (I-4) as defined above (6.12 g; carbamate functions 12.48mmol) was dissolved in 250ml of anhydrous Tetrahydrofuran (THF) at ambient temperature under an inert atmosphere (Ar) in a dry round-bottom reaction flask. In a second dry round bottom reaction flask under inert atmosphere (Ar), sodium hydride (NaH; 0.6023 g; 25.10 mmol; 60% dispersed in mineral oil) was washed twice under inert atmosphere (Ar) with 20ml of anhydrous Tetrahydrofuran (THF) to remove mineral oil. 10ml of Tetrahydrofuran (THF) were introduced into the round-bottom reaction flask. The reaction medium is cooled using an ice-water bath (5 ℃) and then stirred under an inert atmosphere. The solution containing the elastomer matrix (I-4) was transferred over 40 minutes through a hollow needle into a round-bottomed flask containing sodium hydride dispersed in THF. At the end of the addition, the ice-water bath was removed and three vacuum-argon cycles were performed in the reaction medium. After stirring for 1 hour, iodomethane (CH) is added dropwise to the reaction medium₃I; 0.51 ml; 8.24 mmol). By proton nuclear magnetic resonance (¹H NMR), reduction of peak by N-H bond (8.90-8.95ppm) and CH₃The presence of an N peak (3.17ppm) to confirm the completion of the reaction. After stirring for 44 h at ambient temperature, the reaction was stopped by adding methanol (MeOH; 1.15 ml; 26.27 mmol). Once the reaction was complete, the product obtained was purified by precipitation in water (1000ml), followed by filtration, washing with water and application in vacuo (10)^-3mbar) at 40 ℃ for 1 day. 6.19g of product are obtained (yield 98%).

Statistically, the polymer (IIa-8) thus obtained had an R ═ H content of 41%, and CH₃The content of (B) is 59%.

10.Preparation of self-healing composition C8

11.49g of a commercially available elastomer base of the formula (I-4) and 4.67g of the polymeric material of the formula (IIa-8) prepared as described in example 10.1 above were dissolved in 150ml of THF and 50ml of THF, respectively. After completion of dissolution by stirring, the solution containing the polymeric material (IIa-8) was added to the solution containing the elastomer matrix (I-4), and then the resulting mixture was stirred for 1 hour. After homogenization, the resulting mixture is transferred into several molds so that the solvent can evaporate slowly. The mould was placed in a fume hood for 24 hours and then under vacuum (10)^-3mbar) at 40 ℃ for 1 day to obtain a self-healing composition C8.

Other embodiments of the self-healing composition

In addition to the foregoing examples of compositions according to the present invention, other compositions utilizing compounds of formulae (I) and (II) in similar proportions to the foregoing examples exhibit their self-healing properties.

Composition C9 comprising a compound of formula (I) and a compound of formula (II):

composition C10 comprising a compound of formula (I) and a compound of formula (IIa):

composition C11 comprising a compound of formula (I) and a compound of formula (II):

fig. 2 shows that one of the self-healing compositions as defined above, which has excellent healing after 24 hours in the absence of external stimuli (temperature, pressure, etc.).