CN116217884A - Self-repairing polyurethane elastomer material and preparation method thereof - Google Patents
Self-repairing polyurethane elastomer material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 79
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
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- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
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- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
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- OYTKINVCDFNREN-UHFFFAOYSA-N amifampridine Chemical compound NC1=CC=NC=C1N OYTKINVCDFNREN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004012 amifampridine Drugs 0.000 claims description 2
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims description 2
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 229920006273 intrinsic self-healing polymer Polymers 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a self-repairing polyurethane elastomer material and a preparation method thereof, comprising the following steps: preparing a polyurethane elastic matrix; the self-repairing polyurethane elastomer material is obtained by adding the polyurethane elastomer matrix, the dimethylglyoxime and the 2,5 dithiobiurea into a container which is anhydrous, dried and sealed, carrying out water bath heating, ultrasonic treatment, curing and baking, the tensile strength of the self-repairing polyurethane elastomer material is up to 35.99MPa, and the self-repairing polyurethane elastomer material can realize self-repairing of the material on the basis of complete cutting of the material under the condition of room temperature without heating or irradiation of an external light source under the stress strain cyclic stretching curve under the condition of 500 percent strain, and has colorless and transparent property and wide application prospect.
Description
Technical Field
The invention relates to the field of elastomer materials, in particular to a self-repairing polyurethane elastomer material and a preparation method thereof.
Background
Self-healing is a beneficial property of biological tissue that allows the structural tissue to effectively self-heal after mechanical damage, which, if incorporated into a composite material, would greatly increase the useful life of the device. The self-repairing material, namely the polymer material which can repair the damaged part spontaneously or under specific conditions (such as heating, ultraviolet light, PH and the like) by virtue of repairing agents or through intermolecular interaction, has great potential in various fields of intelligent medical appliances, electronic skin, wearable electronic products and the like. The self-repairing materials can be classified into external-aid self-repairing materials and intrinsic-type self-repairing materials according to the difference of repairing strategies. The external-aid type self-repairing material has been developed for twenty years, and the repairing of the matrix material is realized by virtue of the repairing agent which is embedded in the microcapsule or the micro-vessel in advance, and the repairing mode is that the obtained material can only be repaired for a limited number of times, so that the application range of the material is greatly limited. The main research direction of the current self-repairing materials is intrinsic self-repairing materials based on reversible covalent bond or dynamic non-covalent bond interactions. The intrinsic self-healing material relies on one or more reversible covalent bonds and intermolecular interactions to achieve self-healing of the material, unlike the foreign self-healing material.
However, the self-healing ability and mechanical properties of the materials are mutually exclusive in nature. In order to solve the problem, researchers design a new structure (Advanced Materials 2019,31,1901402) capable of improving the self-healing capacity and mechanical property of a polymer material at the same time, the idea is to introduce copper ions and dimethylglyoxime to form a metal coordination complex, so as to construct a covalent cross-linked polyurethane elastomer with a triple dynamic network. However, the tensile strength of 14.8MPa of the polyurethane material still limits the application range of the polyurethane material in practical use, and the addition of copper ions enhances the mechanical properties of the material and simultaneously changes the material into yellow, thereby limiting the application of the material. Materials Horizons 2022,9,640-652 shows that besides the construction of complex crosslinked networks, the synergy of multiple bonds to improve the mechanical properties of the materials, elastomer materials with excellent self-healing ability and excellent mechanical properties can be synthesized by introducing a large number of hydrogen bonds into polyurethane elastomers and forming multiple dynamic networks through layered hydrogen bond crosslinking. It has extremely strong stretchability, softness and puncture resistance. Journal of Colloid and Interface Science,2021,393-400 indicates that the addition of fillers to polyurethane elastomers, while enhancing mechanical properties, also gives the elastomer the ability to conduct electricity or heat, but fillers in most cases do not participate in the condensation reaction of isocyanate groups, as a hard phase to increase the tensile strength of the material, while the toughness and self-healing efficiency of the elastomer are often low, limiting the range of applications of the material. Therefore, the polyurethane elastomer material which can finish self-repairing at room temperature has important research value and practical significance if the polyurethane elastomer material can be prepared with the tensile strength of more than 20MPa and has transparency and flexibility.
Disclosure of Invention
In order to improve the toughness and self-healing efficiency of an elastomer, the invention provides a preparation method of a self-repairing polyurethane elastomer material, which comprises the following steps:
preparing a polyurethane elastic matrix;
and adding the polyurethane elastic matrix, the dimethylglyoxime and the 2,5 dithiobiurea into a dry and airtight container, and carrying out water bath heating, ultrasonic treatment, solidification and baking to obtain the self-repairing polyurethane elastomer material.
Preferably, the step of preparing the polyurethane elastomer matrix comprises:
adding polytetrahydrofuran ether glycol into a container, and vacuumizing to remove water;
adding synthetic monomers, a chain extender, a catalyst and a solvent into the dehydrated container, and heating in a water bath to obtain a solid product;
and drying the solid product to constant weight to obtain the polyurethane elastic matrix.
Preferably, the synthetic monomer of the polyurethane elastic matrix is one or two of dicyclohexylmethane 4,4' -diisocyanate and isophorone diisocyanate.
Preferably, the chain extender is one or more of 3, 4-diaminopyridine, 2, 6-diaminopyridine, glycerol and ethylene glycol.
Preferably, the parts ratio of the polyurethane elastic matrix, the dimethylglyoxime and the 2,5 dithiobiurea is 100:40:60.
preferably, the parts ratio of polytetrahydrofuran ether glycol, diisocyanate, chain extender and catalyst is 50: 30-70:20-40: 0.5 to 1.
Preferably, the temperature of the water bath heating is 50-90 ℃, and the heating time is not less than 1h.
Preferably, the baking temperature is 50-90 ℃, and the baking time is not less than 24 hours.
The invention also provides a self-repairing polyurethane elastomer material prepared by the method.
According to the high-strength self-repairing polyurethane elastomer provided by the invention, a plurality of reversible covalent bonds and non-covalent interactions are introduced, and a principle of synergistic interaction of multiple bonds is adopted to construct a cross-linked network with alternate soft segments and hard segments, so that excellent mechanical properties are achieved, and meanwhile, good self-healing rate can be maintained. The molecules of the hard segment are mainly concentrated near the diisocyanate molecules, and a reversible covalent bond with stronger bond energy is formed through condensation of carbamate functional groups and hydroxyl groups or amino groups; the soft segments are then mainly provided by polytetrahydrofuran ether glycol, the presence of which can be displaced relatively to the hard phase acting as network node, which is reversible. The hydrogen bond formed by N, O, S and other atoms serves as a sacrificial bond in the whole system, after the external load is unloaded and relaxed, the broken hydrogen bond in the stretching process is re-bonded, the hydrogen bond energy is weaker than that of a reversible covalent bond, but the O, S atoms in the dimethylglyoxime and the 2,5 dithiobiurea can form a large number of hydrogen bonds with hydrogen, and the plurality of hydrogen bonds endow the whole covalent crosslinking system with high toughness and good elasticity.
The mechanical property of the high-strength flexible self-repairing elastomer provided by the invention is tested by adopting a GB 13022-1991 specified test method, the tensile strength is 16.7-35.99MPa, and the elongation at break is 325-900%. Characterization of self-healing efficiency according to the original sample of specified size, scratches were preformed on the surface of the sample using a blade, and then left standing at room temperature for a period of time, and tensile strength and elongation at break after healing were measured again, repair efficiency (%) = (mechanical properties after rubber repair/original mechanical properties of rubber) ×100, resulting in a self-healing efficiency of 20-60% for the rapid self-healing thermoplastic polyurethane elastomer. The test shows that the high-strength flexible self-repairing polyurethane elastomer prepared by the invention not only has excellent mechanical properties, but also has great potential application value in actual life application.
The raw materials used in the invention are all conventional chemicals, the preparation process is simple and easy to operate, and the prepared high-strength flexible self-repairing polyurethane elastomer has good mechanical properties and high self-healing efficiency.
Drawings
FIG. 1 is a flow chart for preparing a polyurethane elastomeric matrix;
FIG. 2 is a flow chart for preparing a self-healing polyurethane elastomeric material;
FIG. 3 is a stress-strain plot of the self-healing polyurethane elastomer material of example 3;
FIG. 4 is a continuous cycle stretch curve at room temperature from 100% to 500% strain for the self-healing polyurethane elastomeric material of example 3;
FIG. 5 is a plot of the repeated cycling stretch of the self-healing polyurethane elastomer material of example 3 at 500% strain;
FIG. 6 is a graph of the repair ability of the self-repairing polyurethane elastomer material of example 3;
FIG. 7 is a schematic illustration of the experimental reaction process.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The present embodiment provides a method for preparing a self-repairing polyurethane elastomer material, please refer to fig. 1 and fig. 2, which includes the following steps:
s110, placing the three-necked flask and the condensing reflux device into a blast oven to be dried at 120 ℃ for 1h so as to remove water molecules attached to the surface of a reaction container; 40 parts of polytetrahydrofuran ether glycol are added into a three-necked round bottom flask and sealed, and vacuum is applied at 100 ℃ for 1h to remove water in the polytetrahydrofuran ether glycol;
s120, connecting the three-neck round-bottom flask with a condensation reflux device, adding the synthetic monomer, the chain extender, the catalyst and the solvent into the three-neck round-bottom flask which is dehydrated and dried and is sealed and filled with the protective gas, and stirring and reacting at the temperature of 50-90 ℃ in a water bath heating mode, wherein the reaction time is not less than 1h. In the embodiment, polytetrahydrofuran ether glycol, dicyclohexylmethane 4,4' -diisocyanate is used as a raw material, dibutyltin dilaurate is used as a catalyst, glycerol is used as a chain extender, and acetone is used as a solvent to synthesize the polyurethane matrix. Polytetrahydrofuran ether glycol is selected as the soft segment because its soft linear structure helps to promote molecular movement to achieve self-healing of the material. Dicyclohexylmethane 4,4' -diisocyanate serves as a hard segment, on the one hand, provides a carbamate group, and is polycondensed with hydroxyl groups, and on the other hand, the bulky structure can inhibit crystallization to enhance the fluidity of the chain so as to realize better self-repair. Furthermore, the carbamate on dicyclohexylmethane 4,4' -diisocyanate has a higher dynamic due to the steric influence of the cyclohexyl ring, which will further promote the crosslinking and reconstruction of the covalent network.
And S130, drying the solid product obtained after the reaction is finished to constant weight, and thus obtaining the polyurethane elastic matrix.
S210, obtaining the polyurethane elastic matrix through the steps.
S220, dissolving the obtained polyurethane elastic matrix by using a solvent, adding 30 parts of dimethylglyoxime and 20 parts of 2,5 dithiobiurea into the solvent, and (3) sealing the flask and introducing a protective gas. And stirring and reacting at 50-90 ℃ by a water bath heating mode, wherein the reaction time is not less than 2h. After the reaction is finished, the three-neck flask is placed in an ultrasonic cleaning machine, small bubbles dissolved in the solution are removed through ultrasonic, the ultrasonic time is not less than 5min, and the oxygen dissolved in the solution is completely removed in the stirring process. And then pouring the liquid in the three-neck flask into silica gel, putting the silica gel into a blast oven at 70 ℃ to cure the material for 48 hours, transferring the mold into a vacuum oven at 90 ℃ after curing is finished until the material is dried to constant weight, demolding, and finishing drying to obtain the high-strength polyurethane elastomer.
In this example, dimethylglyoxime as a chain extender introduces reversible DOU groups in which methyl groups can act to inhibit hard segment crystallization and promote chain movement. The addition of 2,5 dithiobiurea plays a vital role in the construction of the whole covalent network, the amino groups at the two ends of the dithiobiurea can be condensed into polyurea with carbamate groups, and the sulfur atoms on thiourea bonds can be combined with hydrogen atoms on polytetrahydrofuran ether glycol and dimethylglyoxime to form hydrogen bonds. The weaker hydrogen bond plays a role in dissipating energy when the polyurethane elastomer is deformed, so that higher toughness is obtained, and the recombination of the hydrogen bond is one of important factors that the material can be automatically repaired. In addition, chemical bonds such as covalent bonds, thiourea bonds and hydrogen bonds are mainly concentrated at hard segments of the polyurethane elastomer, movement of soft segment molecular chains cannot be influenced, synergistic effect is integrally achieved, the purpose of improving material performance together by various chemical bonds is achieved, and the tensile strength and toughness of one-to-two numbers in the self-repairing elastomer at room temperature are obtained.
In this embodiment, the self-repairing method of the strength flexible polyurethane elastomer is as follows: if the surface of the material is scratched, the material is placed in a horizontal state and the applied load is removed, and if necessary the polyurethane elastomer surface is wetted with cotton balls. If the material is in a broken state, sufficient contact of the broken section of the polyurethane elastomer material is ensured, if necessary wetting with ethanol at the broken section is possible, and a close fit of the material at the broken section is ensured.
Example 2
The present embodiment provides a method for preparing a self-repairing polyurethane elastomer material, please refer to the attached body 1 and fig. 2, comprising the following steps:
s110, placing the three-necked flask and the condensing reflux device into a blast oven to be dried at 120 ℃ for 1h so as to remove water molecules attached to the surface of a reaction container; 60 parts of polytetrahydrofuran ether glycol are added into a three-necked round bottom flask and sealed, and vacuum is applied at 100 ℃ for 1h to remove water in the polytetrahydrofuran ether glycol;
and S120, connecting the three-neck round bottom flask with a condensing reflux device, adding 100 parts of dicyclohexylmethane 4,4' -diisocyanate, 5 parts of dibutyltin dilaurate and 20 parts of glycerol into the three-neck round bottom flask at room temperature, taking dimethylacetamide as a solvent, and stirring the mixture for 6 hours at 70 ℃ in a nitrogen atmosphere to fully perform the reaction.
And S130, drying the solid product obtained after the reaction is finished to constant weight, and thus obtaining the polyurethane elastic matrix.
S210, obtaining the polyurethane elastic matrix through the steps.
S220, dissolving the obtained polyurethane elastic matrix by using a solvent, adding 30 parts of dimethylglyoxime and 40 parts of 2,5 dithiobiurea, stirring for 1h at 70 ℃ to fully dissolve various raw materials in a polar solvent, sealing the flask, and introducing a protective gas. And stirring and reacting at 50-90 ℃ by a water bath heating mode, wherein the reaction time is not less than 2h. After the reaction is finished, the three-neck flask is placed in an ultrasonic cleaning machine, small bubbles dissolved in the solution are removed through ultrasonic, the ultrasonic time is not less than 5min, and the oxygen dissolved in the solution is completely removed in the stirring process. And then pouring the liquid in the three-neck flask into silica gel, putting the silica gel into a blast oven at 70 ℃ to cure the material for 48 hours, transferring the mold into a vacuum oven at 90 ℃ after curing is finished until the material is dried to constant weight, demolding, and finishing drying to obtain the high-strength polyurethane elastomer.
Example 3
The present embodiment provides a method for preparing a self-repairing polyurethane elastomer material, please refer to the attached body 1 and fig. 2, comprising the following steps:
s110, placing the three-necked flask and the condensing reflux device into a blast oven to be dried at 120 ℃ for 1h so as to remove water molecules attached to the surface of a reaction container; 35 parts of polytetrahydrofuran ether glycol are added into a three-necked round bottom flask and sealed, and vacuum is applied at 100 ℃ for 1h to remove water in the polytetrahydrofuran ether glycol;
and S120, connecting the three-neck round bottom flask with a condensing reflux device, adding 100 parts of dicyclohexylmethane 4,4' -diisocyanate, 5 parts of dibutyltin dilaurate and 10 parts of glycerol in a room temperature state, taking acetone as a solvent, and stirring at 40 ℃ for 6 hours under a nitrogen atmosphere to fully carry out the reaction.
And S130, drying the solid product obtained after the reaction is finished to constant weight, and thus obtaining the polyurethane elastic matrix.
S210, obtaining the polyurethane elastic matrix through the steps.
S220, dissolving the obtained polyurethane elastic matrix by using a solvent, adding 35 parts of dimethylglyoxime, 20 parts of 2,5 dithiobiurea, 10 parts of glycerol and 10ml of acetone solution, stirring at 40 ℃ for 1h, fully dissolving various raw materials in a polar solvent, sealing the flask, and introducing a protective gas. And stirring and reacting at 50-90 ℃ by a water bath heating mode, wherein the reaction time is not less than 2h. After the reaction is finished, the three-neck flask is placed in an ultrasonic cleaning machine, small bubbles dissolved in the solution are removed through ultrasonic, the ultrasonic time is not less than 5min, and the oxygen dissolved in the solution is completely removed in the stirring process. And then pouring the liquid in the three-neck flask into silica gel, putting the silica gel into a blast oven at 55 ℃ to cure the material for 48 hours, transferring the mold into a vacuum oven at 90 ℃ after curing is finished until the material is dried to constant weight, demolding, and finishing drying to obtain the high-strength polyurethane elastomer.
Example 4
The present embodiment provides a method for preparing a self-repairing polyurethane elastomer material, please refer to the attached body 1 and fig. 2, comprising the following steps:
s110, placing the three-necked flask and the condensing reflux device into a blast oven to be dried at 120 ℃ for 1h so as to remove water molecules attached to the surface of a reaction container; 35 parts of polytetrahydrofuran ether glycol are added into a three-necked round bottom flask and sealed, and vacuum is applied at 100 ℃ for 1h to remove water in the polytetrahydrofuran ether glycol;
and S120, connecting the three-neck round bottom flask with a condensing reflux device, adding 100 parts of isophorone diisocyanate, 5 parts of dibutyltin dilaurate and 10 parts of glycerol in a room temperature state, taking acetone as a solvent, and stirring at 40 ℃ for 6 hours under a nitrogen atmosphere to fully carry out the reaction.
And S130, drying the solid product obtained after the reaction is finished to constant weight, and thus obtaining the polyurethane elastic matrix.
S210, obtaining the polyurethane elastic matrix through the steps.
S220, dissolving the obtained polyurethane elastic matrix by using a solvent, adding 35 parts of dimethylglyoxime and 20 parts of 2,5 dithiobiurea, stirring for 1h at 40 ℃, fully dissolving various raw materials in a polar solvent, sealing the flask, and introducing a protective gas. And stirring and reacting at 50-90 ℃ by a water bath heating mode, wherein the reaction time is not less than 2h. After the reaction is finished, the three-neck flask is placed in an ultrasonic cleaning machine, small bubbles dissolved in the solution are removed through ultrasonic, the ultrasonic time is not less than 5min, and the oxygen dissolved in the solution is completely removed in the stirring process. And then pouring the liquid in the three-neck flask into silica gel, putting the silica gel into a blast oven at 55 ℃ to cure the material for 48 hours, transferring the mold into a vacuum oven at 90 ℃ after curing is finished until the material is dried to constant weight, demolding, and finishing drying to obtain the high-strength polyurethane elastomer.
Example 5
The present embodiment provides a method for preparing a self-repairing polyurethane elastomer material, please refer to the attached body 1 and fig. 2, comprising the following steps:
s110, placing the three-necked flask and the condensing reflux device into a blast oven to be dried at 120 ℃ for 1h so as to remove water molecules attached to the surface of a reaction container; 35 parts of polytetrahydrofuran ether glycol are added into a three-necked round bottom flask and sealed, and vacuum is applied at 100 ℃ for 1h to remove water in the polytetrahydrofuran ether glycol;
and S120, connecting the three-neck round bottom flask with a condensing reflux device, adding 100 parts of dicyclohexylmethane 4,4' -diisocyanate, 10 parts of dibutyltin dilaurate and 15 parts of glycerol in a room temperature state, taking acetone as a solvent, and stirring at 40 ℃ for 6 hours under a nitrogen atmosphere to fully carry out the reaction.
And S130, drying the solid product obtained after the reaction is finished to constant weight, and thus obtaining the polyurethane elastic matrix.
S210, obtaining the polyurethane elastic matrix through the steps.
S220, dissolving the obtained polyurethane elastic matrix by using a solvent, adding 15 parts of dimethylglyoxime and 40 parts of 2,5 dithiobiurea, stirring for 1h at 40 ℃, fully dissolving various raw materials in a polar solvent, sealing the flask, and introducing a protective gas. And stirring and reacting at 50-90 ℃ by a water bath heating mode, wherein the reaction time is not less than 2h. After the reaction is finished, the three-neck flask is placed in an ultrasonic cleaning machine, small bubbles dissolved in the solution are removed through ultrasonic, the ultrasonic time is not less than 5min, and the oxygen dissolved in the solution is completely removed in the stirring process. And then pouring the liquid in the three-neck flask into silica gel, putting the silica gel into a blast oven at 55 ℃ to cure the material for 48 hours, transferring the mold into a vacuum oven at 90 ℃ after curing is finished until the material is dried to constant weight, demolding, and finishing drying to obtain the high-strength polyurethane elastomer.
Example 6
In this example, mechanical experiments are performed on the polyurethane elastomer prepared by the invention, and the results are shown in fig. 3 to 6, and fig. 3 is a stress-strain curve diagram of the polyurethane elastomer in example 3, which can be seen that the mechanical properties of the polyurethane elastomer after dimethylglyoxime and 2,5 dithiobiurea are respectively added are greatly improved. The actual performance of the material can be regulated by changing the amount of the added compound according to the actual requirement; fig. 4 is a continuous cyclic stretching curve of the polyurethane elastomer of example 3 at room temperature from 100% to 500% strain with no waiting time between two consecutive loads. After the load is removed after the test is finished, the elastic body can recover 105% of the original length in 5 minutes, which shows that the elastic modulus is successfully recovered in a limited test time, the residual strain is small, and the performance is excellent; fig. 5 is a graph of the repeated cycle stretch profile of the polyurethane elastomer of example 3 at 500% strain for a total of 10 cycles with no waiting time between two consecutive cycle stretches. Then the film is relaxed for 2 hours at 25 ℃ before 11 th cycle stretch experiments, and the stress-strain curve of 11 th cycle is basically similar to that of 1 st cycle, which shows that the polyurethane elastomer material basically restores the original stretching performance; FIG. 6 shows that the polyurethane elastomer of example 3 has fracture spliced together on the basis of complete cut-off, and is repaired for 1 hour respectively at room temperature (25 ℃) and the tensile stress at break after 2 hours is up to 5MPa and 6MPa respectively, showing that the material itself can reach a certain degree of repair capability in a short time.
Fig. 7 is a schematic illustration of the experimental reaction process, incorporating dynamic oxime urethane and thiourea linkages in the polyurethane elastomer, PTMEG (polytetramethylene ether glycol) was chosen as the soft segment because its chain is flexible and can promote chain movement for better self-healing. HMDI (dicyclohexylmethane 4,4' -diisocyanate) is selected as the hard segment because its bulky structure inhibits crystallization and increases chain mobility to achieve better self-repair. DMG (dimethylglyoxime) as a chain extender introduces reversible DOU groups, methyl groups in DMG inhibiting crystallization of hard segments and promoting chain movement, multiple dynamic bonds including reversible DOU covalent bonds, thiourea bonds and hydrogen bonds. The dissociation process of weak bonds (hydrogen bonds) can significantly dissipate energy during mechanical deformation, thereby achieving high toughness. Their recombination results in effective self-repair.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the self-repairing polyurethane elastomer material is characterized by comprising the following steps of:
preparing a polyurethane elastic matrix;
and adding the polyurethane elastic matrix, the dimethylglyoxime and the 2,5 dithiobiurea into a dry and airtight container, and carrying out water bath heating, ultrasonic treatment, solidification and baking to obtain the self-repairing polyurethane elastomer material.
2. The method of preparing a self-healing polyurethane elastomer material according to claim 1, wherein the step of preparing the polyurethane elastomer matrix comprises:
adding polytetrahydrofuran ether glycol into a container, and vacuumizing to remove water;
adding synthetic monomers, a chain extender, a catalyst and a solvent into the dehydrated container, and heating in a water bath to obtain a solid product;
and drying the solid product to constant weight to obtain the polyurethane elastic matrix.
3. The method for preparing a self-repairing polyurethane elastomer material according to claim 2, wherein the synthetic monomer is one or two of dicyclohexylmethane 4,4' -diisocyanate and isophorone diisocyanate.
4. The method of producing a self-healing polyurethane elastomer material according to claim 2, wherein the chain extender is one or more of 3, 4-diaminopyridine, 2, 6-diaminopyridine, glycerol, and ethylene glycol.
5. The method of preparing a self-healing polyurethane elastomer material according to claim 2, wherein the catalyst is dibutyltin dilaurate.
6. The method for preparing a self-repairing polyurethane elastomer material according to claim 1, wherein the ratio of parts of polyurethane elastomer matrix, dimethylglyoxime and 2,5 dithiobiurea is 100:40:60.
7. the method for preparing a self-repairing polyurethane elastomer material according to claim 2, wherein the ratio of parts of polytetrahydrofuran ether glycol, diisocyanate, chain extender and catalyst is 50: 30-70:20-40: 0.5 to 1.
8. The method for preparing a self-repairing polyurethane elastomer material according to claim 1, wherein the water bath heating temperature is 50-90 ℃ and the heating time is not less than 1h.
9. The method for producing a self-repairing polyurethane elastomer material according to claim 1, wherein the baking temperature is 50 to 90 ℃ and the baking time is not less than 24 hours.
10. A self-healing polyurethane elastomer material prepared by the method of any one of claims 1 to 9.
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