CN115181347B - High-strength self-repairing elastomer material and preparation method thereof - Google Patents
High-strength self-repairing elastomer material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of self-repairing materials, in particular to a high-strength self-repairing elastomer material and a preparation method thereof. The invention provides a high-strength self-repairing elastomer material which comprises the following raw materials in parts by weight: 100 parts of an epoxidized elastomer or an elastomer containing unsaturated double bonds, 1-10 parts of a combined dynamic cross-linking agent and 0.1-1 part of a catalyst; the structural formula of the combined dynamic cross-linking agent is shown as a formula I, wherein R in the formula I is selected from phenylborate or ester bonds. The invention constructs a dynamic covalent cross-linking network through the reaction of the combined dynamic bond and the elastomer, and stretches the elastomer and fixes the strain by utilizing the characteristic that the combined dynamic bond can realize bond-bond exchange above the activation temperature; an elastomer material with high strength and self-repairing performance is obtained. HS-R-SH formula I.
Description
Technical Field
The invention relates to the field of self-repairing materials, in particular to a high-strength self-repairing elastomer material and a preparation method thereof.
Background
The self-repairing elastomer is an intelligent material prepared by introducing reversible dynamic non-covalent or/and dynamic covalent bonds into a high molecular framework to form a crosslinked structure instead of traditional irreversible covalent bonds. The self-repairing elastomer has the outstanding advantages of high elasticity, high toughness, long service life and the like, so that the self-repairing elastomer has wide application prospect in the fields of flexible electronics, expensive coatings, biomedical materials, nuclear storage materials, aerospace and the like. However, dynamic chemical bonds tend to be low in bond energy due to their inherent high reactivity and reversibility, and the strength of the resulting materials is weak. The contradiction between strength and self-healing properties is a problem that needs to be solved in this field.
In recent years, researchers have tuned the mechanical strength and repair properties of self-repairing elastomeric materials by designing different dynamic structures. Elastomers crosslinked by dynamic non-covalent bonds, such as hydrogen bonds, coordination, pi stacking, etc. supermolecular interactions, such as the patent of application publication No. CN 109280143A, have been devised as self-healing elastomers crosslinked by metal coordination bonds, and elastomers crosslinked by dynamic covalent bonds, such as ester bonds, boron bonds, carbamates, alkoxyamines, etc., such as Journal ofMaterials Chemistry A (2019,7, 1459-1467) have been reported as covalently crosslinked elastomers composed of silyl ethers. Dynamic covalent bonds generally have stronger strengths than supramolecular interactions, so that self-healing elastomers crosslinked by dynamic covalent networks generally have higher mechanical properties and more reliable service properties. However, the tensile strength of self-healing elastomers prepared by dynamic covalent bonding is much less than 10MPa, still at a relatively low level.
Increasing the crosslink density can further increase the tensile strength of self-healing elastomers, such as the highly crosslinked elastomers reported by Nano Energy (2021,87,105822), and the addition of a large amount of crosslinking agent can impair the inherent excellent properties of the elastomer, such as high elasticity, low hysteresis, etc., and more importantly, the high crosslink density can significantly inhibit the ability of molecular chains to move, greatly extend the relaxation time, and result in a significant decrease in the healing properties of the elastomer. Therefore, how to combine strength and self-repairing performance is a primary technical difficulty in the field.
Disclosure of Invention
In order to solve the defects in the prior art, the invention constructs a dynamic covalent cross-linking network through the reaction of the combined dynamic bond and the elastomer, and the characteristic of bond-to-bond exchange can be realized by utilizing the combined dynamic bond above the activation temperature; stretching the elastomer above the activation temperature, fixing the strain, and realizing stress relaxation through the exchange of the combined dynamic bonds so as to keep an oriented structure; the tensile strength of the oriented elastomer is obviously improved in the orientation direction, and a good repairing effect can be realized under a relatively mild condition; namely, the self-repairing elastomer with an oriented structure and crosslinked by the combined dynamic bonds is obtained; thus obtaining the elastomer material with high strength and self-repairing performance.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a high-strength self-repairing elastomer material, wherein the raw materials of the elastomer material comprise the following components in parts by weight: 100 parts of an epoxidized elastomer or an elastomer containing unsaturated double bonds, 1-10 parts of a combined dynamic cross-linking agent and 0.1-1 part of a catalyst; the structural formula of the combined dynamic cross-linking agent is shown in formula I:
HS-R-SH
i is a kind of
R in the formula I is selected from phenylborate or ester bond. In the present invention, the binding type dynamic crosslinking agent is a substance that can react with an elastomer to form a binding type dynamic bond crosslinking network.
Further, the binding dynamic cross-linking agent is selected from the group consisting of: at least one of 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolane ] (BDB), ethylene bis (3-mercaptopropionic acid), ethylene bis (mercaptoacetic acid) ester, pentaerythritol bis (mercaptoacetate) 1, 4-butanediol, or tetrakis (3-mercaptopropionic acid).
Further, the epoxidized elastomer is selected from the group consisting of: at least one of epoxidized natural rubber, epoxidized ethylene propylene rubber, epoxidized styrene-butadiene rubber, epoxidized butyl rubber or epoxidized butadiene rubber.
Further, the unsaturated double bond-containing elastomer is at least one selected from natural rubber, styrene-butadiene rubber, butyl rubber, nitrile rubber, isoprene rubber and butadiene rubber.
Further, the catalyst is selected from: at least one of 4-dimethylaminopyridine, zinc acetate or tetrabutyl titanate.
The second technical problem to be solved by the invention is to provide a preparation method of the high-strength self-repairing elastomer material, which comprises the following steps: firstly uniformly blending an epoxidized elastomer or an elastomer containing unsaturated double bonds, a combined dynamic cross-linking agent and a catalyst to obtain a blend; then carrying out hot press curing on the blend to obtain a cured product, wherein in the curing process, the combined dynamic cross-linking agent carries out click reaction with double bonds or epoxy groups of the elastomer through mercaptan to form a dynamic bond cross-linking network; and finally, stretching the obtained cured product to a strain of 100-1000% above the bond exchange reaction temperature of the dynamic bond, so that the molecular chain of the elastomer is oriented, and then maintaining for 30-300 min to obtain the high-strength self-repairing elastomer material.
Further, the bond exchange reaction temperature of the dynamic bond is 80-200 ℃.
Further, the preparation method of the high-strength self-repairing elastomer material comprises the following steps: firstly uniformly blending an epoxidized elastomer or an elastomer containing unsaturated double bonds, a combined dynamic cross-linking agent and a catalyst to obtain a blend; then carrying out hot press curing on the blend to obtain a cured product, wherein in the curing process, the combined dynamic cross-linking agent forms a combined dynamic bond cross-linking network through click reaction of mercaptan and double bonds or epoxy groups of the elastomer; and finally, stretching the obtained cured product to a strain of 100-1000% above the bond exchange reaction temperature of the combined dynamic bond, so that the molecular chain of the elastomer is oriented, and then keeping for 30-300 min, wherein the relaxation of the internal stress of the elastomer is realized through the bond exchange of the combined dynamic bond, the orientation recovery caused by the rebound resilience of the elastomer is reduced, the fixation of an orientation structure is finally realized through the fixation of a cross-linked network, and the high-strength self-repairing elastomer material is prepared.
Further, in the above method, the respective raw materials may be blended by melt blending or open blending.
Further, the preparation method comprises the following steps:
1) The method comprises the steps of (1) carrying out melt blending or open mill blending on an epoxidized elastomer or an elastomer containing unsaturated double bonds, a combined dynamic cross-linking agent and a catalyst to obtain a blend; the proportion of the raw materials is as follows: 100 parts by weight of an epoxidized elastomer or an elastomer containing unsaturated double bonds, 1-10 parts by weight of a combined dynamic cross-linking agent and 0.1-1 part by weight of a catalyst;
2) Carrying out hot press curing on the blend obtained in the step 1) for 30-180 min at the temperature of 100-200 ℃ and the pressure of 5-20 MP to obtain a cured product;
3) Stretching the cured product obtained in the step 2) to a strain of 100-1000% at 80-200 ℃ so as to orient the molecular chains of the elastomer, and keeping for 30-300 min to obtain the high-strength self-repairing elastomer material.
In the step 1), the melt blending equipment is a two-roll open mill or an internal mixer.
In the step 1), the blending temperature is 20-100 ℃, and the blending time is 5-15 min.
The third technical problem to be solved by the invention is to provide a method for improving the strength of a self-repairing elastomer material, which comprises the following steps: selecting an epoxidized elastomer or an elastomer containing unsaturated double bonds as a matrix, and introducing a combined dynamic cross-linking agent and a catalyst into the matrix; firstly, uniformly blending all the raw materials to obtain a blend, then, carrying out hot pressing and curing on the blend to obtain a cured product, and finally, carrying out stretching treatment on the cured product; wherein, the proportion of each raw material is as follows: 100 parts by weight of an epoxidized elastomer or an elastomer containing unsaturated double bonds, 1-10 parts by weight of a combined dynamic cross-linking agent and 0.1-1 part by weight of a catalyst; the structural formula of the combined dynamic cross-linking agent is shown as formula I:
HS-R-SH
i is a kind of
R in the formula I is selected from phenylborate or ester bond.
Further, the hot press curing method comprises the following steps: and (3) carrying out hot press curing on the obtained blend for 30-180 min at the temperature of 100-200 ℃ and the pressure of 5-20 MP.
Further, the method for stretching the cured product comprises the following steps: stretching the obtained cured product to strain of 100-1000% at 80-200 ℃ to orient the elastomer molecular chain, and keeping for 30-300 min.
The invention has the beneficial effects that:
(1) The present invention uses the bond exchange characteristic of the bond type dynamic bond above the activation temperature to relax the stress existing in the elastomer, thereby fixing the orientation of the elastomer molecular chain along the stretching direction, and greatly improving the stretching strength (table 1).
(2) Compared with the traditional permanent crosslinking bond, the self-repairing elastomer crosslinked by the combined dynamic bond can realize repairing under the condition of a temperature field after the material is damaged; compared with the supermolecule acting force, the high-strength and high-reliability application performance (figure 2) are realized.
(3) Adjustment of the elastomer strength over a wide range can be achieved by controlling the relaxation behavior during stretch orientation (fig. 3).
Description of the drawings:
FIG. 1 is a drawing showing tensile properties of examples 1 to 3 and comparative examples 1 to 3 according to the present invention, in which the strength of the elastomer increases continuously with increasing crosslinking agent content, and the difference in strength between the samples increases in the longitudinal direction; the tensile strength of example 1 exceeds 30MPa, indicating that the elastomer obtained according to the invention has excellent mechanical properties.
Fig. 2 is a drawing showing tensile properties of the present invention after 24h of repair at 80 ℃ for examples 1 to 3 and comparative examples 1 to 3, showing that the elastic body after the repair has higher mechanical strength after the stretch orientation than the elastic body after the non-stretch orientation, indicating that the elastic body has good repair properties.
FIG. 3 is a tensile property test chart of examples 1,4, 5 of the present invention, showing that a self-healing elastomer having high strength can be produced by adjusting the orientation time.
FIG. 4 is a schematic diagram showing the curing and orientation process of an elastomer, wherein the mercapto groups at both ends of the crosslinking agent react with the epoxy functional groups or unsaturated carbon-carbon double bonds of the elastomer to form a crosslinked network; stretching the elastomer to a fixed strain above the bond exchange reaction temperature of a cross-linked network constructed by the bonded dynamic covalent bonds so that the molecular chains of the elastomer are oriented and then held for a suitable time; the stretching makes the molecular chain of the elastomer orient, realizes the relaxation of internal stress of the elastomer through the bond exchange of the used combined dynamic bond, reduces the orientation recovery caused by rebound resilience of the elastomer, combines the fixing function of a cross-linked network, finally realizes the fixing of an orientation structure, and prepares the high-strength self-repairing elastomer material.
Detailed Description
The invention provides a high-strength self-repairing elastomer material, which consists of the following materials: 100 parts of an elastomer or an epoxidized elastomer containing unsaturated double bonds, 1-10 parts of a combined dynamic cross-linking agent and 0.1-1 part of a catalyst; the preparation process can adopt the following modes: (1) Melt blending or open milling the elastomer, the combined dynamic cross-linking agent and the catalyst uniformly; (2) Placing the mixture in the step (1) in a flat vulcanizing instrument for hot press curing; (3) Stretching the cured product in the step (2) to a fixed strain under high temperature conditions so as to orient the molecular chains of the elastomer, keeping the elastomer for a proper time, and fixing the oriented structure through the relaxation of internal stress of the combined dynamic bonds. According to the self-repairing elastomer, the molecular chain orientation structure is fixed through dynamic bond crosslinking, so that the strength of the elastomer can be remarkably improved, and meanwhile, the self-repairing elastomer has good self-repairing performance; thus, the elastomer material with the combined dynamic bond cross-linking and orientation structure is prepared.
In the preparation process of the high-strength self-repairing elastomer material, the combined dynamic cross-linking agent forms a combined dynamic bond cross-linking network through clicking reaction of mercaptan and double bonds or epoxy groups of the elastomer, and as the combined dynamic bond is subjected to combined exchange reaction above the exchange reaction temperature, old bond fracture and new bond formation occur simultaneously, so that the cross-linking density of the material is kept unchanged; taking epoxidized natural rubber and BDB crosslinking agent as an example, the crosslinking reaction and the combined exchange reaction formula are shown as follows, and the mercapto group of the crosslinking agent BDB reacts with the epoxy functional group on the epoxidized natural rubber under the catalysis of DMAP to obtain a crosslinked elastomer; above the bond exchange temperature of the dynamic bonds, the boron ester bonds are activated, and the bond exchange occurs.
The following describes the invention in further detail with reference to examples, which are not intended to limit the invention thereto.
Example 1
6.0g of 1, 4-phenyldiboronic acid and 8.02g of 1-thioglycerol are dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate are added, stirred for 24 hours at 25℃and filtered off, the anhydrous magnesium sulfate is removed and the mixture is distilled off to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolan ] (BDB).
Uniformly mixing 45g of epoxidized natural rubber (epoxidized isoprene) with the epoxy degree of 30%, 4.5g of BDB and 0.45g of 2-Dimethylaminopyridine (DMAP) on a two-roll mill at 25 ℃; cutting the mixture into small particles, and then placing the small particles into a flat rheometer for hot press curing at 160 ℃ under 10MPa for 45min. Cutting the cured sample into rectangular sample strips with the length of 60mm and the width of 27mm, clamping the sample strips by a stretching clamp, and stretching the sample strips to 300% of strain at the stretching rate of 10mm/min at the temperature of 120 ℃, fixing the strain, and keeping the sample strips for 90min to obtain the high-strength self-repairing elastomer. The tensile strength and the repair performance of the obtained elastomer material are shown in Table 1, and in the embodiment of the invention, the repair condition is that the elastomer material is repaired for 24 hours at 80 ℃.
Example 2
6.0g of 1, 4-phenyldiboronic acid and 8.02g of 1-thioglycerol are dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate are added, stirred for 24 hours at 25℃and filtered off, the anhydrous magnesium sulfate is removed and the mixture is distilled off to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolane ] (BDB).
45g of epoxy natural rubber with the epoxy degree of 30%, 2.25g of BDB and 0.225g of 2-dimethylaminopyridine DMAP are uniformly mixed on a two-roll mill at 25 ℃. Cutting the mixture into small particles, and then placing the small particles into a flat rheometer for hot press curing at 160 ℃ under 10MPa for 45min. Cutting the cured sample into rectangular sample strips with the length of 60mm and the width of 27mm, clamping the sample strips by a stretching clamp, and stretching the sample strips to 300% of strain at the stretching rate of 10mm/min at the temperature of 120 ℃, fixing the strain, and keeping the sample strips for 90min. The properties and repair properties of the compounds are shown in Table 1.
Example 3
6.0g of 1, 4-phenyldiboronic acid and 8.02g of 1-thioglycerol are dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate are added, stirred for 24 hours at 25℃and filtered off, the anhydrous magnesium sulfate is removed and the mixture is distilled off to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolane ] (BDB).
45g of epoxy natural rubber with the epoxy degree of 30%, 0.45g of BDB and 0.045g of 2-dimethylaminopyridine DMAP are uniformly mixed on a two-roll mill at 25 ℃. Cutting the mixture into small particles, and then placing the small particles into a flat rheometer for hot press curing at 160 ℃ under 10MPa for 45min. Cutting the cured sample into rectangular sample strips with the length of 60mm and the width of 27mm, clamping the sample strips by a stretching clamp, and stretching the sample strips to 300% of strain at the stretching rate of 10mm/min at the temperature of 120 ℃, fixing the strain, and keeping the sample strips for 90min. The properties and repair properties of the compounds are shown in Table 1.
Example 4
6.0g of 1, 4-phenyldiboronic acid and 8.02g of 1-thioglycerol are dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate are added, stirred for 24 hours at 25℃and filtered off, the anhydrous magnesium sulfate is removed and the mixture is distilled off to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolane ] (BDB).
45g of epoxy natural rubber with the epoxy degree of 30%, 4.5g of BDB and 0.45g of 2-dimethylaminopyridine DMAP are uniformly mixed on a two-roll mill at 25 ℃. Cutting the mixture into small particles, and then placing the small particles into a flat rheometer for hot press curing at 160 ℃ under 10MPa for 45min. Cutting the cured sample into rectangular sample strips with the length of 60mm and the width of 27mm, clamping the sample strips by a stretching clamp, and stretching the sample strips to 300% of strain at the stretching rate of 10mm/min at the temperature of 120 ℃, fixing the strain, and keeping the sample strips for 30min. The properties of the compounds are shown in Table 1.
Example 5
6.0g of 1, 4-phenyldiboronic acid and 8.02g of 1-thioglycerol are dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate are added, stirred for 24 hours at 25℃and filtered off, the anhydrous magnesium sulfate is removed and the mixture is distilled off to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolane ] (BDB).
45g of epoxy natural rubber with the epoxy degree of 30%, 4.5g of BDB and 0.45g of 2-dimethylaminopyridine DMAP are uniformly mixed on a two-roll mill at 25 ℃. Cutting the mixture into small particles, and then placing the small particles into a flat rheometer for hot press curing at 160 ℃ under 10MPa for 45min. Cutting the cured sample into rectangular sample strips with the length of 60mm and the width of 27mm, clamping the sample strips by a stretching clamp, and stretching the sample strips to 300% of strain at the stretching rate of 10mm/min at the temperature of 120 ℃, fixing the strain, and keeping the sample strips for 60min. The properties of the compounds are shown in Table 1.
Comparative example 1
6.0g of 1, 4-phenyldiboronic acid and 8.02g of 1-thioglycerol are dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate are added, stirred for 24 hours at 25℃and filtered off, the anhydrous magnesium sulfate is removed and the mixture is distilled off to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolane ] (BDB).
45g of epoxy natural rubber with the epoxy degree of 30%, 4.5g of BDB and 0.45g of 2-dimethylaminopyridine DMAP are uniformly mixed on a two-roll mill at 25 ℃. Cutting the mixture into small particles, and then placing the small particles into a flat rheometer for hot press curing at 160 ℃ under 10MPa for 45min. The properties of the compounds are shown in Table 1.
Comparative example 2
6.0g of 1, 4-phenyldiboronic acid and 8.02g of 1-thioglycerol are dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate are added, stirred for 24 hours at 25℃and filtered off, the anhydrous magnesium sulfate is removed and the mixture is distilled off to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolane ] (BDB).
45g of epoxy natural rubber with the epoxy degree of 30%, 2.25g of BDB and 0.225g of 2-dimethylaminopyridine DMAP are uniformly mixed on a two-roll mill at 25 ℃. Cutting the mixture into small particles, and then placing the small particles into a flat rheometer for hot press curing at 160 ℃ under 10MPa for 45min. The properties of the compounds are shown in Table 1.
Comparative example 3
6.0g of 1, 4-phenyldiboronic acid and 8.02g of 1-thioglycerol are dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate are added, stirred for 24 hours at 25℃and filtered off, the anhydrous magnesium sulfate is removed and the mixture is distilled off to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolane ] (BDB).
45g of epoxy natural rubber with the epoxy degree of 30%, 0.45g of BDB and 0.045g of 2-dimethylaminopyridine DMAP are uniformly mixed on a two-roll mill at 25 ℃. Cutting the mixture into small particles, and then placing the small particles into a flat rheometer for hot press curing at 160 ℃ under 10MPa for 45min. The properties of the compounds are shown in Table 1.
TABLE 1 comparative performance tables for inventive examples 1-5 and comparative examples 1-3
The tensile strength of the sample and the tensile strength after repair are tested by using a universal material tester of INSTRON corporation in America, the test sample is a dumbbell-shaped sample with the length of 37.5mm, the thickness of 1mm and the width of 2mm, the tensile rate is 500mm/min, the tensile strength after repair of the sample is that the sample is cut off, the section is attached for 1min, and the sample is automatically healed for 24 hours at 80 ℃.
As can be seen from the data in Table 1, examples 1 to 3 have higher tensile strength, up to 30MPa or more, than comparative examples 1 to 3, and also have higher tensile strength after 24 hours of repair at 80℃than the repair bars of comparative examples 1 to 3. Comparing examples 1,4 and 5, it was found that samples of different properties could be obtained by controlling different relaxation times. In summary, the present invention provides a high strength self-healing elastomeric material and a viable method of preparation.
Claims (11)
1. The high-strength self-repairing elastomer material is characterized by comprising the following components in parts by weight: 100 parts of an epoxidized elastomer or an elastomer containing unsaturated double bonds, 1-10 parts of a combined dynamic cross-linking agent and 0.1-1 part of a catalyst; the structural formula of the combined dynamic cross-linking agent is shown in formula I:
HS--R--SH
i is a kind of
R in the formula I is selected from phenylborate or ester bond;
and the high-strength self-repairing elastomer material is prepared by the following method: firstly uniformly blending an epoxidized elastomer or an elastomer containing unsaturated double bonds, a combined dynamic cross-linking agent and a catalyst to obtain a blend; then carrying out hot press curing on the blend to obtain a cured product, wherein in the curing process, the combined dynamic cross-linking agent carries out click reaction with double bonds or epoxy groups of the elastomer through mercaptan to form a dynamic bond cross-linking network; and finally, stretching the obtained cured product to a strain of 100-1000% above the bond exchange reaction temperature of the dynamic bond, so that the molecular chain of the elastomer is oriented, and then maintaining for 30-300 min to obtain the high-strength self-repairing elastomer material.
2. A high strength self-healing elastomeric material according to claim 1, wherein said binding dynamic cross-linking agent is selected from the group consisting of: at least one of 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolane ], ethylene bis (3-mercaptopropionate), ethylene bis (mercaptoacetic acid) ester, 1, 4-butanediol bis (mercaptoacetic acid) ester, or pentaerythritol tetrakis (3-mercaptopropionic acid) ester.
3. A high strength self-healing elastomeric material according to claim 1 or 2, wherein the epoxidized elastomer is selected from the group consisting of: at least one of epoxidized natural rubber, epoxidized ethylene propylene rubber, epoxidized styrene-butadiene rubber, epoxidized butyl rubber or epoxidized butadiene rubber.
4. A high strength self-repairing elastomeric material according to claim 1 or 2, wherein said unsaturated double bond containing elastomer is selected from at least one of natural rubber, styrene-butadiene rubber, butyl rubber, nitrile rubber, isoprene rubber or butadiene rubber.
5. A high strength self-healing elastomeric material according to claim 1 or 2, wherein the catalyst is selected from the group consisting of: at least one of 4-dimethylaminopyridine, zinc acetate or tetrabutyl titanate.
6. A method of preparing a high strength self-healing elastomeric material according to any one of claims 1 to 5, wherein the method is: firstly uniformly blending an epoxidized elastomer or an elastomer containing unsaturated double bonds, a combined dynamic cross-linking agent and a catalyst to obtain a blend; then carrying out hot press curing on the blend to obtain a cured product, wherein in the curing process, the combined dynamic cross-linking agent carries out click reaction with double bonds or epoxy groups of the elastomer through mercaptan to form a dynamic bond cross-linking network; and finally, stretching the obtained cured product to a strain of 100-1000% above the bond exchange reaction temperature of the dynamic bond, so that the molecular chain of the elastomer is oriented, and then maintaining for 30-300 min to obtain the high-strength self-repairing elastomer material.
7. The method of producing a high strength self-healing elastomer material according to claim 6, wherein the bond exchange reaction temperature of the dynamic bond is 80 ℃ to 200 ℃.
8. The method of preparing a high strength self-healing elastomeric material according to claim 6, wherein the method of preparing comprises the steps of:
1) The method comprises the steps of (1) carrying out melt blending or open mill blending on an epoxidized elastomer or an elastomer containing unsaturated double bonds, a combined dynamic cross-linking agent and a catalyst to obtain a blend; the proportion of the raw materials is as follows: 100 parts by weight of an epoxidized elastomer or an elastomer containing unsaturated double bonds, 1-10 parts by weight of a combined dynamic cross-linking agent and 0.1-1 part by weight of a catalyst;
2) Carrying out hot press curing on the blend obtained in the step 1) for 30-180 min at the temperature of 100-200 ℃ and the pressure of 5-20 MP to obtain a cured product;
3) Stretching the cured product obtained in the step 2) to a strain of 100-1000% at 80-200 ℃ so as to orient the molecular chains of the elastomer, and keeping for 30-300 min to obtain the high-strength self-repairing elastomer material.
9. The method for producing a high-strength self-repairing elastomer material according to claim 8, wherein in the step 1), the blending temperature is 20 to 100 ℃ and the blending time is 5 to 15min.
10. A method of improving the strength of a self-healing elastomeric material, the method comprising: selecting an epoxidized elastomer or an elastomer containing unsaturated double bonds as a matrix, and introducing a combined dynamic cross-linking agent and a catalyst into the matrix; firstly, uniformly blending all the raw materials to obtain a blend, then, carrying out hot pressing and curing on the blend to obtain a cured product, and finally, carrying out stretching treatment on the cured product, wherein the stretching treatment method of the cured product comprises the following steps: stretching the obtained cured product to a strain of 100-1000% at 80-200 ℃ to orient the elastomer molecular chain, and keeping for 30-300 min;
wherein, the proportion of each raw material is as follows: 100 parts by weight of an epoxidized elastomer or an elastomer containing unsaturated double bonds, 1-10 parts by weight of a combined dynamic cross-linking agent and 0.1-1 part by weight of a catalyst; the structural formula of the combined dynamic cross-linking agent is shown as formula I:
HS--R-SH
i is a kind of
R in the formula I is selected from phenylborate or ester bond.
11. The method of claim 10, wherein the hot press curing method is: and (3) carrying out hot press curing on the obtained blend for 30-180 min at the temperature of 100-200 ℃ and the pressure of 5-20 MP.
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