CN117384350A - Functionalized elastomer and application thereof - Google Patents
Functionalized elastomer and application thereof Download PDFInfo
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- CN117384350A CN117384350A CN202311380581.1A CN202311380581A CN117384350A CN 117384350 A CN117384350 A CN 117384350A CN 202311380581 A CN202311380581 A CN 202311380581A CN 117384350 A CN117384350 A CN 117384350A
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- glycol
- healing
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 36
- 239000000806 elastomer Substances 0.000 title claims abstract description 36
- 150000002009 diols Chemical class 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 41
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 125000001931 aliphatic group Chemical group 0.000 claims description 18
- 235000011187 glycerol Nutrition 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- XBXFGOSIPGWNLZ-UHFFFAOYSA-N O=C1C=C(CC(C)(C)C1)C.N=C=O Chemical compound O=C1C=C(CC(C)(C)C1)C.N=C=O XBXFGOSIPGWNLZ-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 4
- 229960002479 isosorbide Drugs 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 229920000263 Rubber seed oil Polymers 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000000306 component Substances 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000002600 sunflower oil Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 229920003225 polyurethane elastomer Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 3
- 230000035876 healing Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229920006273 intrinsic self-healing polymer Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013005 self healing agent Substances 0.000 description 1
- 235000008113 selfheal Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
Classifications
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a functional elastomer and application thereof, and belongs to the technical field of new materials. The invention introduces a multiple dynamic network composed of rich H bonds, disulfide bonds and metal coordination bonds into an elastomer, wherein the H bonds are composed of urethane bonds and U 2 The UPy segment in diol provides that the metal coordination bond is composed of a ligand provided by dimethylglyoxime and a metal ion, and the functionalized elastomer capable of self-healing at low temperature is prepared by a one-pot method. The obtained functional elastomer has good mechanical property, can realize self-healing at the low temperature of-15 ℃, and has great application prospect in the fields of low-temperature-resistant flexible wearable and the like.
Description
Technical Field
The invention belongs to the technical field of new materials, and relates to a functional elastomer and application thereof.
Background
Self-healing is a biological tissue property that enables them to effectively self-repair after mechanical injury. Therefore, inspired by nature, the self-healing properties are introduced into the elastomer, greatly improving their lifetime and stability, reducing maintenance costs, and enabling novel applications. Therefore, the self-repairing material attracts great attention in many fields of automobile paint, electronic skin, soft robot, etc., and shows great prospect. Exogenous self-healing has limited ability to heal due to the reliance on self-healing agents, limiting their widespread use. Therefore, intrinsic self-healing materials based on dynamic non-covalent interactions or reversible covalent bonds are currently becoming an important research point. However, intrinsic type healing processes typically require external energy input, such as heat, light, pressure, or other agents. Since many materials in real life are damaged under ambient conditions without available external stimuli, it is highly desirable to develop elastomeric materials that can spontaneously self-heal at room temperature or even low temperatures.
Currently, developing elastomeric materials with low Wen Ziyu performance remains a significant challenge. Common methods for designing self-healing materials combine dynamic covalent bonds (disulfide bonds, imine bonds, etc.) with dynamic non-covalent bonds (H bonds, metal coordination bonds, ionic interactions, etc.). However, the materials obtained in this way are generally relatively weak. In contrast, a large number of non-covalent interactions may lead to better mechanical properties, but may impair the self-healing, stretchability and toughness of the material. Furthermore, due to their linear molecular structure, these materials may suffer from limited elasticity and potential creep. Thus, some researchers have chemically crosslinked structures based on dynamic covalent bonds such as urea bonds, boron oxygen bonds, and disulfide bonds to build relatively strong healable materials. However, the crosslinked network limits the movement of the chains and reduces the healing capacity. Overall, the self-healing ability and mechanical properties of the material are inherently mutually exclusive. Achieving both high mechanical robustness and healing efficiency remains a great challenge, especially under ambient conditions, as their requirements on molecular structure are often contradictory.
Disclosure of Invention
In order to solve the problems in the prior art, the invention adopts the following technical scheme:
the invention aims to provide a preparation method of a functionalized elastomer capable of self-healing at low temperature, which comprises the following steps:
(1) Obtaining hydroxyl end-capped bio-based aliphatic prepolymer by using bio-based diacid and dihydric alcohol to react;
(2) Mixing and reacting the hydroxyl-terminated bio-based aliphatic prepolymer with isocyanate, glycol components, glycerol, metal salt and ligand to obtain the functional elastomer.
In one embodiment of the invention, the functionalized elastomer capable of self-healing at low temperature is obtained by reacting glycol, glycerin, isocyanate and metal ions, and the topology structure of the functionalized elastomer contains a plurality of dynamic networks formed by rich hydrogen bonds, carbamate, disulfide bonds and metal coordination bonds, so that the elastomer has low Wen Ziyu bonding performance.
In one embodiment of the present invention, the bio-based glycol is one or a combination of propylene glycol, butylene glycol, rubber seed oil based glycol, palm oil based glycol, sunflower seed oil based glycol, isosorbide, pentylene glycol, ethylene glycol, and dimer alcohol.
In one embodiment of the invention, the bio-based diacid is one or a combination of itaconic acid, sebacic acid, succinic acid, azelaic acid, dimer fatty acid (DAA), dodecyl diacid, fumaric acid.
In one embodiment of the invention, the molar ratio of biobased diol to diacid is (1-2): 1.
in one embodiment of the present invention, the polymerization inhibitor in the step (1) is any one of 4-methoxyphenol and hydroquinone, and the addition amount is 0.05 to 0.5wt%.
In one embodiment of the present invention, the catalyst in the step (1) is tetrabutyl titanate, p-toluenesulfonic acid, antimony acetate, dibutyl tin laurate; the dosage is 0.05-0.5wt% of the total mass.
In one embodiment of the present invention, the reaction in step (1) is carried out at a temperature of 130 to 190℃for a period of 1 to 8 hours.
In one embodiment of the present invention, the hydroxyl terminated biobased aliphatic prepolymer in step (1) has a number average molecular weight of 1000 to 13000.
In one embodiment of the present invention, the glycol component in step (2) is U 2 -diol, or U 2 -combinations of diol with other glycol agents; the other glycol reagents are any one or more of bis (2-hydroxyethyl) disulfide, dimethylglyoxime, butanediol, propylene glycol and isosorbide.
In one embodiment of the present invention, the molar ratio of the total amount of the hydroxyl terminated biobased aliphatic prepolymer and glycol component to glycerin in step (2) is 2 to 8:1.
in one embodiment of the present invention, the molar ratio of the total amount of hydroxyl groups to isocyanate groups in the hydroxyl terminated biobased aliphatic prepolymer and diol component in step (2) is 1:1 to 2.
In one embodiment of the present invention, the isocyanate in step (2) is one or a combination of isophorone isocyanate, hexamethylene diisocyanate, toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), lysine Diisocyanate (LDI).
In one embodiment of the invention, the ligand in step (2) is dimethylglyoxime capable of forming a metal coordination bond with a metal ion.
In one embodiment of the invention, the molar ratio of ligand to glycerol in step (2) is (2-5): 1.
in one embodiment of the present invention, the metal salt in step (2) is one of copper chloride and zinc chloride.
In one embodiment of the invention, the molar ratio of metal salt to ligand in step (2) is 1:10 to 30 percent.
In one embodiment of the invention, the reaction in the step (2) is carried out by stirring at 50-80 ℃ for 1-6h, then 40-60 reacting for 12-24h under nitrogen environment, and then heating to 70-90 ℃ for continuing the reaction for 12-36 h.
In one embodiment of the present invention, the method for preparing an elastomer specifically includes:
(1) Preparing hydroxyl end capped biological aliphatic prepolymer: adding bio-based dibasic acid, dihydric alcohol, polymerization inhibitor and catalyst into a reactor, reacting at 130-190 ℃ for 1-8 h, changing an esterification system into a vacuumizing system, and reacting for 2-8 h to obtain hydroxyl end-capped bio-based aliphatic prepolymer;
(2) Vacuum dewatering the prepolymer at 90-120 deg.c for 1-3 hr, adding isocyanate, bis (2-hydroxyethyl) disulfide and U into the prepolymer at 50-80 deg.c 2 Stirring the diol, the glycerol and the metal ions for 1-6 hours, pouring the reactants into a die, putting the die into an environment with nitrogen to react for 12-24 hours at 40-60 ℃, and then reacting for 12-36 hours at 70-90 ℃.
The invention provides a low-temperature self-healing functionalized elastomer based on the preparation method.
The invention also provides application of the low-temperature self-healing functionalized elastomer in the field of self-powered friction generators and wearable equipment.
The invention also provides application of the low-temperature self-healing functionalized elastomer in the fields of automobile paint, electronic skin and soft robots.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a bio-based crosslinked elastomer containing multiple dynamic networks and a preparation method thereof, which are prepared by a one-pot method. It is characterized by that a multiple dynamic network formed from rich H bond, disulfide bond and metal coordination bond is introduced into the elastomer, in which the H bond is formed from urethane bond and U 2 The UPy section in diol provides, and the metal coordination bond is formed by a ligand provided by dimethylglyoxime and metal ions, so that a strong and weak cross-linked network is formed, and good mechanical properties are further provided for the elastomer; in addition, the bio-based prepolymer as a soft segment imparts sufficient flexibility to the elastomer and a lower glass transition temperature.
Compared with the prior reported self-healing elastomer, the low-temperature self-healing bio-based crosslinked elastomer provided by the invention has the advantages that due to abundant hydrogen bonds, metal coordination bonds and low bond energy disulfide bonds, the self-healing can be realized at the low temperature of minus 15 ℃ by matching with lower glass transition temperature. Has great application prospect in the fields of low temperature resistance, flexibility, wearing and the like.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Example 1
(1) Into a 100ml three-necked flask, 7.8 g (0.060 mol) of itaconic acid, 8.09 g (0.040 mol) of sebacic acid, 4.18 g (0.055 mol) of 1, 3-propanediol, 4.95 g (0.055 mol) of 1, 4-butanediol and 0.05wt% of 4-methoxyphenol and 0.05wt% of tetrabutyl titanate were charged, water produced by the reaction was collected using a water separator and a condenser, the amount of nitrogen gas was set to 0.15L/min, the rotational speed at magnetic stirring was set to 380r/min, the reaction temperature was 180℃and the reaction time was 2h; then changing the reaction system into a vacuum pumping system to continue the reaction for 5 hours to obtain the light yellow hydroxyl end capped bio-based unsaturated aliphatic prepolymer, wherein the number average molecular weight is 3680g/mol.
(2) The molar ratio of the total amount of diol components and prepolymer to glycerin is 8:1 to a three-necked flask of 100ml at 50℃were charged 10mmol of prepolymer, 10mmol of dimethylglyoxime, 3mmol of bis (2-hydroxyethyl) disulfide, 1mmol of U 2 Diol, 3mmol of glycerol, in a molar ratio of total hydroxyl groups to isocyanate groups of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
Example 2
(1) The corresponding pale yellow hydroxyl-terminated biobased unsaturated aliphatic prepolymer was prepared as in example 1.
(2) To 50 ℃ and 100mlInto a three-necked flask, 10mmol of prepolymer, 10mmol of dimethylglyoxime, 2mmol of bis (2-hydroxyethyl) disulfide and 2mmol of U were added 2 Diol, 3mmol glycerol, in a molar ratio of total hydroxyl groups to isocyanate of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
Example 3
(1) The corresponding pale yellow hydroxyl-terminated biobased unsaturated aliphatic prepolymer was prepared as in example 1.
(2) Into a 100ml three-necked flask at 50℃were added 10mmol of prepolymer, 10mmol of dimethylglyoxime, 1mmol of bis (2-hydroxyethyl) disulfide and 3 mmole U 2 Diol, 3mmol glycerol, in a molar ratio of total hydroxyl groups to isocyanate of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
Example 4
(1) The corresponding pale yellow hydroxyl-terminated biobased unsaturated aliphatic prepolymer was prepared as in example 1.
(2) 10mmol of prepolymer, 10mmol of dimethylglyoxime and 4mmol of U were put into a 100ml three-necked flask at 50℃ 2 Diol, 3mmol glycerol, in a molar ratio of total hydroxyl groups to isocyanate of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
Comparative example 1
No U in the diol component 2 -diol, and no sulphur component:
(1) The corresponding pale yellow hydroxyl-terminated biobased unsaturated aliphatic prepolymer was prepared as in example 1.
(2) To a 100ml three-necked flask at 50℃were added 10mmol of prepolymer, 14mmol of dimethylglyoxime and 3mmol of glycerol in a molar ratio of the total amount of hydroxyl groups to isocyanate of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
Comparative example 2
Sulfur-containing components, but no U, in glycol components 2 -diol:
(1) The corresponding pale yellow hydroxyl-terminated biobased aliphatic prepolymer was produced as in example 1.
(2) To a 100ml three-necked flask at 50℃were added 10mmol of prepolymer, 10mmol of dimethylglyoxime, 4mmol of bis (2-hydroxyethyl) disulfide and 3mmol of glycerol in a molar ratio of the total amount of hydroxyl groups to isocyanate of 1:1, 28.5mmol of isophorone isocyanate, 3 drops of dibutyl tin laurate, 0.32mmol of copper chloride and 40ml of acetone are added in proportion, stirred and reacted for 2 hours, poured into a mould, dried for 24 hours at 50 ℃, then heated to 75 ℃, dried for 24 hours, and the drying process is carried out under nitrogen atmosphere, so as to obtain the cross-linked polyurethane elastomer with low Wen Ziyu synthetic property.
The properties of the elastomers obtained in examples 1 to 4 and comparative examples 1 to 2 were measured, and the results are shown in Table 1.
TABLE 1 Performance test results
As can be seen from Table 1, the low Wen Ziyu biobased crosslinked elastomers of the present invention, due to the abundance of hydrogen bonds, metal coordination bonds, and low bond energy disulfide bonds, combine with lower glass transition temperatures to achieve self-healing at low temperatures of-10 to-15 ℃. In comparative example 2, however, U was not added 2 The diol case can only achieve self-healing at 30 c,temperatures below 30 ℃ are not effective for self-healing. In addition, disulfide bonds are bonds having a relatively low bond energy which, when incorporated into an elastomer, impart self-healing properties but reduce the strength of the elastomer. Along with U 2 An increase in diol content, a gradual increase in the tensile strength of the elastomer and a gradual decrease in the elongation at break.
Example 5
Referring to example 2, the preparation temperature of the hydroxyl terminated biobased unsaturated aliphatic prepolymer was varied, and the other was unchanged, to prepare a corresponding elastomer film. The results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the low Wen Ziyu biobased crosslinked elastomer of the present invention has a gradually increasing molecular weight as the prepolymer preparation temperature increases, and thus the mechanical properties of the resulting low Wen Ziyu biobased crosslinked elastomer gradually increase, because the chain entanglement effect between crosslinking points is enhanced with the crosslinking density unchanged, resulting in an improved mechanical properties.
Example 6
Comparative optimization in different glycol components:
referring to example 2, U was changed 2 -diol is replaced by other diols, the others being unchanged, to produce the corresponding crosslinked polyurethane elastomer.
The properties of the resulting crosslinked polyurethane elastomer were measured, and the results are shown in Table 3.
TABLE 3 Table 3
The above examples are not intended to limit the scope of the invention nor the order of execution of the steps described. The present invention is obviously modified by a person skilled in the art in combination with the prior common general knowledge, and falls within the scope of protection defined by the claims of the present invention.
Claims (10)
1. The preparation method of the functionalized elastomer capable of self-healing at low temperature is characterized by comprising the following steps of:
(1) Obtaining hydroxyl end-capped bio-based aliphatic prepolymer by using bio-based diacid and dihydric alcohol to react;
(2) Mixing and reacting the hydroxyl-terminated bio-based aliphatic prepolymer with isocyanate, glycol components, glycerol, metal salt and ligand to obtain the functional elastomer.
2. The method of claim 1, wherein the bio-based glycol is one or a combination of propylene glycol, butylene glycol, rubber seed oil based glycol, palm oil based glycol, sunflower oil based glycol, isosorbide, pentylene glycol, ethylene glycol, dimer alcohol; the bio-based dibasic acid is one or a combination of itaconic acid, sebacic acid, succinic acid, azelaic acid, dimer fatty acid, dodecyl dibasic acid and fumaric acid; the mol ratio of the bio-based dihydric alcohol to the dibasic acid is (1-2): 1.
3. the method according to claim 1, wherein the polymerization inhibitor in the step (1) is any one of 4-methoxyphenol and hydroquinone, and the addition amount is 0.05 to 0.5wt%; the catalyst is tetrabutyl titanate, p-toluenesulfonic acid, antimony acetate and dibutyl tin laurate; the dosage is 0.05-0.5wt% of the total mass.
4. The process of claim 1 wherein the glycol component of step (2) is U 2 -diol, or U 2 -combinations of diol with other glycol agents; the other glycol reagents are any one or more of bis (2-hydroxyethyl) disulfide, dimethylglyoxime, butanediol, propylene glycol and isosorbide.
5. The method of claim 1, wherein the molar ratio of the total amount of hydroxyl terminated biobased aliphatic prepolymer and glycol component to glycerin in step (2) is from 2 to 8:1.
6. the method of claim 1, wherein the molar ratio of total hydroxyl groups to isocyanate groups in the hydroxyl terminated biobased aliphatic prepolymer and diol component of step (2) is 1:1 to 2; the isocyanate is one or a combination of isophorone isocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and lysine diisocyanate.
7. The method according to any one of claims 1 to 6, wherein the metal salt in step (2) is selected from one of copper chloride and zinc chloride; the molar ratio of the metal salt to the ligand is 1:10 to 30 percent; the molar ratio of the ligand to glycerol is (2-5): 1.
8. a functionalized elastomer capable of low temperature self-healing prepared by the method of any one of claims 1-7.
9. Use of the low temperature self-healing functionalized elastomer of claim 8 in the field of self-powered triboelectric generators, wearable devices.
10. Use of the low temperature self-healing functionalized elastomer according to claim 8 in the fields of automotive coatings, electronic skin and soft robotics.
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