CN115181347A - 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, and relates 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 epoxidized elastomer or unsaturated double bond-containing elastomer, 1 to 10 parts of combined dynamic cross-linking agent and 0.1 to 1 part of catalyst; the structural formula of the combined dynamic cross-linking agent is shown in a formula I, wherein R in the formula I is selected from phenylboronate or an ester bond. The invention constructs a dynamic covalent cross-linking network by the reaction of the combined dynamic bond and the elastomer, and utilizes the characteristic that the combined dynamic bond can realize bond-bond exchange above the activation temperature to stretch the elastomer and fix the strain; an elastomeric material having both high strength and self-healing properties 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 noncovalent or/and dynamic covalent bonds into a macromolecular skeleton to form a cross-linked 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 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, due to the intrinsic high activity and reversibility of the dynamic chemical bonds, the bond energy is often low, and the strength of the prepared material is weak. The contradiction between strength and self-repairing performance is a problem to be solved urgently in the field.
In recent years, researchers have adjusted the mechanical strength and the repair performance of self-repairing elastomer materials by designing different dynamic structures. The main category of elastomers that can be classified as those crosslinked by dynamic noncovalent bonds, such as hydrogen bonds, coordination, pi stacking, and other supramolecular interactions, is that patent application publication No. CN 109280143A discloses a self-healing elastomer crosslinked by metal-coordinate bonds, and elastomers crosslinked by dynamic covalent bonds, such as ester bonds, borate bonds, urethanes, alkoxyamines, and the like, and Journal of materials Chemistry a (2019, 7, 1459-1467) reports a covalently crosslinked elastomer composed of silyl ethers. The action strength of the dynamic covalent bond is generally stronger than that of the supermolecular interaction, so the self-repairing elastomer crosslinked by the dynamic covalent network generally has higher mechanical property and more reliable service performance. However, the tensile strength of the self-repairing elastomer prepared by the dynamic covalent bond is more than 10MPa and still stays at a relatively low level.
Increasing the crosslinking density can further improve the tensile strength of the self-repairing elastomer, such as the high-crosslinking elastomer reported by Nano Energy (2021, 87, 105822), and the addition of a large amount of crosslinking agent can damage the inherent excellent properties of the elastomer, such as high elasticity, low hysteresis, and the like, and more importantly, the high crosslinking density can significantly inhibit the mobility of molecular chains, and the relaxation time is greatly prolonged, so that the repairing performance of the elastomer is significantly reduced. Therefore, how to combine the strength and the self-repairing performance is the first technical difficulty in the field.
Disclosure of Invention
In order to solve the defects in the prior art, the invention constructs a dynamic covalent crosslinking network by the reaction of a combined dynamic bond and an elastomer, and utilizes the characteristic that the combined dynamic bond can realize bond-to-bond exchange above the activation temperature; and stretching the elastomer above the activation temperature, fixing the strain, and realizing stress relaxation by exchange of the combined dynamic bond so as to maintain the oriented structure; the tensile strength of the oriented elastomer in the orientation direction is obviously improved, and a good repairing effect can be realized under a relatively mild condition; namely, the invention obtains a self-repairing elastomer which is crosslinked by a combined dynamic bond and has an oriented structure; thus obtaining the elastomer material with high strength and self-repairing performance.
The technical scheme of the invention is as follows:
the invention aims to solve the first technical problem of providing a high-strength self-repairing elastomer material, which comprises the following raw materials in parts by weight: 100 parts of epoxidized elastomer or unsaturated double bond-containing elastomer, 1 to 10 parts of combined dynamic cross-linking agent and 0.1 to 1 part of catalyst; wherein, the structural formula of the combined dynamic cross-linking agent is shown in formula I:
HS-R-SH
formula I
In the formula I, R is selected from phenylboronate or an ester bond. In the present invention, the binding dynamic crosslinking agent is a substance that can react with the elastomer to form a binding dynamic bond crosslinked network.
Further, the binding type dynamic cross-linking agent is selected from: 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborocyclopentane ] (BDB), ethylene bis (3-mercaptopropionate), ethylene glycol bis (thioglycolate), 1, 4-butanediol bis (thioglycolate), or pentaerythritol tetrakis (3-mercaptopropionate).
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 selected from at least one of natural rubber, styrene butadiene rubber, butyl rubber, nitrile butadiene rubber, isoprene rubber or butadiene rubber.
Further, the catalyst is selected from the group consisting of: 4-dimethylaminopyridine, zinc acetate or tetrabutyl titanate.
The second technical problem to be solved by the present invention is to provide a preparation method of the above high-strength self-repairing elastomer material, wherein the method comprises: 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, the blend is cured by hot pressing to obtain a cured product, and the combined dynamic cross-linking agent forms a dynamic bond cross-linking network by click reaction between mercaptan and double bonds or epoxy groups of the elastomer in the curing process; and finally, stretching the obtained cured material to the strain of 100-1000% above the temperature of the bond exchange reaction of the dynamic bond, so that the molecular chain of the elastomer is oriented, and then keeping for 30-300 min, thereby preparing the high-strength self-repairing elastomer material.
Further, the temperature of the bond exchange reaction 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-pressing 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 between mercaptan and double bonds or epoxy groups of the elastomer; and finally, stretching the obtained cured substance above the temperature of the bond exchange reaction of the bonded dynamic bonds until the strain is 100-1000%, so that molecular chains of the elastomer are oriented, then keeping the molecular chains for 30-300 min, realizing the relaxation of the internal stress of the elastomer through the bond exchange of the bonded dynamic bonds, reducing the orientation recovery caused by the resilience of the elastomer, and finally realizing the fixation of an oriented structure by combining the fixation effect of a cross-linking network, thereby preparing the high-strength self-repairing elastomer material.
Further, in the above method, the blending of the respective raw materials may be performed by melt blending or roll mixing.
Further, the preparation method comprises the following steps:
1) The epoxy elastomer or the elastomer containing unsaturated double bonds, the combined dynamic cross-linking agent and the catalyst are subjected to melt blending or open mixing to obtain a blend; the proportion of each raw material is as follows: 100 parts of epoxidized elastomer or elastomer containing unsaturated double bonds, 1-10 parts of combined dynamic cross-linking agent and 0.1-1 part of catalyst;
2) Hot-pressing and curing the blend obtained in the step 1) for 30-180 min at 100-200 ℃ and under the pressure of 5-20 MP to obtain a cured product;
3) And (3) stretching the cured product obtained in the step 2) to 100-1000% of strain at 80-200 ℃ so as to orient the molecular chain of the elastomer, and keeping the molecular chain oriented 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 raw materials to obtain a blend, then carrying out hot-pressing 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 of epoxidized elastomer or elastomer containing unsaturated double bonds, 1-10 parts of combined dynamic cross-linking agent and 0.1-1 part of catalyst; the structural formula of the combined dynamic cross-linking agent is shown in a formula I:
HS-R-SH
formula I
In the formula I, R is selected from phenylboronate or an ester bond.
Further, the hot-pressing curing method comprises the following steps: the obtained blend is hot-pressed and solidified for 30-180 min at 100-200 ℃ and 5-20 MP.
Further, the method for stretching the cured product comprises: the obtained condensate is pulled to be under the strain of 100-1000% at the temperature of 80-200 ℃, so that the molecular chain of the elastomer is oriented and kept for 30-300 min.
The invention has the beneficial effects that:
(1) The invention utilizes the bond exchange characteristic of the combined dynamic bond above the activation temperature to relax the stress existing in the elastomer, thereby fixing the orientation of the molecular chain of the elastomer along the stretching direction and greatly improving the stretching strength (table 1).
(2) Compared with the traditional permanent cross-linked bond, the self-repairing elastomer cross-linked by the combined dynamic bond can realize repair under the condition of a temperature field after the material is damaged; compared with supermolecule acting force, the material has higher mechanical strength and more reliable use performance (figure 2).
(3) The control of the relaxation behavior during the orientation by stretching allows a wide range of elastomer strength adjustment (fig. 3).
Description of the drawings:
FIG. 1 is a drawing showing the tensile properties of examples 1 to 3 of the present invention and comparative examples 1 to 3, and it can be seen that as the content of the crosslinking agent increases, the strength of the elastomer continuously increases, and the difference in strength between the samples before and after orientation increases; the tensile strength of example 1 exceeds 30MPa, indicating that the elastomer obtained by the present invention has excellent mechanical properties.
FIG. 2 is a test chart of tensile properties of examples 1 to 3 and comparative examples 1 to 3 of the present invention after being repaired at 80 ℃ for 24 hours, and it can be seen that the elastomer after being repaired has higher mechanical strength after being stretched and oriented than the elastomer without being stretched and oriented, which indicates that the elastomer has good repairing properties.
FIG. 3 is a graph of tensile property tests of examples 1,4, and 5 of the present invention, which show that self-healing elastomers with high strength can be prepared by adjusting and controlling the orientation time.
FIG. 4 is a schematic diagram illustrating the mechanism of the present invention, i.e. the curing and orientation process of the elastomer, from which it can be seen that the mercapto groups at both ends of the cross-linking agent react with the epoxy functional groups or unsaturated carbon-carbon double bonds of the elastomer to form a cross-linked network; stretching the elastomer to a fixed strain above the bond exchange reaction temperature of a cross-linked network constructed by a combined dynamic covalent bond so that molecular chains of the elastomer are oriented, and then keeping for a proper time; the molecular chains of the elastomer are oriented by stretching, the relaxation of the internal stress of the elastomer is realized through the bond exchange of the used combined dynamic bonds, the orientation recovery caused by the resilience of the elastomer is reduced, and the fixation of an oriented structure is finally realized by combining the fixation effect of a cross-linked network, so that the high-strength self-repairing elastomer material is prepared.
Detailed Description
The invention provides a high-strength self-repairing elastomer material which is composed of the following materials: 100 parts of unsaturated double bond-containing elastomer or epoxidized elastomer, 1-10 parts of combined dynamic cross-linking agent and 0.1-1 part of catalyst; the preparation process can adopt the following modes: (1) The elastomer, the combined dynamic cross-linking agent and the catalyst are melted, blended or milled uniformly; (2) Putting the mixture obtained in the step (1) into a flat vulcanizing instrument for hot-pressing and curing; (3) And (3) stretching the product cured in the step (2) to a fixed strain under a high temperature condition to orient the molecular chain of the elastomer, keeping the proper time, and fixing the oriented structure by relaxing the internal stress through a combined dynamic bond. The self-repairing elastomer disclosed by the invention has the advantages that the molecular chain orientation structure is fixed by crosslinking of dynamic bonds, the strength of the elastomer can be obviously improved, and meanwhile, the self-repairing elastomer has good self-repairing performance; thus obtaining the combined dynamic bond crosslinked elastomer material with an oriented structure.
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 click reaction of mercaptan and double bonds or epoxy groups of an elastomer, and as the combined dynamic bond is subjected to combined exchange reaction above the exchange reaction temperature, old bond breakage and new bond formation occur simultaneously, so that the cross-linking density of the material is kept unchanged; taking epoxidized natural rubber and a BDB cross-linking agent as an example, the cross-linking reaction and the combined exchange reaction formula are shown as follows, and the mercapto group of the BDB cross-linking agent reacts with the epoxy functional group on the epoxidized natural rubber under the catalysis of DMAP to obtain a cross-linked elastomer; the boroester bond is activated above the bond exchange temperature of the dynamic bond, and an inter-bond exchange occurs.
The following examples are given to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
6.0g of 1, 4-benzenediboronic acid and 8.02g of 1-thioglycerol were dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate was added, and the mixture was stirred at 25 ℃ for 24 hours, filtered, subjected to removal of the anhydrous magnesium sulfate, and rotary evaporated to obtain 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborole ] (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 the temperature of 25 ℃; shearing the mixture into small particles, placing the small particles into a flat rheometer, and curing the small particles by hot pressing at the curing temperature of 160 ℃, the curing pressure of 10MPa and the curing time of 45min. Cutting the cured sample into a rectangular sample strip with the length of 60mm and the width of 27mm, clamping the sample strip by a stretching clamp, stretching the sample strip to 300% strain at the stretching speed of 10mm/min at the temperature of 120 ℃, fixing the strain, and keeping 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-benzenediboronic acid and 8.02g of 1-thioglycerol were dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate was added thereto, and the mixture was stirred at 25 ℃ for 24 hours, filtered, freed of the anhydrous magnesium sulfate, and rotary-evaporated to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolan ] (BDB).
45g of epoxidized natural rubber with an epoxy degree of 30%, 2.25g of BDB and 0.225g of 2-dimethylaminopyridine DMAP are mixed uniformly on a two-roll mill at 25 ℃. Shearing the mixture into small particles, placing the small particles into a flat rheometer, and curing the small particles by hot pressing at the curing temperature of 160 ℃, the curing pressure of 10MPa and the curing time of 45min. The cured sample is cut into a rectangular sample strip with the length of 60mm and the width of 27mm, the sample strip is clamped by a stretching clamp, the sample strip is stretched to 300% strain at the stretching speed of 10mm/min under the condition of 120 ℃, the strain is fixed, and the sample strip is kept for 90min. The sizing properties and repair properties are shown in table 1.
Example 3
6.0g of 1, 4-benzenediboronic acid and 8.02g of 1-thioglycerol were dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate was added thereto, and the mixture was stirred at 25 ℃ for 24 hours, filtered, freed of the anhydrous magnesium sulfate, and rotary-evaporated to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolan ] (BDB).
45g of epoxidized natural rubber with an epoxy degree of 30%, 0.45g of BDB and 0.045g of 2-dimethylaminopyridine DMAP were mixed uniformly on a two-roll mill at 25 ℃. Shearing the mixture into small particles, placing the small particles into a flat rheometer, and curing the small particles by hot pressing at the curing temperature of 160 ℃, the curing pressure of 10MPa and the curing time of 45min. The cured sample is cut into a rectangular sample strip with the length of 60mm and the width of 27mm, the sample strip is clamped by a stretching clamp, the sample strip is stretched to 300% strain at the stretching speed of 10mm/min under the condition of 120 ℃, the strain is fixed, and the sample strip is kept for 90min. The sizing properties and repair properties are shown in table 1.
Example 4
6.0g of 1, 4-benzenediboronic acid and 8.02g of 1-thioglycerol were dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate was added thereto, and the mixture was stirred at 25 ℃ for 24 hours, filtered, freed of the anhydrous magnesium sulfate, and rotary-evaporated to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolan ] (BDB).
45g of epoxidized natural rubber with an epoxy degree of 30%, 4.5g of BDB and 0.45g of 2-dimethylaminopyridine DMAP are mixed uniformly on a two-roll mill at 25 ℃. Shearing the mixture into small particles, placing the small particles into a flat rheometer, and curing the small particles by hot pressing at the curing temperature of 160 ℃, the curing pressure of 10MPa and the curing time of 45min. The cured sample is cut into a rectangular sample strip with the length of 60mm and the width of 27mm, the sample strip is clamped by a stretching clamp, the sample strip is stretched to 300% strain at the stretching speed of 10mm/min under the condition of 120 ℃, the strain is fixed, and the sample strip is kept for 30min. The sizing properties are shown in Table 1.
Example 5
6.0g of 1, 4-benzenediboronic acid and 8.02g of 1-thioglycerol were dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate was added thereto, and the mixture was stirred at 25 ℃ for 24 hours, filtered, freed of the anhydrous magnesium sulfate, and rotary-evaporated to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolan ] (BDB).
45g of epoxidized natural rubber with an epoxy degree of 30%, 4.5g of BDB and 0.45g of 2-dimethylaminopyridine DMAP are mixed uniformly on a two-roll mill at 25 ℃. Shearing the mixture into small particles, placing the small particles into a flat rheometer, and curing the small particles by hot pressing at the curing temperature of 160 ℃, the curing pressure of 10MPa and the curing time of 45min. Cutting the cured sample into a rectangular sample strip with the length of 60mm and the width of 27mm, clamping the sample strip by a stretching clamp, stretching the sample strip to 300% strain at the stretching speed of 10mm/min under the condition of 120 ℃, fixing the strain, and keeping for 60min. The properties of the compounds are shown in Table 1.
Comparative example 1
6.0g of 1, 4-benzenediboronic acid and 8.02g of 1-thioglycerol were dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate was added thereto, and the mixture was stirred at 25 ℃ for 24 hours, filtered, freed of the anhydrous magnesium sulfate, and rotary-evaporated to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolan ] (BDB).
45g of epoxidized natural rubber with an epoxy degree of 30%, 4.5g of BDB and 0.45g of 2-dimethylaminopyridine DMAP are mixed uniformly on a two-roll mill at 25 ℃. Shearing the mixture into small particles, placing the small particles into a flat rheometer, and curing the small particles by hot pressing at the curing temperature of 160 ℃, the curing pressure of 10MPa and the curing time of 45min. The properties of the compounds are shown in Table 1.
Comparative example 2
6.0g of 1, 4-benzenediboronic acid and 8.02g of 1-thioglycerol were dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate was added thereto, and the mixture was stirred at 25 ℃ for 24 hours, filtered, freed of the anhydrous magnesium sulfate, and rotary-evaporated to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolan ] (BDB).
45g of epoxidized natural rubber with an epoxy degree of 30%, 2.25g of BDB and 0.225g of 2-dimethylaminopyridine DMAP are mixed uniformly on a two-roll mill at 25 ℃. Shearing the mixture into small particles, placing the small particles into a flat rheometer, and curing the small particles by hot pressing at the curing temperature of 160 ℃, the curing pressure of 10MPa and the curing time of 45min. The sizing properties are shown in Table 1.
Comparative example 3
6.0g of 1, 4-benzenediboronic acid and 8.02g of 1-thioglycerol were dissolved in 200ml of tetrahydrofuran, 10.0g of anhydrous magnesium sulfate was added thereto, and the mixture was stirred at 25 ℃ for 24 hours, filtered, freed of the anhydrous magnesium sulfate, and rotary-evaporated to give 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborolan ] (BDB).
45g of epoxidized natural rubber with an epoxy degree of 30%, 0.45g of BDB and 0.045g of 2-dimethylaminopyridine DMAP were mixed uniformly on a two-roll mill at 25 ℃. Shearing the mixture into small particles, placing the small particles into a flat rheometer, and curing the small particles by hot pressing at the curing temperature of 160 ℃, the curing pressure of 10MPa and the curing time of 45min. The sizing properties are shown in Table 1.
TABLE 1 comparison of Properties of 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 testing machine of INSTRON company in America, the test sample strip is a dumbbell-shaped sample strip with the length of 37.5mm, the thickness of 1mm and the width of 2mm, the tensile rate is 500mm/min, and the repair tensile strength of the sample strip is measured after the sample strip is cut off, the section is attached for 1min, and then the sample strip is placed at 80 ℃ for self-healing for 24h.
As can be seen from the data in Table 1, examples 1 to 3 had higher tensile strengths, up to 30MPa or more, than comparative examples 1 to 3, and also had higher tensile strengths after repair at 80 ℃ for 24 hours than the repaired specimens of comparative examples 1 to 3. Comparing examples 1,4 and 5, it can be seen that samples of different properties can be obtained by controlling different relaxation times. In conclusion, the invention prepares a high-strength self-repairing elastomer material and provides a feasible preparation method.
Claims (10)
1. The high-strength self-repairing elastomer material is characterized by comprising the following raw materials in parts by weight: 100 portions of epoxidized elastomer or elastomer containing unsaturated double bonds, 1 to 10 portions of combined dynamic cross-linking agent and 0.1 to 1 portion of catalyst; wherein, the structural formula of the combined dynamic cross-linking agent is shown in formula I:
HS-R-SH
formula I
In the formula I, R is selected from phenylboronate or an ester bond.
2. The high strength self-healing elastomeric material of claim 1, wherein said bonded dynamic crosslinker is selected from the group consisting of: 2,2' - (1, 4-phenylene) -bis [ 4-thiol 1,3, 2-dioxaborocyclopentane ], ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (thioglycolate), 1, 4-butanediol bis (thioglycolate), or pentaerythritol tetrakis (3-mercaptopropionate).
3. The high strength self-healing elastomeric material of 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;
further, the elastomer containing unsaturated double bonds is selected from at least one of natural rubber, styrene butadiene rubber, butyl rubber, nitrile rubber, isoprene rubber or butadiene rubber;
further, the catalyst is selected from the group consisting of: at least one of 4-dimethylaminopyridine, zinc acetate or tetrabutyl titanate.
4. The preparation method of the high-strength self-repairing elastomer material as claimed in any one of claims 1 to 3, characterized in that the method 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 the blend is cured by hot pressing to obtain a cured product, and the combined dynamic cross-linking agent performs click reaction with double bonds or epoxy groups of the elastomer through mercaptan in the curing process to form a dynamic bond cross-linking network; and finally, stretching the obtained cured material to the strain of 100-1000% above the temperature of the bond exchange reaction of the dynamic bond, so that the molecular chain of the elastomer is oriented, and then keeping for 30-300 min, thereby preparing the high-strength self-repairing elastomer material.
5. The preparation method of the high-strength self-repairing elastomer material according to claim 4, wherein the temperature of the bond exchange reaction of the dynamic bond is 80-200 ℃.
6. The preparation method of the high-strength self-repairing elastomer material of claim 4, wherein 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-pressing 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 between mercaptan and double bonds or epoxy groups of the elastomer; and finally, stretching the obtained cured substance above the temperature of the bond exchange reaction of the bonded dynamic bonds until the strain is 100-1000%, so that molecular chains of the elastomer are oriented, then keeping the molecular chains for 30-300 min, realizing the relaxation of the internal stress of the elastomer through the bond exchange of the bonded dynamic bonds, reducing the orientation recovery caused by the resilience of the elastomer, and finally realizing the fixation of an oriented structure by combining the fixation effect of a cross-linking network, thereby preparing the high-strength self-repairing elastomer material.
7. The preparation method of the high-strength self-repairing elastomer material as claimed in any one of claims 4 to 6, characterized in that the preparation method comprises the following steps:
1) The epoxy elastomer or the elastomer containing unsaturated double bonds, the combined dynamic cross-linking agent and the catalyst are subjected to melt blending or open mixing to obtain a blend; the proportion of each raw material is as follows: 100 parts of epoxidized elastomer or elastomer containing unsaturated double bonds, 1-10 parts of combined dynamic cross-linking agent and 0.1-1 part of catalyst;
2) Hot-pressing and curing the blend obtained in the step 1) for 30-180 min at 100-200 ℃ and under the pressure of 5-20 MP to obtain a cured product;
3) And (3) stretching the cured substance obtained in the step 2) to a strain of 100-1000% at 80-200 ℃, so that the molecular chain of the elastomer is oriented, and maintaining for 30-300 min to obtain the high-strength self-repairing elastomer material.
8. The preparation method of the high-strength self-repairing elastomer material according to claim 7, wherein in the step 1), the blending temperature is 20-100 ℃ and the blending time is 5-15 min.
9. A method for improving the strength of a self-repairing elastomer material is characterized by comprising the following steps: selecting an epoxidized elastomer or an elastomer containing unsaturated double bonds as a substrate, and introducing a combined dynamic cross-linking agent and a catalyst into the substrate; firstly, uniformly blending all raw materials to obtain a blend, then carrying out hot-pressing 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 of epoxidized elastomer or unsaturated double bond-containing elastomer, 1 to 10 parts of combined dynamic cross-linking agent and 0.1 to 1 part of catalyst; the structural formula of the combined dynamic cross-linking agent is shown in a formula I:
HS-R-SH
formula I
In the formula I, R is selected from phenylboronate or an ester bond.
10. The method for improving the strength of the self-healing elastomeric material of claim 9, wherein the hot press curing is performed by: hot-pressing and curing the obtained blend at 100-200 ℃ and 5-20 MP for 30-180 min;
further, the method for subjecting the cured product to a stretching treatment comprises: the obtained condensate is pulled to be strained to 100-1000% at 80-200 ℃, so that the molecular chain of the elastomer is oriented and kept for 30-300 min.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010128007A1 (en) * | 2009-05-06 | 2010-11-11 | Technische Universiteit Eindhoven | Self-healing polymers |
| US20170008999A1 (en) * | 2014-02-28 | 2017-01-12 | Fundación Cidetec | Self-healing elastomer and process for its preparation |
| US20180231486A1 (en) * | 2015-08-17 | 2018-08-16 | Technion Research & Development Foundation Limited | Self-healing platform unit for pressure and analyte sensing |
| CN108570139A (en) * | 2018-04-20 | 2018-09-25 | 上海交通大学 | A method of preparing cross-linked elastomer using dynamic covalent bond |
| CN109134986A (en) * | 2018-06-27 | 2019-01-04 | 华南理工大学 | A kind of dual crosslinking selfreparing epoxy natural rubber and its preparation method and application |
| CN109705348A (en) * | 2018-12-24 | 2019-05-03 | 西北工业大学 | A kind of selfreparing photocuring based on the exchange of boric acid ester bond can structure system again preparation method |
| US20200024192A1 (en) * | 2016-08-15 | 2020-01-23 | Battelle Memorial Institute | Self-repairing cement polymer composites and processes of making and using same |
| CN113603919A (en) * | 2021-08-12 | 2021-11-05 | 清华大学 | Method for orienting, patterning, repairing, removing, welding polymeric materials |
| CN113801615A (en) * | 2021-10-21 | 2021-12-17 | 合肥工业大学 | Dynamically crosslinked SBS hot-melt pressure-sensitive adhesive and preparation method thereof |
| WO2022086317A1 (en) * | 2020-10-19 | 2022-04-28 | Petroliam Nasional Berhad (Petronas) | Boronic esters and coatings comprising them |
| US20220153907A1 (en) * | 2018-10-16 | 2022-05-19 | Centre National De La Recherche Scientifique | Double dynamic polymers |
| US20220162402A1 (en) * | 2020-11-24 | 2022-05-26 | Board Of Trustees Of Michigan State University | Thermally reversibile crosslinked polyolefins and related polymers, and related methods |
-
2022
- 2022-06-27 CN CN202210732504.7A patent/CN115181347B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010128007A1 (en) * | 2009-05-06 | 2010-11-11 | Technische Universiteit Eindhoven | Self-healing polymers |
| US20170008999A1 (en) * | 2014-02-28 | 2017-01-12 | Fundación Cidetec | Self-healing elastomer and process for its preparation |
| US20180231486A1 (en) * | 2015-08-17 | 2018-08-16 | Technion Research & Development Foundation Limited | Self-healing platform unit for pressure and analyte sensing |
| US20200024192A1 (en) * | 2016-08-15 | 2020-01-23 | Battelle Memorial Institute | Self-repairing cement polymer composites and processes of making and using same |
| CN108570139A (en) * | 2018-04-20 | 2018-09-25 | 上海交通大学 | A method of preparing cross-linked elastomer using dynamic covalent bond |
| CN109134986A (en) * | 2018-06-27 | 2019-01-04 | 华南理工大学 | A kind of dual crosslinking selfreparing epoxy natural rubber and its preparation method and application |
| US20220153907A1 (en) * | 2018-10-16 | 2022-05-19 | Centre National De La Recherche Scientifique | Double dynamic polymers |
| CN109705348A (en) * | 2018-12-24 | 2019-05-03 | 西北工业大学 | A kind of selfreparing photocuring based on the exchange of boric acid ester bond can structure system again preparation method |
| WO2022086317A1 (en) * | 2020-10-19 | 2022-04-28 | Petroliam Nasional Berhad (Petronas) | Boronic esters and coatings comprising them |
| US20220162402A1 (en) * | 2020-11-24 | 2022-05-26 | Board Of Trustees Of Michigan State University | Thermally reversibile crosslinked polyolefins and related polymers, and related methods |
| CN113603919A (en) * | 2021-08-12 | 2021-11-05 | 清华大学 | Method for orienting, patterning, repairing, removing, welding polymeric materials |
| CN113801615A (en) * | 2021-10-21 | 2021-12-17 | 合肥工业大学 | Dynamically crosslinked SBS hot-melt pressure-sensitive adhesive and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| YI CHEN 等: "Mechanically Robust, Self-Healable, and Reprocessable Elastomers Enabled by Dynamic Dual Cross-Links", MACROMOLECULES * |
| ZHAO, YB 等: "Mechanically Robust, Heat-Resistant, and Reprocessable Polyethylene Vitrimers Cross-Linked by ss-Hydroxy Ester Bonds via Reactive Processing", INDUSTRIAL & ENGINEERING CHEMISTR RESEARCH * |
| 陈梦 等: "双重热可逆响应氨酯基/酯基环氧树脂网络的设计及自愈合性能", 中国胶粘剂 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926580A (en) * | 2023-01-13 | 2023-04-07 | 江苏恒美幕墙材料有限公司 | Light curtain wall aluminum plate and preparation method thereof |
| CN115926580B (en) * | 2023-01-13 | 2024-03-19 | 江苏恒美幕墙材料有限公司 | Light curtain wall aluminum plate and preparation method thereof |
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