CN115873256B - Crosslinked polydimethylsiloxane elastomer material and preparation method thereof - Google Patents
Crosslinked polydimethylsiloxane elastomer material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000004205 dimethyl polysiloxane Substances 0.000 title claims abstract description 53
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 title claims abstract description 53
- -1 polydimethylsiloxane Polymers 0.000 title claims abstract description 43
- 229920001971 elastomer Polymers 0.000 title claims abstract description 31
- 239000000806 elastomer Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 13
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 239000013638 trimer Substances 0.000 claims description 5
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000013536 elastomeric material Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004970 Chain extender Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- 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
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 description 1
- QAQOLRCTTDVBAK-UHFFFAOYSA-N 5-bromobenzene-1,3-dicarbaldehyde Chemical compound BrC1=CC(C=O)=CC(C=O)=C1 QAQOLRCTTDVBAK-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- MOAAMPQMKNSCEL-UHFFFAOYSA-N N-phenylaniline toluene Chemical compound C1(=CC=CC=C1)NC1=CC=CC=C1.C1(=CC=CC=C1)C MOAAMPQMKNSCEL-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 125000002228 disulfide group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
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- WNYIBZHOMJZDKN-UHFFFAOYSA-N n-(2-acetamidoethyl)acetamide Chemical compound CC(=O)NCCNC(C)=O WNYIBZHOMJZDKN-UHFFFAOYSA-N 0.000 description 1
- UQVKNKXDSWRQJE-UHFFFAOYSA-N n-(3-acetamidophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(NC(C)=O)=C1 UQVKNKXDSWRQJE-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
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- PMWXGSWIOOVHEQ-UHFFFAOYSA-N pyridine-2,6-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=N1 PMWXGSWIOOVHEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a crosslinked polydimethylsiloxane elastomer material and a preparation method thereof, wherein an isocyanate group-containing compound and a siloxane base compound are dissolved in a solvent and react for a period of time under a heating condition to obtain a precursor solution, an amino chain extender is added into the precursor solution, the mixture is stirred at room temperature until the solid reaction is complete, and then the mixture is placed in an oven to volatilize the solvent, so that the crosslinked polydimethylsiloxane elastomer material is obtained. The crosslinked polydimethylsiloxane elastomer material prepared by the invention has excellent mechanical properties, the hard segment of the crosslinked polydimethylsiloxane elastomer material can form multiple hydrogen bonds, the mechanical properties of the material are enhanced, meanwhile, the crosslinked polydimethylsiloxane elastomer material has good self-repairing property, can bear larger load, greatly widens the application range of the material, and has huge application potential in the emerging intelligent field. The raw materials are simple, the method can be used for mass production and development, and can be used for recovery treatment, thereby being hopeful to become a product with high economic added value.
Description
Technical Field
The invention belongs to the field of preparation of high polymer materials, and particularly relates to a crosslinked polydimethylsiloxane elastomer material and a preparation method thereof.
Background
In recent years, with the development of the field of intelligent electronics, flexible electronic devices have become a popular choice for research in the world today. The flexible electronic technology is mainly based on flexible materials, and is a subverted scientific technology formed by high cross fusion with 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 making flexible electronic devices, and the development of the elastomer materials plays a key role. Polydimethylsiloxane (PDMS) is widely used as one of main base materials of elastomer materials in the fields of electronic skin, flexible wearable electronic devices, soft robots, optical devices, etc., due to its excellent elasticity, excellent hydrophobicity, good weatherability, excellent biocompatibility, etc. However, because of the low chemical bond strength of PDMS, the mechanical properties are poor, generally lower than 7MPa, and the low mechanical strength leads to easy damage when bearing external stress, so that the PDMS loses the original properties and purposes. In response to the above problems, dynamic bonds are typically introduced into PDMS to impart self-healing properties to the material so that it can be recovered under specific conditions when damage occurs, however the unique exchange mechanism of dynamic polymers further limits the mechanical properties of the material.
Patent CN114195972a provides a PDMS material containing dynamic covalent bond of benzimidazolyl, and preparation method and application thereof, the tensile strength of which is about 7MPa at maximum; the self-repairing and repeatedly-processed polysiloxane elastomer prepared by the patent CN107814937A has the tensile strength of about 3.25MPa; the patent CN114133570A is a self-repairing polysiloxane elastomer prepared by taking aminopropyl double-end-capped polydimethylsiloxane (NH 2-PDMS-NH 2), diisocyanate and citric acid chloride converted from citric acid as raw materials to react, and the tensile strength is 408.2kPa; the self-repairing polysiloxane elastomer prepared by the patent CN111393651A has the tensile strength of 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, so that the mechanical strength is required to be improved while the self-repairing performance is maintained from the aspect of molecular structure design. Patent CN109265636a discloses a novel high-performance reversible covalent cross-linked polymer based on amido urea bonds and a preparation method thereof, which achieves high mechanical strength by introducing amido urea groups into a polymer matrix. However, as the polarity difference between the amidourea group and the PDMS is too large, it is difficult to find a good solvent common to the hydrazide and the PDMS to make them fully react, so as to obtain the PDMS with ideal mechanical properties and self-repairing function. Therefore, by reasonably designing the terminal structure of the amido urea, the amido urea can be well dissolved in a certain solvent for full reaction with PDMS, and the preparation of the self-repairing PDMS material with ultra-high strength is important for the development of the self-repairable PDMS with high performance in the future.
Disclosure of Invention
Aiming at the technical problem that good solvents common to the hydrazide and the PDMS are difficult to find, a specific set of hydrazide and PDMS combination is explored through reasonable design of the reactant structure, and the specific set of hydrazide and the PDMS combination can be dissolved in a specific solvent together for full reaction;
further, aiming at the technical problem that the self-repairing PDMS material with ultra-high strength does not exist in the prior art, the invention is reasonably designed and provides the preparation method of the crosslinked polydimethylsiloxane elastomer material, so that 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 can reach 17.2MPa, and the elastic modulus of the self-repairing PDMS can reach 20.4MPa. The tensile strength of the material is improved by about two times compared with various self-repairing PDMS materials in articles and patents published in the world, and the tensile strength is unexpectedly improved. 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-based compound in a reaction solvent, and reacting for a period of time under the heating condition to obtain a precursor;
adding an amino chain extender into the precursor, stirring at room temperature for reacting for a period of time, placing the solid in an oven for volatilizing and removing the solvent after the solid is completely reacted, and obtaining the colorless and transparent crosslinked polydimethylsiloxane elastomer material.
The crosslinked polydimethylsiloxane elastomer material prepared by the invention can be mechanically crushed or manually cut into fine PDMS particles, and the fine PDMS particles are subjected to hot pressing, extrusion, injection molding or 3D printing to prepare the material with specific shape and performance.
Further, the compound containing isocyanate groups is one or more of tetramethyl-m-xylylene diisocyanate, 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 weights are 1000-5000.
Further, the chain extender is one or more of amino-containing compounds, aldehyde group-containing compounds, disulfide group-containing compounds and hydrazide-containing compounds.
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, phthalaldehyde, trialdehyde phloroglucinol, isophthalaldehyde and terephthalaldehyde.
Further, the disulfide-containing compound is one or more of 4,4' -diaminodiphenyl disulfide, 2' -diaminodiphenyl disulfide and 3,3' -dithiodipropionic dihydrazide.
Further, the hydrazide-containing compound is one or more of oxalyl dihydrazide, adipoyl dihydrazide and terephthaloyl dihydrazide.
Further, the reaction solvent is one or more of hexane, dioxane, tetrahydrofuran, N, N-dimethylformamide and dimethyl sulfoxide.
Further, the heating condition is that the heating is carried out for 6-12 hours at 60-100 ℃.
Further, the solvent volatilization temperature was 80 ℃.
The invention also discloses a crosslinked polydimethylsiloxane elastomer material prepared by adopting any one of the preparation methods.
Further, the crosslinked polydimethylsiloxane elastomer material has a tensile strength of 12.8 to 18.6MPa and an elongation at break of 160 to 330%.
Further, the crosslinked polydimethylsiloxane elastomeric material had a rework efficiency of 98.2% at 130℃for 10min, based on tensile strength.
Further, the repairing efficiency of the crosslinked polydimethylsiloxane elastomer material reaches 80.2% after self-repairing for 3 hours at 140 ℃ in terms of toughness.
The invention has the beneficial effects that:
1) According to the invention, a plurality of different diisocyanates are reacted with the polydimethyl siloxane with different molecular weight and end hydroxypropyl groups under the heating condition to generate a prepolymer, and then a stoichiometric chain extender is added for further reaction, so that the produced group not only can endow the material with self-repairing performance, but also can form multiple hydrogen bonds among molecules, and the mechanical property of the material is increased.
2) The cross-linked polydimethylsiloxane elastomer material prepared by the invention overcomes the problem that the polarity difference between the siloxane serving as a soft segment and the hard segment amidourea is too large to fully react, and the compatibility between the hard segment and the soft segment is good by adjusting the side group, so that the soft segment of the siloxane can be well inserted into the hard segment.
3) The invention does not need to use a catalyst, all materials can be purchased conveniently, the synthesis process is simple, and the invention is expected to realize industrial production.
4) The cross-linked polydimethylsiloxane elastomer material prepared by the invention has excellent mechanical properties, the hard segment of the cross-linked polydimethylsiloxane elastomer material can form multiple hydrogen bonds, 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 crosslinked polydimethylsiloxane elastomer material prepared by the invention has high mechanical property and good self-repairing property, and the repairing efficiency reaches 80.2% after self-repairing 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 widens the application range of the material, and has huge application potential in the emerging intelligent field.
Drawings
FIG.1isaschematicdiagramshowingthereactionofexample1(TM-A-C15)andcomparativeexample1(IP-A-C15)andcomparativeexample2(HM-A-C15);
FIG.2isaself-repairingandrestoringmapofexample1(TM-A-C15forshort);
FIG.3isaninfraredspectrumofexample1(TM-A-C15forshort);
FIG.4isastress-straincurveofthesamplebarofexample1(TM-A-C15forshort);
FIG.5isastress-straincurveafterself-healingatvarioustemperaturesforexample1(TM-A-C15forshort);
FIG.6isaphotographofexample1(TM-A-C15)beforeandafterself-healingat130℃;
FIG. 7 is a stress-strain curve of the reprocessed and self-repaired spline of comparative example 1 (abbreviated as IP-A-C15);
FIG.8isastressstrain-curveofthere-processedandself-repairedsplinesofcomparativeexample2(HM-A-C15forshort).
Detailed Description
The specific technical scheme of the invention is described by combining the embodiments.
Example 1
A method for preparing a crosslinked polydimethylsiloxane elastomer material, comprising the steps of:
preparing a precursor: the precursor is prepared by dissolving tetramethyl-m-xylylene diisocyanate (TMXDI, 2.125g,8.7 mmol) and hexamethylene diisocyanate trimer (tri-HDI) (0.433 g,0.87 mmol) as cross-linking agent in 20ml of dimethylacetamide, stirring to fully dissolve and disperse, adding corresponding hydroxypropyl-blocked polysiloxane according to the molar ratio of isocyanate to hydroxyl of 2:1, placing the mixture in an oil bath pot at 80 ℃, and stirring and reacting for 8 hours.
preparationofpolydimethylsiloxaneelastomer(TM-A-C15forshort): stoichiometric adipic dihydrazide (0.871 g,5 mmol) is added into the precursor after the reaction, stirring is carried out for 30min at normal temperature, when adipic dihydrazide solid disappears, the product is placed into an oven at 80 ℃ to volatilize the solvent, and after 12-24 hours, the transparent film is obtained.
theself-repairingpolysiloxaneelastomer(TM-A-C15forshort)withexcellentmechanicalpropertiespreparedintheexamplehastensilestrengthof17.2MPa,elongationatbreakof264.64%,elasticmodulusof20.3MPaandself-repairingefficiencyof80%at140℃for3hintermsoftoughness.
Comparative example 1
Preparing a precursor: the precursor is prepared by dissolving isophorone diisocyanate (IPDI, 1.934g,8.7 mmol) and hexamethylene diisocyanate trimer (tri-HDI) (0.433 g,0.87 mmol) as a crosslinking agent in 20ml of dimethylacetamide, stirring to fully dissolve and disperse the components, adding corresponding hydroxypropyl-terminated polysiloxane according to the molar ratio of isocyanate to hydroxyl of 2:1, placing the components in an oil bath at 80 ℃, and stirring and reacting for 8 hours.
Preparation of polydimethylsiloxane elastomer (abbreviated as IP-a-C15): stoichiometric adipic dihydrazide (0.871 g,5 mmol) is added into the precursor after the reaction, stirring is carried out for 30min at normal temperature, when adipic dihydrazide solid disappears, the product is placed into an oven at 80 ℃ to volatilize the solvent, and after 12-24 hours, the transparent film is obtained.
The polysiloxane elastomer (IP-A-C15 for short) prepared in the comparative example has higher mechanical strength, the tensile strength is 16.27MPa, the elongation at break is 139.66 percent, the elastic modulus is 79.88MPa, the self-repairing capability is sacrificed, and the repairing efficiency can reach 96 percent based on the tensile strength under the condition of 140 ℃ and 15MPa and 1 hour of processing under the action of mechanical force.
Comparative example 2
Preparing a precursor: the precursor is prepared by dissolving 4,4' -dicyclohexylmethane diisocyanate (HMDI, 2.282g,8.7 mmol) and hexamethylene diisocyanate trimer (tri-HDI) (0.433 g,0.87 mmol) as a crosslinking agent in 20ml of dimethylacetamide, stirring to fully dissolve and disperse the materials, adding corresponding hydroxypropyl-terminated polysiloxane according to the molar ratio of isocyanate to hydroxyl of 2:1, placing the materials in an oil bath pot at 80 ℃, and stirring and reacting the materials for 8 hours.
preparationofpolydimethylsiloxaneelastomer(HM-A-C15forshort): stoichiometric adipic dihydrazide (0.871 g,5 mmol) is added into the precursor after the reaction, stirring is carried out for 30min at normal temperature, when adipic dihydrazide solid disappears, the product is placed into an oven at 80 ℃ to volatilize the solvent, and after 12-24 hours, the transparent film is obtained.
thepolysiloxaneelastomer(HM-A-C15forshort)preparedinthiscomparativeexamplehadthebestmechanicalproperties,andhadatensilestrengthof18.21MPa,anelongationatbreakof87.9%andanelasticmodulusof32.59MPa,butwasdifficulttorepair.
FIG. 1 is a schematic illustration of the reaction principle of example 1 and comparative examples 1 and 2. Comprises the steps of firstly reacting reactants containing isocyanate groups with hydroxypropyl-terminated polysiloxane to form a precursor, and then adding a chain extender ADH to form the polydimethylsiloxane elastomer material with high mechanical strength.
FIG. 2 is a graph of the self-healing mechanism of example 1, wherein the amide urea groups in the material undergo dynamic dissociation and recombination at high temperature to form isocyanate and hydrazide, which upon cooling, reform the amide urea groups.
FIG. 3 is an infrared spectrum of example 1, 2250cm in the figure -1 There is no peak indicating that the NCO groups have reacted completely.
Fig. 4 is a stress-strain curve of example 1, from which the mechanical properties of example 1 can be understood: the tensile strength was 17.2MPa, the elongation at break was 264.64% and the elastic modulus was 20.3MPa.
FIG.5isagraphofstress-straincurvesofexample1afterself-healingatvarioustemperatures,showingthattheself-healingefficiencyofTM-A-C15at140℃for3his80%.
Fig. 6 is a photograph of example 1 before and after self-healing, and it can be seen that the notch is completely repaired.
FIG. 7 is a stress strain-curve of the reprocessed and self-repaired spline of comparative example 1 (abbreviated as IP-A-C15), and it can be seen that the material synthesized from IPDI has a higher elastic modulus, but the self-repair efficiency is low and only the reprocessing experiment can be performed.
FIG.8isastress-straincurveofthereprocessedandself-repairedsplinesofcomparativeexample2(HM-A-C15forshort),whichshowsthattheHPDIcompositematerialhashighertensilestrengthbutlowself-repairandre-workefficiencies.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (1)
1. A crosslinked polydimethylsiloxane elastomer material having a tensile strength of 17.2MPa, an elongation at break of 264.64%, an elastic modulus of 20.3MPa, and a self-healing efficiency of 80% in terms of toughness at 140 ℃ for 3 hours; wherein:
the material is prepared by the following steps:
(1) Preparing a precursor: dissolving 2.125g,8.7mmol of tetramethyl-m-xylylene diisocyanate and 0.436g,0.87mmol of crosslinking agent hexamethylene diisocyanate trimer in 20ml of dimethylacetamide, stirring to fully dissolve and disperse the components, adding corresponding hydroxypropyl-terminated polysiloxane according to the molar ratio of isocyanate to hydroxyl of 2:1, placing the components in an oil bath kettle at 80 ℃, stirring and reacting for 8 hours to form a precursor;
(2) Preparation of a crosslinked polydimethylsiloxane elastomeric material: 0.871g and 5mmol adipic dihydrazide are added into the precursor, stirring is carried out for 30min at normal temperature, when adipic dihydrazide solid disappears, the product is placed into an oven at 80 ℃ to volatilize the solvent, and after 12-24 hours, the crosslinked polydimethylsiloxane elastomer material is obtained.
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