CN115677972A - Tough type light-operated self-repairing lignin-based polyurethane and preparation method and application thereof - Google Patents
Tough type light-operated self-repairing lignin-based polyurethane and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 26
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 93
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 32
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 20
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 17
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
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- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
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- 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 7
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- RJNRKZBHLCOHNM-UHFFFAOYSA-N 2-(3-hydroxypyridin-2-yl)pyridin-3-ol Chemical compound OC1=CC=CN=C1C1=NC=CC=C1O RJNRKZBHLCOHNM-UHFFFAOYSA-N 0.000 claims description 5
- POJMWJLYXGXUNU-UHFFFAOYSA-N 6-(6-oxo-1h-pyridin-2-yl)-1h-pyridin-2-one Chemical compound N1C(=O)C=CC=C1C1=CC=CC(=O)N1 POJMWJLYXGXUNU-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RRXGRDMHWYLJSY-UHFFFAOYSA-N [2-[4-(hydroxymethyl)pyridin-2-yl]pyridin-4-yl]methanol Chemical compound OCC1=CC=NC(C=2N=CC=C(CO)C=2)=C1 RRXGRDMHWYLJSY-UHFFFAOYSA-N 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 5
- WTHJTVKLMSJXEV-UHFFFAOYSA-N 2-(4-aminopyridin-2-yl)pyridin-4-amine Chemical compound NC1=CC=NC(C=2N=CC=C(N)C=2)=C1 WTHJTVKLMSJXEV-UHFFFAOYSA-N 0.000 claims description 4
- YKSWVQYWQSZDPR-UHFFFAOYSA-N 6-(6-aminopyridin-2-yl)pyridin-2-amine Chemical compound NC1=CC=CC(C=2N=C(N)C=CC=2)=N1 YKSWVQYWQSZDPR-UHFFFAOYSA-N 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 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 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 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
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- 238000003786 synthesis reaction Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 claims description 2
- QEIRCDAYPQFYBI-UHFFFAOYSA-N 6-(5-aminopyridin-2-yl)pyridin-3-amine Chemical compound N1=CC(N)=CC=C1C1=CC=C(N)C=N1 QEIRCDAYPQFYBI-UHFFFAOYSA-N 0.000 claims description 2
- QWFXMCQPHDPMLA-UHFFFAOYSA-N 6-(5-hydroxypyridin-2-yl)pyridin-3-ol Chemical compound N1=CC(O)=CC=C1C1=CC=C(O)C=N1 QWFXMCQPHDPMLA-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000007789 gas Substances 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
- 239000002904 solvent Substances 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 44
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 16
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000012975 dibutyltin dilaurate Substances 0.000 description 16
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- 238000007731 hot pressing Methods 0.000 description 12
- 239000003513 alkali Substances 0.000 description 7
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- 239000011159 matrix material Substances 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses tough light-operated self-repairing lignin-based polyurethane and a preparation method and application thereof. The lignin-based polyurethane is obtained by reacting the following components in parts by mass: 70-95 parts of long-chain dihydric alcohol, 5-30 parts of low-molecular-weight lignin, 100 parts of the total amount of the lignin and the long-chain dihydric alcohol, 1-5 parts of isocyanate (R = 1.1-1.5), 1-5 parts of reactive ligand, 1-5 parts of complexing agent and 0.2-0.5 part of catalyst. According to the invention, the phenolic hydroxyl of low-molecular-weight lignin is utilized to construct a dynamic phenolic hydroxyl urethane bond, and an interface metal coordination bond is constructed between a polyurethane chain segment and lignin to form a dynamic double-crosslinked network structure, so that the strength and toughness of lignin-based polyurethane are greatly improved; meanwhile, the prepared lignin-based polyurethane material has excellent light-operated self-repairing performance, and the damaged part is irradiated by near infrared light, so that the repairing rate of more than 95% can be realized within 10 minutes.
Description
Technical Field
The invention belongs to the technical field of polyurethane materials, and particularly relates to tough type light-operated self-repairing lignin-based polyurethane and a preparation method and application thereof.
Background
Polyurethane (PU) is a polymeric material having urethane structural units in the backbone, which is polymerized from isocyanate and polyol. The polyurethane material has excellent mechanical property, high strength, good elasticity, wear resistance and chemical resistance, and can be widely applied to the fields of home furnishing, buildings, daily necessities, traffic, household appliances and the like. Due to the shortage of petrochemical resources and the environmental pollution, the development of biomass-based degradable polyurethane materials by partially replacing petrochemical resources with biomass is a pressing task.
The lignin is the second most natural polymer in nature, has wide sources and low price, is green and degradable, and is widely concerned by people. The lignin is rich in a plurality of functional groups such as benzene rings, phenolic hydroxyl groups, alcoholic hydroxyl groups, carboxyl groups and the like, has excellent ultraviolet resistance and ageing resistance [ Green chem.,2015,17,320], and is widely researched for synthesizing polyurethane materials by using the lignin. The polyurethane is directly synthesized by using the industrial lignin, and the prepared polyurethane has poor mechanical properties [ Acs sustatin. Chem.Eng.,2017,5,4276] due to low reaction activity and poor compatibility with the polyurethane; the reactivity of lignin can be improved by chemical modification, such as conversion of phenolic hydroxyl groups to alcoholic hydroxyl groups or increase of hydroxyl group content [ ACS appl.mater.inter.,2012,4,2840; compositions Part B,2020,200,108295], but chemical modification is usually tedious and costly; how to prepare the high-strength high-toughness lignin-based polyurethane material by adopting a simple and efficient method remains a great challenge.
The need for long-life and durable materials has driven the need for self-healing polyurethane materials. Self-repairing is generally to rearrange the damaged polymer network through the action of heat or light, so as to recover the mechanical properties of the material. Thermal self-repair is often difficult to achieve with localized temperature control and precise repair, and requires repair times of hours or more, which can cause aging of the material. The light self-repairing can realize the accurate repairing of the damaged part by adjusting the size and the intensity of the light source, and has obvious advantages; in order to realize the self-light-repairing function, expensive photo-thermal conversion media, such as carbon materials, nano metal particles, polydopamine and the like, are usually added into the high polymer material, which undoubtedly increases the cost of the self-light-repairing material. Recently, lignin has been found to be an excellent low-cost photothermal conversion medium, and a polymer material prepared from lignin can be used for seawater desalination, photothermal driving, etc. under the driving of light [ ACS appl.mater.inter.,2021,13,7600; green chem.,2022,24,823]. Although the prior art discloses that polyurethane dynamic repair is realized by using urethane bonds, coordination bonds, disulfide bonds or ketoxime urethane bonds, the lignin-based polyurethane material with the light-operated self-repair function is prepared based on the photo-thermal conversion capacity of lignin, and reports are not found at present.
Therefore, how to improve the reaction activity of the lignin and exert the advantages of the lignin to prepare the lignin-based polyurethane material with high strength and toughness and excellent light-operated self-repairing function is an important difficult problem. The material is expected to broaden the application prospect of polyurethane in the aspects of renewable, intelligent elastomers, functional coatings and the like.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the tough light-control self-repairing lignin-based polyurethane.
The invention also aims to provide a preparation method of the tough light-operated self-repairing lignin-based polyurethane.
The invention further aims to provide application of the tough light-operated self-repairing lignin-based polyurethane.
The purpose of the invention is realized by the following technical scheme:
the tough light-operated self-repairing lignin-based polyurethane is prepared from the following components in parts by mass:
wherein the total mass of the low molecular weight lignin and the long-chain dihydric alcohol is 100 parts; the isocyanate index R = 1.1-1.5.
The tough light-operated self-repairing lignin-based polyurethane is prepared from the following components in parts by mass:
wherein the total mass of the low molecular weight lignin and the long-chain dihydric alcohol is 100 parts; the isocyanate index R = 1.1-1.5.
The long-chain dihydric alcohol is at least one of polycaprolactone diol (PCL), polytetrahydrofuran diol (PTMG), polydimethylsiloxane Diol (PDMS), polyethylene glycol (PEG) and polypropylene glycol (PPG); the number average molecular weight of the long-chain dihydric alcohol is 500-5000 g/mol; more preferably at least one of Polydimethylsiloxane Diol (PDMS), polycaprolactone diol (PCL), and polytetrahydrofuran diol (PTMG).
The low molecular weight lignin is obtained by extracting industrial lignin with the weight average molecular weight of 3000-6000 g/mol serving as a raw material with ethanol, acetone or ethyl acetate, and the weight average molecular weight of the lignin is 800-1500 g/mol.
The isocyanate is at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI) and Hexamethylene Diisocyanate (HDI); more preferably at least one of dicyclohexylmethane diisocyanate (HMDI), toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and Hexamethylene Diisocyanate (HDI).
The difunctional reactive ligand is at least one of triazole containing amino, sulfydryl or hydroxyl and bipyridyl containing amino, sulfydryl or hydroxyl; more preferably at least one of 3,5-diamino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 2,2 '-bipyridine-3,3' -diol, 2,2 '-bipyridine-5,5' -diol, 2,2 '-bipyridine-6,6' -diol, 2,2 '-bipyridine-4,4' -dimethanol, 4,4 '-diamino-2,2' -bipyridine, 5,5 '-diamino-2,2' -bipyridine, and 6,6 '-diamino-2,2' -bipyridine; most preferably 2,2 '-bipyridine-4,4' -dimethanol, 6,6 '-diamino-2,2' -bipyridine, 4,4 '-diamino-2,2' -bipyridine, 2,2 '-bipyridine-6,6' -diol, 2,2 '-bipyridine-3,3' -diol, 3,5-diamino-1,2,4-triazole and 3-amino-5-mercapto-1,2,4-triazole.
The complexing agent is at least one of zinc chloride, ferric chloride, copper chloride, zinc acrylate and zinc methacrylate; more preferably at least one of zinc chloride, ferric chloride, cupric chloride and zinc acrylate.
The catalyst is a common organic tin catalyst for polyurethane synthesis; more preferably dibutyltin dilaurate (DBTDL).
The preparation method of the tough light-operated self-repairing lignin-based polyurethane comprises the following steps:
under the protection of inert gas atmosphere at 60-100 ℃, uniformly mixing long-chain dihydric alcohol, isocyanate and a catalyst, and carrying out prepolymerization reaction for 0.5-2 hours; then adding a reactive ligand to react for 0.5 to 2 hours; then adding low molecular weight lignin for reaction for 2-5 hours; finally adding a coordination agent for reaction for 0.5-1 hour; curing to obtain the lignin-based polyurethane.
The reaction temperature is 70-90 ℃.
The low molecular weight lignin is added in the form of a solution, the concentration of the solution is 10-30 wt%, and the solvent is at least one of dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), 1,4-dioxane and acetone.
The curing temperature is 40-70 ℃ and the curing time is 6-24 h.
The inert gas refers to at least one of a rare gas and nitrogen.
The lignin-based polyurethane can be further hot-pressed for 10 to 30 minutes at the temperature of between 140 and 180 ℃.
The application of the tough light-control self-repairing lignin-based polyurethane in the fields of renewable and intelligent elastomers and functional coatings.
The invention adopts low molecular weight lignin with high reaction activity to synthesize degradable lignin-based polyurethane material. The phenolic hydroxyl of low-molecular-weight lignin is utilized to construct a dynamic phenolic hydroxyl urethane bond, and a nitrogen heterocyclic diol/amine monomer is introduced to construct an interface dynamic metal coordination bond with a polar group of the lignin, so that a dynamic double-crosslinked network structure is formed, the interface effect of the lignin and a polyurethane matrix is improved, and the mechanical property of the material is improved; the tensile strength of the prepared lignin-based polyurethane can reach more than 30MPa, and the breaking tensile rate reaches 1500%. Meanwhile, the dynamic metal coordination bond can also strengthen the photo-thermal conversion performance of lignin; based on the photo-thermal conversion performance and the dynamic double-crosslinked network structure of the lignin, the material is endowed with an excellent light-operated self-repairing function. The damaged part is irradiated by near infrared light, the self-healing rate of more than 95 percent can be realized within 10 minutes, and the service life of the material is effectively prolonged.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, the polyurethane is synthesized by adopting the low-molecular-weight lignin, so that the reaction activity of the lignin and the compatibility of the lignin and a polyurethane matrix are improved, and the uniform dispersion of the lignin is promoted, thereby improving the mechanical property of the lignin-based polyurethane material.
2. According to the invention, a dynamic phenolic hydroxyl urethane bond is constructed by utilizing phenolic hydroxyl of low-molecular-weight lignin, a reactive ligand is introduced into a polyurethane main chain, and an interface dynamic metal coordination bond is constructed with a polar group of the lignin, so that a dynamic double-crosslinked network structure is formed, and the interaction between the lignin and a polyurethane chain segment is promoted. Under the action of external force, the dynamic coordination bonds are repeatedly broken and reconstructed, and a large amount of external mechanical energy is dissipated, so that the strength and the toughness of the lignin-based polyurethane material are greatly improved.
3. The lignin-based polyurethane prepared by the method has excellent photo-thermal conversion capability, and the photo-thermal conversion capability of the material is enhanced by the metal coordination bond. Near infrared light is adopted to irradiate the damaged or broken part of the lignin-based polyurethane, and the self-repairing rate of over 95 percent can be realized after 10 minutes of irradiation, so that the light-operated self-repairing performance is fast and efficient.
Drawings
FIG. 1 shows the variation of the maximum temperature of the surface of lignin-based polyurethane with the time of illumination.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
The low molecular weight lignin in the following examples and comparative examples was extracted from industrial alkali lignin by using absolute ethanol, the weight average molecular weight of the industrial alkali lignin used was 3000g/mol, and the weight average molecular weight of the low molecular weight lignin obtained was 1000g/mol, and specific relevant characteristic parameters of both are shown in table 1. As can be seen from Table 1, the low molecular weight lignin has low molecular weight, good homogeneity, high hydroxyl content, small reaction steric hindrance, higher reaction activity and contribution to the synthesis of polyurethane.
In the following examples and comparative examples, the total mass of lignin and long-chain glycol was 100 parts; the number average molecular weight of the long-chain dihydric alcohol is 2000g/mol; the amount of isocyanate used is determined in accordance with the isocyanate index R.
Unless otherwise specified, the parts in the following examples and comparative examples are parts by mass.
TABLE 1 characteristic parameters of technical alkali lignin and low molecular weight lignin
Example 1
Under the protection of nitrogen and 70 ℃, controlling an isocyanate index R =1.1, uniformly mixing 95 parts of PTMG, a certain amount of HDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 2 parts of 3,5-diamino-1,2,4-triazole for continuous reaction for 1 hour, then dissolving 5 parts of low molecular weight lignin in DMF (10 wt%), adding the mixture into the system for reaction for 4 hours, and finally adding 2 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold to be hot-pressed for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Example 2
Under the protection of nitrogen and 70 ℃, controlling an isocyanate index R =1.1, uniformly mixing 90 parts of PTMG, quantitative HDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 2 parts of 3,5-diamino-1,2,4-triazole for continuous reaction for 1 hour, then dissolving 10 parts of low molecular weight lignin in DMF (10 wt%), adding the mixture into the system for reaction for 4 hours, and finally adding 2 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold to be hot-pressed for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Example 3
Under the protection of nitrogen and 70 ℃, controlling an isocyanate index R =1.1, uniformly mixing 80 parts of PTMG, quantitative HDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 2 parts of 3,5-diamino-1,2,4-triazole for continuous reaction for 1 hour, then dissolving 20 parts of low molecular weight lignin in DMF (10 wt%), adding the obtained solution into the system for reaction for 4 hours, and finally adding 2 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold to carry out hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Example 4
Under the protection of nitrogen and 70 ℃, controlling an isocyanate index R =1.1, uniformly mixing 70 parts of PTMG, quantitative HDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 2 parts of 3,5-diamino-1,2,4-triazole for continuous reaction for 1 hour, then dissolving 30 parts of low molecular weight lignin in DMF (10 wt%), adding the mixture into the system for reaction for 4 hours, and finally adding 2 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold for hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Example 5
Controlling isocyanate index R =1.2 under the protection of nitrogen at 70 ℃, uniformly mixing 90 parts of PTMG, quantitative HDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 2 parts of 3-amino-5-mercapto-1,2,4-triazole for continuous reaction for 1 hour, then dissolving 10 parts of low molecular weight lignin in DMF (10 wt%), adding into the system for reaction for 4 hours, and finally adding 2 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold for hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Example 6
Under the protection of nitrogen and 70 ℃, controlling an isocyanate index R =1.4, uniformly mixing 90 parts of PTMG, quantitative HDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 2 parts of 3-amino-5-mercapto-1,2,4-triazole for continuous reaction for 1 hour, then dissolving 10 parts of low molecular weight lignin in DMF (10 wt%), adding the obtained solution into the system for reaction for 4 hours, and finally adding 2 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold for hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Example 7
Under the protection of nitrogen and 70 ℃, controlling an isocyanate index R =1.5, uniformly mixing 90 parts of PTMG, quantitative HDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 2 parts of 3-amino-5-mercapto-1,2,4-triazole for continuous reaction for 1 hour, then dissolving 10 parts of low molecular weight lignin in DMF (10 wt%), adding the obtained solution into the system for reaction for 4 hours, and finally adding 2 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold to carry out hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Example 8
Under the protection of nitrogen and 70 ℃, controlling an isocyanate index R =1.1, uniformly mixing 90 parts of PTMG, quantitative MDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 5 parts of 3,5-diamino-1,2,4-triazole for continuous reaction for 1 hour, then dissolving 10 parts of low molecular weight lignin in DMF (10 wt%), adding the obtained solution into the system for reaction for 4 hours, and finally adding 2 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold for hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Example 9
Under the protection of nitrogen and 70 ℃, controlling the isocyanate index R =1.1, uniformly mixing 90 parts of PTMG, quantitative TDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 5 parts of 3,5-diamino-1,2,4-triazole for continuous reaction for 1 hour, then dissolving 10 parts of low molecular weight lignin in DMF (10 wt%), adding the obtained solution into the system for reaction for 4 hours, and finally adding 5 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold to carry out hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Example 10
Under the protection of nitrogen and 70 ℃, controlling an isocyanate index R =1.1, uniformly mixing 90 parts of PTMG, quantitative HMDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 5 parts of 3,5-diamino-1,2,4-triazole for continuous reaction for 1 hour, then dissolving 10 parts of low molecular weight lignin in DMF (10 wt%), adding the obtained mixture into the system for reaction for 4 hours, and finally adding 5 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold for hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Example 11
The complexing agent is ferric chloride, the reactive ligand is 2,2 '-bipyridine-3,3' -diol, and the other conditions are the same as in example 2.
Example 12
The long chain diol was PDMS, the reactive ligand was 2,2 '-bipyridine-6,6' -diol, and the other conditions were the same as in example 11.
Example 13
The long chain diol is PCL, the reactive ligand is 4,4 '-diamino-2,2' -bipyridine, and the other conditions are the same as in example 11.
Example 14
The complexing agent is copper chloride, the reactive ligand is 6,6 '-diamino-2,2' -bipyridine, and the other conditions are the same as in example 11.
Example 15
The complexing agent is zinc acrylate, the reactive ligand is 2,2 '-bipyridine-4,4' -dimethanol, and the other conditions are the same as in example 11.
Comparative example 1 (direct use of Industrial alkali Lignin)
Under the protection of nitrogen and 70 ℃, controlling an isocyanate index R =1.1, uniformly mixing 95 parts of PTMG, quantitative HDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 2 parts of 3,5-diamino-1,2,4-triazole for continuous reaction for 1 hour, then dissolving 5 parts of industrial alkali lignin in DMF (10 wt%), adding the obtained solution into the system for reaction for 4 hours, and finally adding 2 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold for hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Comparative example 2 (without addition of reactive ligand and complexing agent)
At 70 ℃ and under the protection of nitrogen, an isocyanate index R =1.1 was controlled, 95 parts of PTMG, a fixed amount of HDI, and 0.4 part of catalyst DBTDL were uniformly mixed, a prepolymerization reaction was performed for 2 hours, and then 5 parts of low molecular weight lignin was dissolved in DMF (10 wt%), added to the system, and reacted for 4 hours. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold for hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Comparative example 3
The lignin used was 5 parts of technical alkali lignin, and the other conditions were the same as in comparative example 2.
Comparative example 4 (no complexing agent added)
Under the protection of nitrogen and 70 ℃, controlling an isocyanate index R =1.1, uniformly mixing 95 parts of PTMG, quantitative HDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then adding 2 parts of 3,5-diamino-1,2,4-triazole for continuous reaction for 1 hour, and finally dissolving 5 parts of low molecular weight lignin in DMF (10 wt%) and adding the mixture into the system for reaction for 4 hours. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold for hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
Comparative example 5 (without addition of reactive ligand)
At 70 ℃ and under the protection of nitrogen, controlling an isocyanate index R =1.1, uniformly mixing 95 parts of PTMG, quantitative HDI and 0.4 part of catalyst DBTDL, carrying out prepolymerization reaction for 2 hours, then dissolving 5 parts of low molecular weight lignin in DMF (10 wt%), adding into the system for reaction for 4 hours, and finally adding 2 parts of zinc chloride for reaction for 0.5 hour. And after the reaction is finished, putting the product into a vacuum oven, drying for 12 hours at 50 ℃, and then putting the product into a mold for hot pressing for 15 minutes at 160 ℃ to obtain the required polyurethane material.
The lignin-based polyurethane materials of the examples and the comparative examples are prepared into dumbbell-shaped splines meeting GB/T528-2009 standards, and an MTS universal tester is adopted to test mechanical property data such as tensile strength, breaking elongation and the like, and the results are shown in Table 2.
Table 2 shows the results of the tensile test of the lignin-based polyurethane materials obtained in some of the examples and comparative examples. It can be seen from table 2 that the polyurethane samples containing dynamic double cross-linked networks prepared from low molecular weight lignin (examples 1 to 6) have excellent mechanical properties, the tensile strength is above 25MPa, wherein the maximum tensile strength reaches 33.5MPa, mainly because the dynamic double cross-linked networks promote the interaction between lignin and polyurethane chain segments, and simultaneously, under the action of external force, the fracture reconstruction of dynamic coordination bonds dissipates a large amount of mechanical energy, thereby greatly improving the strength and toughness of lignin-based polyurethane. Increasing the amount of lignin used (examples 1 to 4) increased the interaction between lignin and polyurethane and increased the crosslink density, thus gradually increasing the young's modulus of the material, but too much lignin reduced the dispersibility and therefore the strength of the material.
Comparing example 1 with comparative example 1, and comparing example 2 with comparative example 3, respectively, it can be seen that the polyurethane material prepared from the low molecular weight lignin has more excellent mechanical properties, mainly because the low molecular weight lignin has high reactivity and good compatibility with the polyurethane matrix. And the industrial alkali lignin has low reaction activity and is easy to agglomerate, so the prepared polyurethane has poor mechanical property.
For the samples in which no metal coordinate bond was constructed (comparative examples 2 to 5), the mechanical properties were poor. In particular, comparative example 5, in which a complexing agent was added to a sample containing no reactive ligand, the presence of the complexing agent weakened the interaction between the polyurethane segments, and therefore its tensile strength was less than 1MPa.
TABLE 2 mechanical Properties of Lignin-based polyurethanes
And testing the photothermal conversion performance of the prepared lignin-based polyurethane based on the natural photothermal conversion capacity of the lignin. The surface of the polyurethane was irradiated with near infrared light of 808nm, and the temperature change of the surface was recorded with an infrared camera, and the curve of the maximum temperature of the surface with the irradiation time was shown in FIG. 1. As can be seen from the figure, the maximum temperature of the surface of the lignin-based polyurethane rapidly increases with the increase of the illumination time, and reaches the maximum value within 2 minutes and keeps stable, which indicates that the prepared lignin-based polyurethane has excellent photothermal conversion capability. Meanwhile, the maximum surface temperature of the sample without coordination bonds (comparative examples 2 to 3) is about 130 ℃, while the maximum surface temperature of the sample with coordination bonds (examples 1 to 4) is about 165 ℃ which is 35 ℃ higher than that of the sample without coordination bonds, which shows that the metal coordination bonds enhance the photo-thermal conversion capability of the lignin-based polyurethane and are more beneficial to realizing the photo-controlled self-repairing performance of the lignin-based polyurethane.
Based on the natural photo-thermal conversion capability of lignin and the dynamic double-crosslinking network structure of lignin-based polyurethane, the prepared polyurethane material is subjected to a light-operated self-repairing test. Polyurethane is cut into two sections, and the polyurethane is healed under the irradiation of near infrared light with the wavelength of 808nm, the irradiation time is 10 minutes, and the mechanical property change before and after healing is compared. The results are shown in Table 3. As can be seen from the table, most of the lignin-based polyurethane can realize the self-repairing rate of more than 95% by the irradiation of near infrared light for 10 minutes, and the repairing speed is high. When the near infrared light irradiates the damaged part of the material, the polyurethane chain segment migrates under the action of high temperature, and the dynamic network structure in the material is dynamically fractured and reconstructed, so that the damaged part is repaired. Therefore, the prepared lignin-based polyurethane has excellent light-operated self-healing performance.
TABLE 3 light control self-healing Properties of Lignin-based polyurethanes
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The tough light-operated self-repairing lignin-based polyurethane is characterized by being prepared from the following components in parts by mass:
wherein the total mass of the low molecular weight lignin and the long-chain dihydric alcohol is 100 parts; the isocyanate index R = 1.1-1.5;
the number average molecular weight of the long-chain dihydric alcohol is 500-5000 g/mol;
the weight average molecular weight of the low molecular weight lignin is 800-1500 g/mol;
the difunctional reactive ligand is at least one of triazole containing amino, sulfydryl or hydroxyl and bipyridyl containing amino, sulfydryl or hydroxyl.
2. The tough type light-operated self-repairing lignin-based polyurethane according to claim 1, wherein the long-chain diol is at least one of polycaprolactone diol, polytetrahydrofuran diol, polydimethylsiloxane diol, polyethylene glycol and polypropylene glycol;
the isocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
3. The tough light-operated self-repairing lignin-based polyurethane as claimed in claim 1, wherein the low molecular weight lignin is obtained by extracting industrial lignin with a weight average molecular weight of 3000-6000 g/mol with ethanol, acetone or ethyl acetate, and the weight average molecular weight of the lignin is 800-1500 g/mol.
4. The tough light-operated self-healing lignin-based polyurethane according to claim 1, wherein the difunctional reactive ligand is at least one of 3,5-diamino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 2,2' -bipyridine-3,3 ' -diol, 2,2' -bipyridine-5,5 ' -diol, 2,2' -bipyridine-6,6 ' -diol, 2,2' -bipyridine-4,4 ' -dimethanol, 3535 ' -diamino-2,2 ' -bipyridine, 5,5' -diamino-2,2 ' -bipyridine and 6,6' -diamino-62 zxft 3562 ' -bipyridine 6262 ' -626245;
the complexing agent is at least one of zinc chloride, ferric chloride, copper chloride, zinc acrylate and zinc methacrylate.
5. The tough type light-operated self-repairing lignin-based polyurethane according to claim 1, wherein the long-chain diol is at least one of polydimethylsiloxane diol, polycaprolactone diol and polytetrahydrofuran diol;
the isocyanate is at least one of dicyclohexylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate;
the difunctional reactive ligand is at least one of 2,2 '-bipyridine-4,4' -dimethanol, 6,6 '-diamino-2,2' -bipyridine, 4,4 '-diamino-2,2' -bipyridine, 2,2 '-bipyridine-6,6' -diol, 2,2 '-bipyridine-3,3' -diol, 3,5-diamino-1,2,4-triazole and 3-amino-5-mercapto-1,2,4-triazole;
the complexing agent is at least one of zinc chloride, ferric chloride, copper chloride and zinc acrylate.
6. The tough type light-operated self-repairing lignin-based polyurethane according to claim 1, wherein the catalyst is an organotin catalyst commonly used in polyurethane synthesis.
7. The preparation method of the tough type light-operated self-repairing lignin-based polyurethane of any one of claims 1 to 6, which is characterized by comprising the following steps:
under the protection of inert gas atmosphere at 60-100 ℃, uniformly mixing long-chain dihydric alcohol, isocyanate and a catalyst, and carrying out prepolymerization reaction for 0.5-2 hours; then adding a reactive ligand to react for 0.5 to 2 hours; then adding low molecular weight lignin for reaction for 2-5 hours; finally adding a coordination agent for reaction for 0.5-1 hour; curing to obtain the lignin-based polyurethane.
8. The preparation method of the tough light-operated self-repairing lignin-based polyurethane of claim 7, wherein the reaction temperature is 70-90 ℃; the curing temperature is 40-70 ℃, and the curing time is 6-24 hours; the lignin-based polyurethane can be further hot-pressed for 10 to 30 minutes at the temperature of between 140 and 180 ℃.
9. The preparation method of the tough type light-operated self-repairing lignin-based polyurethane as claimed in claim 7, wherein the low molecular weight lignin is added in the form of a solution, the concentration of the solution is 10-30 wt%, and the solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, 1,4-dioxane and acetone;
the inert gas means at least one of a rare gas and nitrogen.
10. The application of the tough light-operated self-repairing lignin-based polyurethane of any one of claims 1 to 6 in the fields of renewable and intelligent elastomers and functional coatings.
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