CN115873256A - Crosslinked polydimethylsiloxane elastomer material and preparation method thereof - Google Patents
Crosslinked polydimethylsiloxane elastomer material and preparation method thereof Download PDFInfo
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- CN115873256A CN115873256A CN202310124683.0A CN202310124683A CN115873256A CN 115873256 A CN115873256 A CN 115873256A CN 202310124683 A CN202310124683 A CN 202310124683A CN 115873256 A CN115873256 A CN 115873256A
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- 239000004205 dimethyl polysiloxane Substances 0.000 title claims abstract description 52
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 title claims abstract description 52
- -1 polydimethylsiloxane Polymers 0.000 title claims abstract description 46
- 229920001971 elastomer Polymers 0.000 title claims abstract description 32
- 239000000806 elastomer Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 238000004519 manufacturing process Methods 0.000 claims description 9
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
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- 238000010438 heat treatment Methods 0.000 claims description 6
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- 239000007787 solid Substances 0.000 claims description 5
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- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 2
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 claims description 2
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 claims description 2
- WNYIBZHOMJZDKN-UHFFFAOYSA-N n-(2-acetamidoethyl)acetamide Chemical compound CC(=O)NCCNC(C)=O WNYIBZHOMJZDKN-UHFFFAOYSA-N 0.000 claims description 2
- UQVKNKXDSWRQJE-UHFFFAOYSA-N n-(3-acetamidophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(NC(C)=O)=C1 UQVKNKXDSWRQJE-UHFFFAOYSA-N 0.000 claims description 2
- 229940054441 o-phthalaldehyde Drugs 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 2
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- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 3
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- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- UODZKAAILJVZGF-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarbonyl chloride Chemical compound ClC(=O)CC(O)(CC(Cl)=O)C(Cl)=O UODZKAAILJVZGF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a cross-linked polydimethylsiloxane elastomer material and a preparation method thereof. The cross-linked polydimethylsiloxane elastomer material prepared by the invention has excellent mechanical properties, multiple hydrogen bonds can be formed in hard sections of the material, the mechanical properties of the material are enhanced, the self-repairing performance is good, larger load can be borne, the application range of the material is greatly widened, and the cross-linked polydimethylsiloxane elastomer material has huge application potential in the emerging intelligent field. The raw materials are simple, can be produced and developed in large batch, can be recycled, and are expected to become products with high economic added values.
Description
Technical Field
The invention belongs to the field of preparation of high polymer materials, and particularly relates to a cross-linked polydimethylsiloxane elastomer material and a preparation method thereof.
Background
In recent years, with the development of the field of intelligent electronics, flexible electronic devices are becoming popular in the world research. The flexible electronic technology is a subversive scientific technology formed by high cross fusion of flexible materials and subjects such as physics, chemistry, material science and engineering, mechanics, optical engineering, biology, biomedical engineering, basic medicine and the like. Elastomer materials are one of the main raw materials for manufacturing flexible electronic devices, and the development of the elastomer materials plays a key role. Polydimethylsiloxane (PDMS) is one of the main matrix materials of elastomer materials, and is widely used in the fields of electronic skins, flexible wearable electronic devices, soft robots, optical devices, etc. due to its advantages of excellent elasticity, excellent hydrophobicity, good weather resistance, and excellent biocompatibility. However, because of the low chemical bond strength of PDMS, the mechanical properties of PDMS are poor, generally lower than 7MPa, and the low mechanical strength makes it easy to break when bearing external stress, so that it loses its original properties and uses. In response to the above problems, dynamic bonds are usually introduced into PDMS to give the material self-healing properties so that it can recover under certain conditions when damaged, however, the unique exchange mechanism of dynamic polymers further limits the mechanical properties of the material.
Patent CN114195972A provides a PDMS material containing benzimidazolyl dynamic covalent bonds, a preparation method and application thereof, wherein the maximum tensile strength is about 7MPa; the tensile strength of the self-repairing repeatable processing polysiloxane elastomer prepared by the patent CN107814937A is about 3.25MPa; CN114133570A is a self-repairing polysiloxane elastomer prepared by reacting aminopropyl double-end-capped polydimethylsiloxane (NH 2-PDMS-NH 2), diisocyanate and citric acid chloride converted from citric acid, wherein the tensile strength is 408.2kPa; the tensile strength of a self-repairing polysiloxane elastomer prepared by CN111393651A is 2.8MPa.
It can be seen that the mechanical strength of the self-repairing PDMS material in the prior art is generally lower than 7MPa, and therefore, the mechanical strength needs to be improved while the self-repairing performance is maintained from the perspective of molecular structure design. Patent CN109265636a discloses a novel high-performance reversible covalent crosslinked polymer based on an amido urea bond and a preparation method thereof, and high mechanical strength is obtained by introducing an amido urea group into a polymer matrix. However, because the polarity difference between the amido urea group and the PDMS is too large, it is difficult to find a good solvent which is common to the hydrazide and the PDMS to allow the hydrazide and the PDMS to react sufficiently, so that the PDMS with ideal mechanical properties and a self-repairing function is obtained. Therefore, the amido urea end group structure is reasonably designed, so that the amido urea end group structure can be well dissolved in a certain solvent to fully react with PDMS, and the preparation of the self-repairing PDMS material with the ultrahigh strength is very important for the development of high-performance self-repairing PDMS in the future.
Disclosure of Invention
Aiming at the technical problem that a good solvent common to hydrazide and PDMS is difficult to find, a specific set of hydrazide and PDMS combination is explored by reasonably designing a reactant structure, and can be dissolved in the specific solvent together for full reaction;
further, aiming at the technical problem that the ultrahigh-strength self-repairing PDMS material does not exist in the prior art, the invention reasonably designs and provides the preparation method of the cross-linked polydimethylsiloxane elastomer material, the mechanical property of the self-repairing PDMS is greatly improved while the good self-repairing property is maintained, the tensile strength of the self-repairing PDMS material can reach 17.2MPa, and the elastic modulus of the PDMS material can reach 20.4MPa. The tensile strength of the material is improved by about two times compared with various self-repairing PDMS materials in published articles and patents in the world, which is an unexpected improvement range. In addition, the self-repairing efficiency of the material is 80%. The invention greatly expands the application range of PDMS.
A method of preparing a crosslinked polydimethylsiloxane elastomeric material, comprising:
dissolving a compound containing isocyanate groups and a siloxane compound in a reaction solvent, and reacting for a period of time under a heating condition to obtain a precursor;
and adding an amino chain extender into the precursor, stirring at room temperature for reaction for a period of time, placing the mixture into an oven to volatilize and remove the solvent after the solid completely reacts, and obtaining the colorless and transparent crosslinked polydimethylsiloxane elastomer material.
The cross-linked polydimethylsiloxane elastomer material prepared by the invention can be mechanically crushed or artificially cut into fine PDMS particles, and the fine PDMS particles are subjected to hot pressing, extrusion, injection molding or 3D printing to prepare a material with a specific shape and performance.
Further, the isocyanate group-containing compound is one or more of tetramethyl m-xylylene diisocyanate, 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate and hexamethylene diisocyanate trimer.
Further, the siloxane-based compound is one or more of hydroxyl-terminated siloxane materials or hydroxyl-terminated siloxane materials with different molecular weights.
Further, the different molecular weight is 1000 to 5000.
Further, the chain extender is one or more of an amino-containing compound, an aldehyde-containing compound, a disulfide-containing compound and a hydrazide-containing compound.
Further, the amino-containing compound is one or more of isophorone diamine, diacetyl m-phenylenediamine, N-dialkyl methyl diamine, diethyl toluene diamine, diacetyl ethylene diamine and dialkyl toluene diphenylamine
Further, the aldehyde group-containing compound is one or more of 5-bromoisophthalaldehyde, pyridine-2,6-dicarboxaldehyde, glutaraldehyde, succinaldehyde, o-phthalaldehyde, trialdehyde phloroglucinol, m-phthalaldehyde and terephthalaldehyde.
Further, the disulfide-containing compound is one or more of 4,4' -diaminodiphenyl disulfide, 2,2' -diaminodiphenyl disulfide and 3,3' -dithio-dipropionic acid dihydrazide.
Further, the hydrazide-containing compound is one or more of oxalyl hydrazide, adipic hydrazide and terephthaloyl hydrazide.
Further, the reaction solvent is one or more of hexane, dioxane, tetrahydrofuran, N, N-dimethylformamide and dimethyl sulfoxide.
Further, the heating condition is 60-100 ℃ for 6-12 hours.
Further, the solvent volatilization temperature is 80 ℃.
The invention also discloses a cross-linked polydimethylsiloxane elastomer material prepared by any one of the preparation methods.
Furthermore, the tensile strength of the cross-linked polydimethylsiloxane elastomer material is 12.8-18.6MPa, and the elongation at break is 160-330%.
Further, the cross-linked polydimethylsiloxane elastomer material has the reworking efficiency of 98.2 percent at the temperature of 130 ℃ for 10min according to the tensile strength.
Furthermore, the self-repairing efficiency of the cross-linked polydimethylsiloxane elastomer material reaches 80.2 percent after the self-repairing is carried out for 3 hours at 140 ℃ in terms of toughness.
The invention has the beneficial effects that:
1) According to the invention, different diisocyanates react with the hydroxypropyl-terminated polydimethylsiloxane with different molecular weights under the heating condition to generate prepolymers, and then stoichiometric chain extenders are added for further reaction, so that the produced groups not only can endow the material with self-repairing performance, but also can form multiple hydrogen bonds among molecules, thereby increasing the mechanical property of the material.
2) The cross-linked polydimethylsiloxane elastomer material prepared by the invention overcomes the problem that the polarity difference between siloxane serving as a soft segment and amide urea of a hard segment is too large and cannot be fully reacted, and the compatibility between the hard segment and the soft segment is good by adjusting the side group, so that the siloxane soft segment can be well inserted into the hard segment.
3) The invention does not need to use a catalyst, the used materials can be purchased conveniently, the synthesis process is simple, and the industrial production is expected to be realized.
4) The cross-linked polydimethylsiloxane elastomer material prepared by the invention has excellent mechanical properties, multiple hydrogen bonds can be formed in the hard section of the material, the mechanical properties of the material are enhanced, the tensile strength is 12.8-18.6MPa, the elongation at break is 160-330%, and the elastic modulus is 20.4-64.5MPa.
5) The cross-linked polydimethylsiloxane elastomer material prepared by the invention has high mechanical property and good self-repairing property, and the repairing efficiency reaches 80.2% after the self-repairing is carried out for 3 hours at 140 ℃.
6) The cross-linked polydimethylsiloxane elastomer material prepared by the invention realizes the combination of excellent mechanical property and self-repairing capability, can bear larger load, greatly broadens the application range of the material, and has huge application potential in the emerging intelligent field.
Drawings
FIG. 1 is a schematic diagram of the reaction of example 1 (TM-A-C15 for short) and comparative example 1 (IP-A-C15 for short) and comparative example 2 (HM-A-C15 for short);
FIG. 2 is a schematic diagram of the self-repairing of embodiment 1 (TM-A-C15);
FIG. 3 is an IR spectrum of example 1 (TM-A-C15 for short);
FIG. 4 is a stress-strain curve of a sample of example 1 (TM-A-C15 for short);
FIG. 5 is a stress-strain curve of example 1 (TM-A-C15 for short) after self-repairing at different temperatures;
FIG. 6 is a photograph of example 1 (TM-A-C15 for short) taken before and after self-repairing at 130 ℃;
FIG. 7 is a stress-strain-curve for the reworked and self-repaired splines of comparative example 1 (IP-A-C15 for short);
FIG. 8 is a stress-strain-curve for the reworked and self-repaired splines of comparative example 2 (HM-A-C15 for short).
Detailed Description
The specific technical scheme of the invention is described by combining the embodiment.
Example 1
A preparation method of a cross-linked polydimethylsiloxane elastomer material comprises the following preparation steps:
preparing a precursor: the precursor is prepared by dissolving tetramethyl m-xylylene diisocyanate (TMXDI, 2.125g,8.7 mmol) and crosslinking agent hexamethylene diisocyanate trimer (tri-HDI) (0.436 g, 0.87mmol) in 20ml of dimethyl acetamide, stirring to dissolve and disperse fully, adding corresponding hydroxypropyl terminated polysiloxane according to the molar ratio of isocyanate to hydroxyl 2:1, placing in an oil bath at 80 ℃, and stirring for 8 h.
Preparation of polydimethylsiloxane elastomer (TM-A-C15 for short): adding stoichiometric adipic dihydrazide (0.871g, 5 mmol) into the reacted precursor, stirring at normal temperature for 30min, placing the product in an oven at 80 ℃ to volatilize the solvent when the adipic dihydrazide solid disappears, and obtaining the transparent film after 12-24 h.
The self-repairing polysiloxane elastomer (TM-A-C15 for short) with excellent mechanical properties prepared by the embodiment has the tensile strength of 17.2MPa, the elongation at break of 264.64 percent, the elastic modulus of 20.3MPa and the self-repairing efficiency of self-repairing for 3 hours at 140 ℃ of 80 percent in terms of toughness.
Comparative example 1
Preparing a precursor: the precursor is prepared by dissolving isophorone diisocyanate (IPDI, 1.934g, 8.7mmol) and crosslinking agent hexamethylene diisocyanate trimer (tri-HDI) (0.436 g, 0.87mmol) in 20ml dimethyl acetamide, stirring to dissolve and disperse fully, adding corresponding hydroxypropyl terminated polysiloxane according to the molar ratio of isocyanate to hydroxyl 2:1, placing in an oil bath kettle at 80 ℃, and stirring for 8 h.
Preparation of polydimethylsiloxane Elastomers (abbreviated to IP-A-C15): and adding stoichiometric adipic dihydrazide (0.871g, 5 mmol) into the reacted precursor, stirring at normal temperature for 30min, placing the product into an oven at 80 ℃ to volatilize the solvent when the adipic dihydrazide solid disappears, and obtaining the transparent film after 12-24 h.
The polysiloxane elastomer (IP-A-C15 for short) prepared by the comparative example has higher mechanical strength, the tensile strength is 16.27MPa, the elongation at break is 139.66%, and the elastic modulus is 79.88MPa, but the self-repairing capability of the polysiloxane elastomer is sacrificed, and under the action of applied mechanical force, the repairing efficiency can reach 96% by a tensile strength meter under the conditions of processing at 140 ℃ and 15MPa for 1 hour.
Comparative example 2
Preparing a precursor: the precursor is prepared by dissolving 4,4' -dicyclohexylmethane diisocyanate (HMDI, 2.282g,8.7 mmol) and crosslinking agent hexamethylene diisocyanate trimer (tri-HDI) (0.436 g, 0.87mmol) in 20ml of dimethyl acetamide, stirring to fully dissolve and disperse the diisocyanate and the hexamethylene diisocyanate trimer, adding corresponding hydroxypropyl terminated polysiloxane according to the molar ratio of isocyanate to hydroxyl of 2:1, placing the mixture in an oil bath at 80 ℃, and stirring for reacting for 8 hours to form the precursor.
Preparation of polydimethylsiloxane Elastomers (abbreviated HM-A-C15): and adding stoichiometric adipic dihydrazide (0.871g, 5 mmol) into the reacted precursor, stirring at normal temperature for 30min, placing the product into an oven at 80 ℃ to volatilize the solvent when the adipic dihydrazide solid disappears, and obtaining the transparent film after 12-24 h.
The silicone elastomer (abbreviated as HM-A-C15) obtained in this comparative example had the best mechanical properties, and had a tensile strength of 18.21MPa, an elongation at break of 87.9%, and an elastic modulus of 32.59MPa, but was difficult to repair.
FIG. 1 is a schematic diagram showing the reaction principle of example 1 and comparative examples 1 and 2. The preparation method comprises the steps of reacting an isocyanate group-containing reactant with hydroxypropyl-terminated polysiloxane to form a precursor, and adding a chain extender ADH to form the polydimethylsiloxane elastomer material with high mechanical strength.
Fig. 2 is a self-repairing mechanism diagram of example 1, in which the amido urea group inside the material is dynamically dissociated and recombined at high temperature to generate isocyanate and hydrazide, and the amido urea group is formed again after cooling.
FIG. 3 is an IR spectrum of 2250cm from example 1 -1 There is no peak indicating that the NCO group has reacted to completion.
Fig. 4 is a stress-strain curve of example 1, from which the mechanical properties of example 1 can be understood: the tensile strength is 17.2MPa, the elongation at break is 264.64 percent, and the elastic modulus is 20.3MPa.
FIG. 5 is a stress-strain curve of the self-repaired strain of example 1 at different temperatures, and it can be seen that the self-repairing efficiency of TM-A-C15 at 140 ℃ for 3h is 80%.
FIG. 6 is a photograph of example 1 before and after self-healing, showing that the gap is completely repaired.
Fig. 7 shows stress strain-curves of the reworked and self-repaired specimens of comparative example 1 (IP-a-C15 for short), and it can be seen that the material synthesized from IPDI has a higher elastic modulus but a low self-repair efficiency, and only the reworking experiment can be performed.
Fig. 8 is a stress strain-curve of the reworked and self-repaired splines of comparative example 2 (HM-a-C15 for short), showing that the HPDI synthesized material has higher tensile strength but low self-repair efficiency and rework efficiency.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method of preparing a crosslinked polydimethylsiloxane elastomeric material, comprising:
dissolving a compound containing isocyanate groups and a siloxane-based compound in a reaction solvent, and reacting for a period of time under a heating condition to obtain a precursor solution;
and adding an amino chain extender into the precursor solution, stirring at room temperature until the solid completely reacts, and then putting the mixture into an oven to volatilize the solvent to obtain the cross-linked polydimethylsiloxane elastomer material.
2. The production method according to claim 1, wherein:
the isocyanate group-containing compound is one or more of tetramethyl m-xylylene diisocyanate, 4,4' -dicyclohexyl methane diisocyanate, isophorone diisocyanate, triphenyl methane triisocyanate and hexamethylene diisocyanate trimer.
3. The production method according to claim 1, wherein:
the siloxane matrix compound is one or more of hydroxyl-terminated siloxane materials with different molecular weights or hydroxyl-terminated siloxane materials.
4. The production method according to claim 3, wherein:
the different molecular weight is 1000-5000.
5. The production method according to claim 1, wherein:
the heating conditions are as follows: heating at 60-100 deg.C for 6-12h.
6. The production method according to claim 1, wherein:
the amino chain extender is one or more of an amino-containing compound, an aldehyde-containing compound, a disulfide-containing compound and a hydrazide-containing compound.
7. The production method according to claim 6, wherein:
the amino-containing compound is one or more of isophorone diamine, diacetyl m-phenylenediamine, N-dialkyl methyl diamine, diethyl toluene diamine, diacetyl ethylene diamine and dialkyl toluene diphenylamine;
the compound containing the aldehyde group is one or more of 5-bromoisophthalaldehyde, pyridine-2,6-diformal, glutaraldehyde, succinaldehyde, o-phthalaldehyde, trialdehyde phloroglucinol, m-phthalaldehyde and terephthalaldehyde;
the disulfide-containing compound is one or more of 4,4' -diaminodiphenyl disulfide, 2,2' -diaminodiphenyl disulfide and 3,3' -dithio-dipropionic acid dihydrazide;
the hydrazide-containing compound is one or more of oxalyl hydrazide, adipamide and terephthaloyl hydrazide.
8. The production method according to claim 1, wherein:
the reaction solvent is one or more of hexane, dioxane, tetrahydrofuran, N, N-dimethyl formamide and dimethyl sulfoxide.
9. The production method according to claim 1, wherein:
the solvent volatilization temperature was 80 ℃.
10. A crosslinked polydimethylsiloxane elastomeric material prepared according to any of the preparation methods of claims 1-9.
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