CN115197393A - Preparation method of self-repairing material with synergistic effect of multiple mechanisms - Google Patents
Preparation method of self-repairing material with synergistic effect of multiple mechanisms Download PDFInfo
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- CN115197393A CN115197393A CN202210788161.6A CN202210788161A CN115197393A CN 115197393 A CN115197393 A CN 115197393A CN 202210788161 A CN202210788161 A CN 202210788161A CN 115197393 A CN115197393 A CN 115197393A
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- 239000000463 material Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 25
- 230000007246 mechanism Effects 0.000 title claims abstract description 12
- 229920002396 Polyurea Polymers 0.000 claims abstract description 54
- 239000012948 isocyanate Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 150000003077 polyols Chemical class 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 5
- -1 aromatic hydrocarbon isocyanate Chemical class 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 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
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical group O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- 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 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical group COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- 229940054441 o-phthalaldehyde Drugs 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical group 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
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 229920001451 polypropylene glycol Polymers 0.000 abstract description 31
- 238000004519 manufacturing process Methods 0.000 abstract description 5
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
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- 238000012512 characterization method Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
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- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FIXBBOOKVFTUMJ-UHFFFAOYSA-N 1-(2-aminopropoxy)propan-2-amine Chemical compound CC(N)COCC(C)N FIXBBOOKVFTUMJ-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
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- 230000037314 wound repair Effects 0.000 description 1
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/043—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24
- C08G12/046—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24 one being urea or thiourea
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
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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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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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
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/838—Chemically modified polymers by compounds containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
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Abstract
The invention belongs to the field of synthesis of high-molecular functional materials, and discloses a preparation method of a self-repairing material with synergistic effect of multiple mechanisms, which comprises the following steps: firstly, mixing a polyol, isocyanate and a solvent, and carrying out polycondensation reaction to obtain a polyurea material (TH-PPG); then mixing the polyurea material, a chain extender, a cross-linking agent and a solvent for cross-linking reaction to obtain an imine bond cross-linked polyurea material (TH-T-PPG); finally, the polyurea material, the imine bond cross-linked polyurea material and the inorganic salt are subjected to coordination reaction according to respective proportions to obtain the self-repairing material (Zn-TH-PPG and Zn-TH-T-PPG). The method is simple, and combines a plurality of action mechanisms together, so that the obtained self-repairing material has good room-temperature self-repairing effect, good mechanical property and recycling property, the service life is prolonged, the production cost is saved, and the material has higher safety and is an environment-friendly functional material.
Description
Technical Field
The invention belongs to the field of synthesis of high-molecular functional materials, and particularly relates to a preparation method of a self-repairing material with synergistic effect of multiple mechanisms.
Background
In recent years, self-repairing materials become an important direction in the research field of novel functional polymer materials, and can repair self-structure and properties by means of external stimulation after being damaged. Self-repairing materials comprise foreign type repair and intrinsic type repair, and a great deal of research is carried out at home and abroad. The research and application of the external-aid type repair are limited to a certain extent due to the limitation of the repair times, the high price of the catalyst and the like. The intrinsic self-repairing material realizes wound repair based on the opening and reconstruction of dynamic covalent bonds or reversible non-covalent bond interaction at the wound and the movement of polymer chain segments. The dynamic covalent bond has higher stability and strength, but the bonding energy of the non-covalent bond is lower than that of the covalent bond and the self-repairing does not need external stimulation. Therefore, the market needs to develop a self-repairing material based on the synergistic effect of non-covalent bonds and covalent bonds, so that the self-repairing material has the advantages of higher mechanical strength, higher safety, longer service life, reduction of pollution and influence on the environment in the application process and the like.
Hydrogen bonds are relatively weak in non-covalent bonds and can dissipate energy significantly during mechanical deformation, resulting in higher toughness, and their recombination can lead to effective self-healing. And strong interaction force exists between metal ions and ligands in coordination bonds, thermodynamic and kinetic parameters of the polymer crosslinked by the metal coordination bonds can be adjusted in a large range, the mechanical property of the material can be well controlled, and the polymer becomes the strongest non-covalent bond in the field of self-repair. The relatively strong covalent bond can ensure the structural integration and the stable mechanical property. Due to the introduction of the cross-linked polymer with multiple valence bond synergistic effects, the material has the performance of single valence bond effect and diversified special performance, greatly widens the application range of the material, has important application value in the aspects of sealing materials, automobile manufacturing industry and biomedicine, and is expected to be applied to the fields of wearable equipment, automobile coatings, electronic skin, 3D printing, orthopedic fixation and the like.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a self-repairing material with synergistic effect of multiple mechanisms.
The technical scheme adopted by the invention is as follows:
a preparation method of a self-repairing material with multiple mechanisms acting together comprises the following steps:
1) Mixing the polyhydric alcohol, isocyanate and a solvent for polycondensation reaction, and then carrying out vacuum drying for 48-72 h to obtain a polyurea material;
2) Mixing the polyurea material obtained in the step 1), a chain extender, a cross-linking agent and a solvent for cross-linking reaction, and then carrying out vacuum drying for 48-72 h to obtain an imine bond cross-linked polyurea material;
3) Carrying out coordination reaction on the polyurea material obtained in the step 1) and the imine bond cross-linked polyurea material obtained in the step 2) and inorganic salt according to respective proportions, and then carrying out vacuum drying for 48-72 h to obtain two self-repairing materials with multi-mechanism synergistic action.
Further, in the above production method, in the step 1), the molar ratio of the polyhydric alcohol to the isocyanate is 1.0 to 10.0.
Further, in the above preparation method, step 1), the conditions of the polycondensation reaction include two reaction stages: in the first stage, the temperature range is-20 to 10 ℃, the dripping time is 0.3 to 2 hours, and the reaction time is 0.5 to 3 hours; in the second stage, the temperature range is 0-60 ℃, and the reaction time is 16-48 h.
Further, in the preparation method, step 1), the polymeric polyol is a polyamino terminated polymeric polyol NH 2 -R 1 -NH 2 Or bishydroxy-terminated polymeric polyols HO-R 1 -OH，R 1 Is a saturated aliphatic carbon chain of C3-C18 containing oxygen atoms.
Further, in the preparation method, step 1), the structural general formula of the isocyanate is OCN-R 2 -NCO，R 2 Is aromatic hydrocarbon or saturated alkane of C4-C15, when R is 2 When it is an aromatic hydrocarbon, the isocyanate is an aromatic hydrocarbon isocyanate, when R is 2 When the isocyanate is C4-C15 saturated alkane, the isocyanate is saturated alkane isocyanate.
Furthermore, in the above preparation method, step 1), the isocyanate is a mixture of saturated alkane isocyanate and aromatic hydrocarbon isocyanate in a molar ratio of 1.
Further, in the above preparation method, step 1), the saturated alkane isocyanate is lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or 1,6-hexamethylene diisocyanate; the aromatic hydrocarbon isocyanate is p-phenylene diisocyanate, m-phenylene dimethylisocyanate, toluene diisocyanate, dimethyl diphenyl diisocyanate or diphenylmethane diisocyanate.
Further, in the above preparation method, step 2), the structure of the chain extender is OHC-R 3 -CHO，R 3 Is aromatic hydrocarbon or saturated aliphatic carbon chain of C0-C6.
Further, in the above preparation method, in step 2), the chain extender is o-phthalaldehyde, m-phthalaldehyde, or p-phthalaldehyde.
Further, in the above preparation method, step 2), the structure of the cross-linking agent is R 4 (OH) 3 Or R 4 (NH 2 ) 3 ，R 4 Is a saturated aliphatic carbon chain containing oxygen atoms of C3-C18.
Further, in the above preparation method, in step 2), the molar ratio of the polyurea material, the chain extender and the crosslinking agent is 1 to 20.
Further, in the above preparation method, step 2), the conditions of the crosslinking reaction are as follows: the reflux temperature is 40-120 ℃, and the reflux time is 18-48 h.
Further, in the preparation method, in the step 1), the solvent is an organic solvent with a boiling point of 40-100 ℃, and the dosage is 30-120 mL.
Further, in the preparation method, in the step 2), the solvent is an organic solvent with a boiling point of 40-120 ℃, and the dosage is 30-120 mL.
Further, in the above preparation method, in step 3), the molar ratio of the polyurea material to the inorganic salt is 0.1 to 5:1; the molar ratio of the imine bond cross-linked polyurea material to the inorganic salt is 0.1-5:1.
Further, in the above preparation method, in step 3), the inorganic salt is zinc chloride, ferric chloride, copper chloride or cobalt chloride.
Further, in the above preparation method, step 3), the coordination reaction conditions are as follows: the temperature range is 30-120 ℃, and the reaction time is 24-96 h.
The beneficial effects of the invention are as follows:
1. the preparation method is simple, the operation is simple and convenient, and all reactions are safe and efficient.
2. The preparation method combines various action mechanisms together, the obtained self-repairing material can realize quick repairing of the material without or with little external energy, and the material has good room temperature self-repairing effect, good mechanical property and recycling performance.
3. The self-repairing material prepared by the invention has the advantages of long service life, low production cost, high safety, cyclic utilization, environmental friendliness and important application value in wearable equipment, automobile manufacturing industry and biomedical aspect.
Drawings
FIG. 1 is a NMR spectrum of the polyurea material (TH-PPG) prepared in example 1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of an imine bond-crosslinked polyurea material (TH-T-PPG) prepared in example 1.
FIG. 3 is the NMR spectrum of the multi-mechanism synergistic self-healing material (Zn-TH-PPG) prepared in example 1.
FIG. 4 is a NMR spectrum of the multi-mechanism synergistic self-healing material (Zn-TH-T-PPG) prepared in example 1.
FIG. 5 is a Fourier transform infrared spectrum of the polyurea material (TH-PPG) and imine bond crosslinked polyurea material (TH-T-PPG) prepared in example 1.
FIG. 6 is a Fourier transform infrared spectrum of the polyurea material (TH-PPG) prepared in example 1 and a multi-mechanism synergistic self-healing material (Zn-TH-PPG).
FIG. 7 is a Fourier transform infrared spectrum of the imine-bonded cross-linked polyurea material (TH-T-PPG) prepared in example 1 and a multi-mechanism synergistic self-healing material (Zn-TH-T-PPG).
FIG. 8 is a microscopic test chart of self-repairing performance of the self-repairing material prepared in example 1, where a) is a self-repairing material (Zn-TH-PPG) with a multi-mechanism synergistic effect a ') after a polyurea material (TH-PPG) is formed into a film, b) is a self-repairing material (Zn-TH-T-PPG) with a multi-mechanism synergistic effect b') after an imine bond cross-linked polyurea material (TH-T-PPG) is formed into a film.
Detailed Description
Example 1 preparation and characterization of self-healing Material with Multi-mechanism synergy
Preparation method of self-repairing material with synergistic effect of multiple mechanisms
1) Preparation of polyurea Material (TH-PPG)
According to the molar ratio, adding 4.0000g of polypropylene glycol bis (2-aminopropyl ether) into a two-neck flask connected with a constant-pressure dropping funnel in a nitrogen atmosphere, dissolving an experimental device into an appropriate amount of acetone, cooling to 0 ℃, dissolving a mixture of 1.1774g of dicyclohexylmethane diisocyanate and 0.7928g of toluene diisocyanate into the appropriate amount of acetone, wherein the volume ratio of acetone solvents in the previous and subsequent two times is 3:1, the total volume of acetone is 60mL, uniformly stirring, adding into the constant-pressure dropping funnel, slowly dropwise adding within 1h, then reacting at 0 ℃ for 2h, heating to 30 ℃ for reacting for 24h, after the reaction is finished, performing rotary evaporation to remove the acetone, adding into cold deionized water for settling, filtering and collecting a solid dropwise, and performing vacuum drying for 60h to obtain a yellow gel-like solid polyurea material (TH-PPG).
2) Preparation of imine bond cross-linked polyurea material (TH-T-PPG)
According to a molar ratio, the polyurea material, the chain extender and the crosslinking agent are as follows, the polyurea material is prepared by the steps of 1, 8.9702g of the polyurea material obtained in the step 1) is weighed in a three-neck flask with a thermometer and a condensation reflux device and dissolved in 60mL of acetone, 0.2320g of m-phthalaldehyde and 0.0660g of triamino-terminated poly-polyol are added, reflux reaction is carried out for 18h at 90 ℃ under nitrogen atmosphere, the reaction is cooled to room temperature after the reaction is finished, the acetone is removed by rotary evaporation, the solution is dropwise added into cold deionized water for settlement, solid is collected by filtration, and light yellow gel-like solid which is imine bond crosslinked polyurea material (TH-T-PPG) is obtained after vacuum drying for 60 h.
3) Preparation of multi-mechanism synergistic self-repairing polymer
According to the molar ratio, the polyurea material: the zinc chloride is 1.0;
the imine bond cross-linked polyurea material comprises the following components in molar ratio: the zinc chloride is 1.0.
(II) characterization
The polyurea material, the imine bond cross-linked polyurea material and the self-repairing material with the synergistic effect of multiple mechanisms are characterized by means of nuclear magnetic resonance hydrogen spectrum, nuclear magnetic resonance carbon spectrum, fourier transform infrared spectrum and optical microscope analysis, as shown in figures 1-8.
FIG. 1 is the NMR hydrogen spectrum of a polyurea material (TH-PPG) 1 H NMR(300MHz,DMSO-d 6 ,298K):δ1.03-1.05(m,-CH 3 ),1.23-1.33(ss,-NH 2 ),2.26(m,-CH 2 -),2.94-2.96(m,-CH 2 -),3.23-3.25(m,-CH 2 -),3.34(m,-CH 2 -),3.42-3.46(m,-CH 2 -),3.66(s,-CH-),5.60(s,-NH-),5.84(s,-NH-),6.57(s,-NH-),7.19-7.21(m,-Ar-),7.29-7.31(d,-Ar-),7.35(s,-Ar-),7.40-7.43(d,-Ar-),7.47(s,-Ar-),7.74(s,-Ar-),7.94-7.97(d,-ArNHCONH-),8.87-8.90ppm(d,-ArNH-)。
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of an imine bond-crosslinked polyurea material (TH-T-PPG) 1 H NMR(300MHz,DMSO-d 6 ,298K):δ1.04(s,-CH 3 ),1.23-1.32(d,-NH 2 ),2.24(s,-CH 2 -),2.95(s,-CH 2 -),3.33-3.44(m,-CH 2 -),3.66(s,-CH-),5.60(s,-NH-),5.83(s,-NH-),6.53(s,-NH-),7.38(m,-Ar-),7.70-7.78(d,-Ar-),7.91(s,-ArNHCONH-),8.29-8.36(d,-CHN-),8.87ppm(s,-ArNH-)。
FIG. 3 is the NMR hydrogen spectrum of a self-repairing material (Zn-TH-PPG) with multi-mechanism synergistic effect 1 H NMR(300MHz,DMSO-d 6 ,298K):δ1.00-1.06(m,-CH 3 ),1.24-1.34(d,-NH 2 ),1.86(s,-NH 2 ),2.06(s,-CH 2 -),2.13(s,-CH 2 -),2.27(s,-CH 2 -),2.95-2.97(d,-CH 2 -),3.18-3.20(d,-CH 2 -),3.43-3.46(d,-CH 2 -),3.54(s,-CH 2 -),3.68(s,-CH 2 -),4.13-4.15(d,-CH 2 -),4.58(s,-CH-),5.60-5.63(d,-NH-),5.85(s,-NH-),6.15(s,-NH-),6.53-6.55(d,-NH-),7.41-7.49(m,-Ar-),7.72(s,-Ar-),7.91-7.97(t,-ArNHCONH-),8.87-8.90ppm(m,-ArNH-)。
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of a multi-mechanism synergistic self-repairing material (Zn-TH-T-PPG) 1 H NMR(300MHz,DMSO-d 6 ,298K):δ1.03-1.05(m,-CH 3 ),1.14(s,-CH 3 ),1.23(s,-NH 2 ),1.33(s,-NH 2 ),2.12(s,-CH 2 -),2.22-2.25(d,-CH 2 -),2.35(s,-CH 2 -),2.94-2.96(m,-CH 2 -),3.42-3.45(m,-CH 2 -),3.66(s,-CH 2 -),4.57(s,-CH-),5.58(s,-NH-),5.82(s,-NH-),6.52(s,-NH-),6.86(s,-NH-),6.91(s,-NH-),7.38-7.39(m,-Ar-),7.61(s,-Ar-),7.67(s,-Ar-),7.78(s,-ArNHCONH-),7.90-7.92(d,-CHN-),8.87ppm(s,-ArNH-)。
The above characterization proves that the polyurea material, the imine bond cross-linked polyurea material and the self-repairing material with the synergistic effect of multiple mechanisms are successfully synthesized.
FIG. 5 is a Fourier transform infrared spectrum of a polyurea material (TH-PPG) and an imine bond crosslinked polyurea material (TH-T-PPG), and it can be seen that the polyurea material and the imine bond crosslinked polyurea material were successfully synthesized.
TABLE 1 Infrared Spectrum data of TH-PPG and TH-T-PPG and their assignment
FIG. 6 is a Fourier transform infrared spectrum of a polyurea material (TH-PPG) and a multi-mechanism synergistic self-healing material (Zn-TH-PPG), and it can be seen that the polyurea material coordinates successfully.
TABLE 2 Infrared Spectrum data of TH-PPG and Zn-TH-PPG and their assignment
FIG. 7 is a Fourier transform infrared spectrum of an imine bond crosslinked polyurea material (TH-T-PPG) and a multi-mechanism synergistic self-repairing material (Zn-TH-T-PPG), and it can be seen that the imine bond crosslinked polyurea material is successfully coordinated.
TABLE 3 Infrared Spectrum data of TH-T-PPG and Zn-TH-T-PPG and their attribution
In FIG. 8, a) is a microscope test chart of self-repairing performance of the polyurea material (TH-PPG) after film formation; a') is a microscope test chart of self-repairing performance of a self-repairing material (Zn-TH-PPG) with multi-mechanism synergistic effect; b) Is a microscope test picture of self-repairing performance of the imine bond cross-linked polyurea material (TH-T-PPG) after film forming; b') is a microscope test picture of self-repairing performance of a self-repairing material (Zn-TH-T-PPG) with multi-mechanism synergistic effect, cuts of the sample strips almost disappear from the test picture, but fine scratch marks are remained, and macroscopically, the obvious repairing behaviors are generated before and after the sample strips are damaged.
Claims (10)
1. A preparation method of a self-repairing material with multiple mechanisms acting synergistically is characterized by comprising the following steps:
1) Mixing the polyhydric alcohol, isocyanate and a solvent for polycondensation reaction, and then carrying out vacuum drying for 48-72 h to obtain a polyurea material;
2) Mixing the polyurea material obtained in the step 1), a chain extender, a cross-linking agent and a solvent for cross-linking reaction, and then carrying out vacuum drying for 48-72 h to obtain an imine bond cross-linked polyurea material;
3) Carrying out coordination reaction on the polyurea material obtained in the step 1) and the imine bond cross-linked polyurea material obtained in the step 2) and inorganic salt according to respective proportions, and then carrying out vacuum drying for 48-72 h to obtain two self-repairing materials with multi-mechanism synergistic action.
2. The method according to claim 1, wherein in step 1), the molar ratio of the polymeric polyol to the isocyanate is 1.0 to 10.0; the conditions of the polycondensation reaction include two reaction stages: in the first stage, the temperature range is-20 to 10 ℃, the dripping time is 0.3 to 2 hours, and the reaction time is 0.5 to 3 hours; in the second stage, the temperature range is 0-60 ℃, and the reaction time is 16-48 h.
3. The method according to claim 1, wherein in step 1), the polymeric polyol is a polyamino-terminated polymeric polyol NH 2 -R 1 -NH 2 Or bishydroxy-terminated polymeric polyols HO-R 1 -OH，R 1 Is a saturated aliphatic carbon chain of C3-C18 containing oxygen atoms; the structural general formula of the isocyanate is OCN-R 2 -NCO，R 2 Is aromatic hydrocarbon or saturated alkane of C4-C15, when R is 2 When it is an aromatic hydrocarbon, the isocyanate is an aromatic hydrocarbon isocyanate, when R 2 When the isocyanate is C4-C15 saturated alkane, the isocyanate is saturated alkane isocyanate.
4. The preparation method according to claim 3, wherein the isocyanate is a mixture of a saturated alkane isocyanate and an aromatic hydrocarbon isocyanate in a molar ratio of 1.
5. The method of claim 4, wherein the saturated alkane isocyanate is lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, or 1,6-hexamethylene diisocyanate; the aromatic hydrocarbon isocyanate is p-phenylene diisocyanate, m-phenylene dimethylisocyanate, toluene diisocyanate, dimethyl diphenyl diisocyanate or diphenylmethane diisocyanate.
6. The method according to claim 1, wherein in step 2), the structure of the chain extender is OHC-R 3 -CHO，R 3 Is aromatic hydrocarbon or saturated aliphatic carbon chain of C0-C6; the structure of the cross-linking agent is R 4 (OH) 3 Or R 4 (NH 2 ) 3 ，R 4 Is a saturated aliphatic carbon chain containing oxygen atoms of C3-C18; the polyurea material, the chain extender and the cross-linking agent have the molar ratio of 1-20.
7. The method according to claim 6, wherein in the step 2), the chain extender is o-phthalaldehyde, m-phthalaldehyde, or p-phthalaldehyde.
8. The method according to claim 1, wherein in step 2), the conditions of the crosslinking reaction are: the reflux temperature is 40-120 ℃, and the reflux time is 18-48 h.
9. The preparation method according to claim 1, wherein in the step 1), the solvent is an organic solvent with a boiling point of 40-100 ℃ and is used in an amount of 30-120 mL; in the step 2), the solvent is an organic solvent with a boiling point of 40-120 ℃, and the dosage is 30-120 mL.
10. The method of claim 1, wherein in step 3), the molar ratio of the polyurea material to the inorganic salt is 0.1 to 5:1; the molar ratio of the imine bond cross-linked polyurea material to the inorganic salt is 0.1-5:1; the inorganic salt is zinc chloride, ferric chloride, copper chloride or cobalt chloride; the coordination reaction conditions are as follows: the temperature range is 30-120 ℃, and the reaction time is 24-96 h.
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| CN115895411A (en) * | 2022-11-24 | 2023-04-04 | 四川大学 | Preparation method and application of bi-component spray-coating self-repairing polyurea coating |
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