CN115160570B - Preparation method of poly-lipoic acid material with light-regulated adhesion performance - Google Patents
Preparation method of poly-lipoic acid material with light-regulated adhesion performance Download PDFInfo
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- 229960002663 thioctic acid Drugs 0.000 title claims abstract description 63
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 50
- 235000019136 lipoic acid Nutrition 0.000 claims abstract description 49
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- -1 hexyl lipoic acid Chemical compound 0.000 claims description 14
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 13
- BEYOBVMPDRKTNR-BUHFOSPRSA-N 4-Hydroxyazobenzene Chemical compound C1=CC(O)=CC=C1\N=N\C1=CC=CC=C1 BEYOBVMPDRKTNR-BUHFOSPRSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- FCMCSZXRVWDVAW-UHFFFAOYSA-N 6-bromo-1-hexanol Chemical compound OCCCCCCBr FCMCSZXRVWDVAW-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012954 diazonium Substances 0.000 claims description 6
- 150000001989 diazonium salts Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 239000000178 monomer Substances 0.000 abstract description 14
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 10
- 238000007634 remodeling Methods 0.000 abstract description 10
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 230000008439 repair process Effects 0.000 abstract description 5
- 238000005886 esterification reaction Methods 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 abstract description 4
- 230000008023 solidification Effects 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 12
- 101001120428 Lithospermum erythrorhizon Phenylalanine ammonia-lyase 2 Proteins 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 101100346764 Mus musculus Mtln gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 239000012304 carboxyl activating agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/06—Polythioethers from cyclic thioethers
Abstract
The invention discloses a preparation method of a poly-lipoic acid material with light-regulated adhesion-controlled performance, which is characterized in that an azo-phenyl-containing lipoic acid monomer is prepared through esterification reaction, and the poly-lipoic acid material containing azo phenyl is further obtained through copolymerization with the lipoic acid monomer. The main chain of the copolymer is dynamic covalent disulfide bond and contains partial carboxyl side chains, so that the copolymer can be subjected to thermal remodeling through dynamic exchange of disulfide bonds and reconstruction of hydrogen bond networks under mild conditions and recycled. The copolymer is in a viscous state with good flowing property at 80 ℃ and in a crystallization and solidification state at room temperature, can be repaired regardless of the type of materials by utilizing the property, and can better resist damage of external force after the repair of the materials capable of forming hydrogen bonds with the copolymer is completed. The side group also contains an azo-benzene group with photoresponsive properties, so that the photo-tunable excellent adhesion properties are achieved.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a poly-lipoic acid material with light-controlled adhesion performance. The novel material contains dynamic covalent disulfide bonds, hydrogen bonds and photo-responsive azo phenyl groups, so that the novel material has thermal remodeling performance and photo-adjustable excellent adhesion performance.
Background
Lipoic acid (Lipoic acid) is taken as a natural small molecule, plays a vital role in aerobic metabolism of animals, is an ideal monomer for constructing a supermolecular system, and is mainly attributed to the fact that dynamic disulfide bonds and carboxyl groups exist in the molecule at the same time, the dynamic disulfide bonds exist after ring-opening polymerization to enable the molecule to have self-repairing performance, and the existence of terminal carboxyl groups constructs a hydrogen bond crosslinking network to endow the molecule with certain mechanical properties, and meanwhile, the molecule can form hydrogen bond interaction with surfaces rich in hydroxyl groups and fluorine so as to have certain adhesive performance. And by the presence of the terminal carboxyl group, it is possible to introduce a functional monomer through an esterification reaction and an amidation reaction, preparing various functional self-repairing materials. However, it is found that most of lipoic acid monomers modified by functional groups lose the ability of thermal ring-opening polymerization, and thiol is required to be added additionally to initiate polymerization, and the thiol is a substance with a certain biotoxicity and does not meet the standard of green chemistry.
Disclosure of Invention
Based on the technical problems, the invention aims to provide a preparation method of a polythiooctanoic acid material with light-controlled adhesion performance. The lipoic acid monomer containing the light-responsive azo-phenyl group is synthesized through esterification reaction, and the lipoic acid monomer loses the capability of thermal ring-opening polymerization like most other functionalized lipoic acid monomers, but the lipoic acid monomer has the capability of generating free radicals through ring opening under the heating condition, so that the lipoic acid monomer is used for initiating polymerization of the monomer, and a novel material containing dynamic covalent disulfide bonds, hydrogen bonds and the light-responsive azo-phenyl group is prepared, and has the thermal remolding property and the light-adjustable excellent adhesion property.
1. Preparation of poly-lipoic acid material with light-regulated adhesion performance
(1) Preparation of 4-hydroxyazobenzene (AzoOH): dissolving aniline in hydrochloric acid under the condition of ice water bath, keeping the temperature of a reaction system at 0-5 ℃, and adding sodium nitrite aqueous solution into the reaction system to prepare diazonium salt solution; dissolving phenol in sodium hydroxide aqueous solution, slowly adding the diazonium salt solution to generate yellow precipitate, filtering and drying to obtain 4-hydroxyazobenzene. Wherein the molar ratio of aniline to sodium nitrite is 1:1-1.5:1; the molar ratio of the aniline to the phenol is 1:1-1.5:1.
(2) 6-hydroxyhexyl-4-azo phenyl ether (AzoC) 6 OH) preparation: adding 4-hydroxyazobenzene, 6-bromohexanol, potassium carbonate (providing an alkaline environment required by the reaction) and potassium iodide (a catalyst) into N, N-dimethylformamide, reacting for 10-15 hours at 75-85 ℃ under the protection of nitrogen atmosphere, adding the product into deionized water after the reaction is cooled to room temperature, extracting with chloroform, adding anhydrous magnesium sulfate into a collected organic phase, stirring for 10-15 hours, suction filtering, rotationally steaming to remove a solvent, recrystallizing with ethanol, suction filtering, and vacuum drying to obtain 6-hydroxyhexyl-4-azo phenyl ether. Wherein the molar ratio of the 4-hydroxyazobenzene to the 6-bromohexanol is 1:1-1:1.5; the molar ratio of the 4-hydroxyazobenzene to the potassium carbonate is 1:1-1:1.5.
(3) 4- (hexyl lipoic acid) oxyazobenzene (AzoC) 6 LA) preparation
6-hydroxyhexyl-4-azo phenyl ether, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), 4-Dimethylaminopyridine (DMAP) and triethylamine (wherein DMAP is a catalyst, EDC is a carboxyl activating agent and triethylamine provides a slightly alkaline environment required by the reaction) are added into anhydrous dichloromethane, an anhydrous dichloromethane solution of lipoic acid is added under stirring, the mixture is stirred for 20-25 hours at 20-30 ℃ under the protection of nitrogen, the solvent is removed by rotary evaporation, and then the mixture is purified by silica gel column chromatography to obtain 4- (lipoic acid hexyl ester) oxyazobenzene.
Wherein the molar ratio of the 6-hydroxyhexyl-4-azo phenyl ether to the lipoic acid is 1:1-1:2; the molar ratio of the 6-hydroxyhexyl-4-azo phenyl ether to EDC is 1:1-1:1.5; the molar ratio of the 6-hydroxyhexyl-4-azo phenyl ether to the DMAP is 4:1-5:1; the molar ratio of the 6-hydroxyhexyl-4-azo phenyl ether to the triethylamine is 1:1-1:2.
（4）PAzoC 6 Preparation of LA-LA copolymer: 4- (hexyl lipoic acid) oxyazobenzene (AzoC) 6 Sequentially adding Dichloromethane (DCM) into LA and Lipoic Acid (LA) to dissolve and mix uniformly, transferring into a polytetrafluoroethylene mold, and polymerizing for 4-6 days at 75-85 ℃ after the solvent volatilizes in the air to obtain the product of the poly lipoic acid material-PAzoC with light-regulating and adhesion-controlling properties 6 LA-LA copolymers (PAL copolymers).
Wherein the mass ratio of the 4- (lipoic acid hexyl ester) oxyazobenzene to the lipoic acid is 2:1-3:1; the product mark is PAL-2 when the mass ratio of the 4- (lipoic acid hexyl ester) oxyazobenzene to the lipoic acid is 2:1; the product was designated PAL-3 when the mass ratio of oxyazobenzene to lipoic acid was 3:1.
FIG. 1 shows PAL-3 copolymer 1 H NMR chart. FIG. 1 shows the appearance of the PAL-3 copolymer at the peak positions, at 2.76 and 1.84 ppm, of broad peaks characteristic of the polythiooctanoic acid chain, and at the position of 7-8 ppm of the azo characteristic peaks, demonstrating the successful preparation of the copolymerization.
2. Properties of PAL copolymer
1. PAL copolymer thermal remodeling Properties
FIG. 2 is a graph of the thermal remodeling properties (a) of PAL-2 copolymer in its original shape; (b 1, b2, b 3) a disruption process; (c) shape after thermal remodeling. The PAL-2 copolymer has the thermal remodeling performance shown in figure 2, the damaged material is filled into a mold, the mold is remolded in an oven at 80 ℃ for 20 minutes, the mold is taken out from the oven and cooled, and then the mold is demolded, thus the PAL-2 copolymer has the shape which is obtained, because the main chain of the copolymer is a dynamic covalent disulfide bond and a non-covalent hydrogen bond crosslinking network formed by carboxyl groups also exists, the PAL-2 copolymer can be quickly subjected to thermal remodeling under milder conditions through dynamic exchange of the disulfide bond and reconstruction of the hydrogen bond.
2. Material repair Properties of PAL copolymer
FIG. 3 shows PAL-3 copolymer repair of different materials (a 1 , a 2 , a 3 ) A plastic; (b) 1 , b 2 , b 3 ) Rubber; (c) 1 , c 2 , c 3 ) Glass. PAL-3 material exhibits good flow property at 80deg.C, so it can be rapidly filled into the broken gap of different materials, and can be cured by crystallization at room temperature to obtain good repairing performance for various materials, and in FIG. 3, repairing of plastics, rubber and glass is shown. Meanwhile, as the polymer contains carboxyl hydrogen bonds, for the material with polyhydroxy on the surface of glass, the material can form hydrogen bond interaction with copolymer, so that the material can bear larger external force without damage, as shown in figure 3 (c) 3 ) The repaired air plug shown can withstand a weight of 200 g.
3. pH response Properties of PAL copolymer
FIG. 4 shows the pH response properties of PAL-3 copolymer (a) saturated sodium chloride solution; (b) an acid solution at ph=1; (c) lye at ph=13. The PAL-3 copolymer has different stability in aqueous solutions of different pH values, and is stable in neutral saturated sodium chloride solution and acid solution of ph=1, and does not swell. And the depolymerization of the material under alkaline conditions is shown in fig. 4 (c), the color of the solution changes, and the polymer becomes hard and brittle and automatically falls off from the notch position, which is based on the degradation of the main chain of the polythiooctanoic acid under alkaline conditions, so that the material is disabled.
4. PAL copolymer adhesion Property (glass plate lap shear test)
The testing method comprises the following steps: placing the prepared polymer in an oven at 80 ℃ for 20 min, coating the polymer between two glass plates when the polymer is in a viscous state, applying a certain force to uniformly distribute the polymer at a lap joint position, and testing the polymer at room temperature by a MOXIN MX-0350 pulling machine after cold cutting and curing at room temperature, wherein the adhesion strength (G) is calculated by the following formula:
f is the force required to pull the overlapping glass sheets apart and S is the overlap area.
The stress strain curve of the PAL copolymer is shown in FIG. 5, and the copolymer has better adhesion performance compared with two monomers because the copolymer not only contains carboxyl groups and can form hydrogen bond interaction with the glass substrate to generate adhesion performance; the adhesive material can be used for achieving good flowing property of a viscous state under a milder condition (80 ℃), filling gaps among required adhesive materials, and then performing crystallization, solidification and enhancement at room temperature, so that the adhesive material has stronger adhesive property. Whereas PAL-2 has better adhesion properties than PAL-3 because PAL-2 contains more lipoic acid components, which contain more carboxyl groups to enable stronger hydrogen bond interactions between glass substrates, resulting in further enhancement of adhesion properties.
5. Photo-response Properties of PAL copolymer
Contact angle test method of copolymer: the prepared polymer is dissolved in a small amount of DCM, the solution is dripped on the surface of a clean silicon wafer, the solvent is volatilized to form a film, then the film is subjected to heat treatment in an oven at 80 ℃ for one minute, the solvent is volatilized completely, and the sample is cooled and then passes through a DAS 10-MK2 droplet shape analyzer to be tested at room temperature.
FIG. 6 shows the contact angle test (a) of PAL copolymer 1 , b 1 ) Preparing a sample; (a) 2 , b 2 ) Ultraviolet light (365 nm) for 10 minutes; (a) 3 , b 3 ) Visible light (470 nm) for 10 minutes. FIG. 7 shows PAL copolymer was subjected to ultraviolet irradiation (365, nm) for 10 minutes and visible irradiation (47)0 nm) stress strain curve after 3 cycles for 10 minutes compared to the untreated sample.
Since the PAL copolymer contains an azobenzene group, the PAL copolymer has stimulus response to ultraviolet light and visible light, the isomerization polarity of azobenzene from trans to cis is increased under the ultraviolet light, and the isomerization polarity of azobenzene from cis to trans is restored under the visible light. However, as can be seen from the contact angle experiment in fig. 6, the contact angle of the new sample is increased after the new sample is irradiated by ultraviolet light for 10 minutes, in theory, the contact angle of the copolymer is reduced because the azobenzene is contained and the polarity is increased after the new sample is irradiated by ultraviolet light, and the opposite result is presumably that the azobenzene group in the copolymer migrates from the bulk of the polymer to the surface after the new sample is irradiated by ultraviolet light, so that the new sample can replace a part of carboxyl on the surface, the hydrophilicity is reduced, and the contact angle is increased; and after irradiation of visible light, the polarity of azobenzene is changed from cis to trans, the hydrophilicity is further reduced, and the contact angle is further increased.
The adhesion performance enhancement after the light treatment in fig. 7 can also be explained by this: the glass substrate is a material containing defects in microcosmic, and the azobenzene groups are converted from rod-shaped trans-cis to surface migration through ultraviolet irradiation, so that the azobenzene groups can enter the defects of the glass substrate, and then return to the rod-shaped trans after visible light irradiation, so that tight contact is formed between the azobenzene groups and the glass substrate, and the adhesion performance of the azobenzene groups is enhanced.
In conclusion, the azobenzene-containing lipoic acid monomer prepared by the esterification reaction and the lipoic acid monomer are copolymerized under a milder condition, so that the material which is crystallized and solidified at room temperature is obtained. The main chain of the copolymer is dynamic covalent disulfide bond and contains partial carboxyl side chains, so that the copolymer can be subjected to thermal remodeling through dynamic exchange of disulfide bonds and reconstruction of hydrogen bond networks under mild conditions and recycled. The copolymer is in a viscous state with good flowing performance at 80 ℃ and is in a crystallization solidification state at room temperature, the copolymer can be repaired regardless of the type of materials by utilizing the property, the copolymer is coated on the damaged position of the materials in the viscous state, and then the materials are repaired by crystallization solidification enhancement at the room temperature, so that the materials capable of forming hydrogen bonds with the copolymer can better resist damage of external force after the repair is completed. The side group also contains an azo phenyl group with photoresponsive property, so that the azo phenyl group has excellent photo-adjustable adhesion property.
Drawings
FIG. 1 shows PAL-3 copolymer 1 H NMR chart.
FIG. 2 is a graph of the thermal remodeling properties (a) of PAL-2 copolymer in its original shape; (b 1, b2, b 3) a disruption process; (c) shape after thermal remodeling.
FIG. 3 shows PAL-3 copolymer repair of different materials (a 1 , a 2 , a 3 ) A plastic; (b) 1 , b 2 , b 3 ) Rubber; (c) 1 , c 2 , c 3 ) Glass.
FIG. 4 shows the pH response properties of PAL-3 copolymer (a) saturated sodium chloride solution; (b) an acid solution at ph=1; (c) lye at ph=13.
FIG. 5 is a stress strain curve of PAL copolymer.
FIG. 6 shows the contact angle test (a) of PAL copolymer 1 , b 1 ) Preparing a sample; (a) 2 , b 2 ) Ultraviolet light (365 nm) for 10 minutes; (a) 3 , b 3 ) Visible light (470 nm) for 10 minutes.
FIG. 7 is a stress strain curve of PAL copolymer after 10 minutes of ultraviolet light (365, nm) and 3 cycles of visible light (470, nm) compared to non-light treated samples.
Detailed Description
The preparation method of the poly-lipoic acid material with the light-regulated adhesion-controlled performance is further described in detail below.
The materials and reagents used in the invention are as follows:
lipoic acid (LA, AR) from MERYER, aniline (AR) from MERYER, phenol (AR) from MERYER, 6-bromohexanol (AR) from Damas-beta,1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC, AR) from Damas-beta, 4-dimethylaminopyrazinePyridine (DMAP, AR) was purchased from Damas-beta, concentrated hydrochloric acid (36.5%) was purchased from Hangzhou double forest chemical reagent Co., ltd, chloroform (AR) was purchased from Hangzhou double forest chemical reagent Co., ltd, methylene chloride (DCM, AR) was purchased from Shanghai laboratory equipment Co., ltd, sodium carbonate (Na) 2 CO 3 AR), potassium iodide (KI, AR) purchased from Shanghai laboratory equipment Co., ltd, sodium hydroxide (NaOH, AR) purchased from Shanghai laboratory equipment Co., ltd, petroleum ether (PE, AR) was purchased from Shanghai laboratory equipment Co., ltd, and ethyl acetate (EA, AR) was purchased from Shanghai laboratory equipment Co., ltd.
The instrument used in the invention is as follows:
the structure of the material was characterized by nuclear magnetic resonance spectrometer AVANCE AV400MHz (Bruker, switzerland), the mechanical properties of the material were tested by tensile machine MOXIN MX-0350 (Jiangsu Moxi industries systems, inc. of China), and the contact angle of the material was tested by droplet shape analyzer DSA 10-MK2 (Kruss, germany).
Examples
(1) Preparation of 4-hydroxyazobenzene (AzoOH): aniline (5.1167 g, 54.94 mmol) was dissolved in hydrochloric acid (32 mL, 6 mol/L) under ice-water bath conditions, the reaction system temperature was kept below 5 ℃, and an aqueous sodium nitrite solution (25 mL, 2 mol/L) was slowly added dropwise to the reaction system to prepare a diazonium salt solution. Phenol (7.8220 g, 53.12 mmol) was dissolved in aqueous sodium hydroxide (50.00 ml,1.01 mol/L) and the diazonium salt solution prepared above was slowly added to give a yellow precipitate which was filtered and the product dried overnight at 80 ℃ to give a yellow powdered solid in 92.90% yield.
(2) Preparation of 6-hydroxyhexyl-4-azo phenyl ether (AzoC 6 OH): 4-hydroxyazobenzene (1.9943 g, 10.06 mmol), 6-bromohexanol (1.9682 g,10.87 mmol), potassium carbonate (1.4249 g, 10.31 mmol) and potassium iodide (trace amounts) were added to a round bottom flask containing 50 mL of N, N-Dimethylformamide (DMF). The reaction system was reacted at 80℃under nitrogen atmosphere for 12h, after the reaction was completed, cooled to room temperature, the product was added to 300mL deionized water, extracted with chloroform (300 mL), and anhydrous magnesium sulfate (3.0162 g, 25.06 mmol) was added to the collected organic phase and stirred for 12 hours, filtered, after the solvent was removed by rotary evaporation, recrystallized from ethanol and filtered by suction to obtain the product, which was dried overnight in a vacuum oven at 70℃to obtain a yellow powdery solid with a yield of 68.71%.
(3) 4- (hexyl lipoic acid) oxyazobenzene (AzoC) 6 LA) preparation
6-hydroxyhexyl-4-azobenzene ether (2.1315 g,6.73 mmol), EDC (1.6157 g,8.43 mmol), DMAP (0.1791 g,1.47 mmol) and triethylamine (1.2276 g,12.13 mmol) were charged to a three-necked round bottom flask containing 30 ml anhydrous Dichloromethane (DCM) under nitrogen. Lipoic acid (2.7009 g,13.44 mmol) was dissolved in anhydrous DCM (8 mL). An anhydrous dichloromethane solution of lipoic acid was added dropwise to the system by stirring. The mixture was stirred at 25 ℃ for 24 hours. The solvent was removed by rotary evaporation without any additional purification. The mixture was then purified by column chromatography on silica gel with PE: EA (8:1 v/v) as eluent. A bright yellow powdery solid was obtained in a yield of 70.23%.
（4）PAzoC 6 Preparation of LA-LA copolymers
In a 50 mL flask, azoC was added sequentially 6 LA (0.3009 g), LA (0.1001 g), and DCM (10 mL) are added to dissolve and mix uniformly, and then transferred into a polytetrafluoroethylene mold, and placed into 80 after the solvent volatilizes in the air o Polymerization was carried out in an oven C, and after 5 days, the product was obtained. The resulting product was designated PAL-3, wherein the number represents AzoC 6 The mass feed ratio of LA to LA was 3:1. AzoC control according to the same method 6 The mass feed ratio of LA to LA is 2:1, standardAnd is designated as PAL-2.
Claims (7)
1. A preparation method of a poly-lipoic acid material with light-regulated adhesion performance comprises the following steps:
(1) Preparation of 4-hydroxyazobenzene: dissolving aniline in hydrochloric acid under the condition of ice water bath, keeping the temperature of a reaction system at 0-5 ℃, and adding sodium nitrite aqueous solution into the reaction system to prepare diazonium salt solution; dissolving phenol in sodium hydroxide aqueous solution, slowly adding the prepared diazonium salt solution to generate yellow precipitate, filtering and drying to obtain 4-hydroxyazobenzene;
(2) Preparation of 6-hydroxyhexyl-4-azo phenyl ether: adding 4-hydroxyazobenzene, 6-bromohexanol, potassium carbonate and potassium iodide into N, N-dimethylformamide, reacting for 10-15 hours at 75-85 ℃ under the protection of nitrogen atmosphere, cooling to room temperature after the reaction is finished, adding the product into deionized water, extracting with chloroform, adding anhydrous magnesium sulfate into the collected organic phase, stirring for 10-15 hours, carrying out suction filtration, removing the solvent by rotary evaporation, recrystallizing with ethanol, carrying out suction filtration, and carrying out vacuum drying to obtain 6-hydroxyhexyl-4-azo phenyl ether;
(3) Preparation of 4- (hexyl lipoic acid) oxyazobenzene
Adding 6-hydroxyhexyl-4-azo phenyl ether, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 4-dimethylaminopyridine and triethylamine into anhydrous dichloromethane, adding an anhydrous dichloromethane solution of lipoic acid under stirring, stirring the mixture at 20-30 ℃ for 20-25 hours under the protection of nitrogen, removing the solvent by rotary evaporation, and purifying the mixture by using silica gel column chromatography to obtain 4- (lipoic acid hexyl ester) oxyazobenzene;
（4）PAzoC 6 preparation of LA-LA copolymers
Sequentially adding 4- (lipoic acid hexyl ester) oxyazobenzene and lipoic acid into methylene dichloride to dissolve and mix uniformly, transferring into a polytetrafluoroethylene mold, and polymerizing for 4-6 days at 75-85 ℃ after the solvent volatilizes in the air to obtain the product of the poly lipoic acid material PAzoC with light-regulated adhesion-controlled performance 6 LA-LA copolymers.
2. The method for preparing the poly-lipoic acid material with the light-regulated adhesion performance according to claim 1, which is characterized in that: in the step (1), the molar ratio of aniline to sodium nitrite is 1:1-1.5:1; the molar ratio of the aniline to the phenol is 1:1-1.5:1.
3. The method for preparing the poly-lipoic acid material with the light-regulated adhesion performance according to claim 1, which is characterized in that: in the step (2), the molar ratio of the 4-hydroxyazobenzene to the 6-bromohexanol is 1:1-1:1.5.
4. The method for preparing the poly-lipoic acid material with the light-regulated adhesion performance according to claim 1, which is characterized in that: in the step (2), the molar ratio of the 4-hydroxyazobenzene to the potassium carbonate is 1:1-1:1.5.
5. The method for preparing the poly-lipoic acid material with the light-regulated adhesion performance according to claim 1, which is characterized in that: in the step (3), the molar ratio of the 6-hydroxyhexyl-4-azo phenyl ether to the lipoic acid is 1:1-1:2.
6. The method for preparing the poly-lipoic acid material with the light-regulated adhesion performance according to claim 1, which is characterized in that: in the step (3), the molar ratio of the 6-hydroxyhexyl-4-azo phenyl ether to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 1:1-1:1.5; the molar ratio of the 6-hydroxyhexyl-4-azo phenyl ether to the 4-dimethylaminopyridine is 4:1-5:1; the molar ratio of the 6-hydroxyhexyl-4-azo phenyl ether to the triethylamine is 1:1-1:2.
7. The method for preparing the poly-lipoic acid material with the light-regulated adhesion performance according to claim 1, which is characterized in that: in the step (4), the mass ratio of the 4- (lipoic acid hexyl ester) oxyazobenzene to the lipoic acid is 2:1-3:1.
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| CN113061263A (en) * | 2021-04-06 | 2021-07-02 | 华东理工大学 | Preparation method of photocrosslinking dynamic reversible supramolecular polymer adhesive based on lipoic acid micromolecular compound |
| CN113583180A (en) * | 2021-08-11 | 2021-11-02 | 浙江理工大学龙港研究院有限公司 | Polyionic liquid containing thioctic acid anions and preparation method thereof |
| WO2022109959A1 (en) * | 2020-11-26 | 2022-06-02 | 苏州大学 | Chiral azobenzene polymer crosslinked thin film and preparation method therefor and application thereof |
| CN114605960A (en) * | 2022-03-23 | 2022-06-10 | 东南大学 | Adhesive with reversible photo-thermal response and preparation method and application thereof |
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| WO2022109959A1 (en) * | 2020-11-26 | 2022-06-02 | 苏州大学 | Chiral azobenzene polymer crosslinked thin film and preparation method therefor and application thereof |
| CN113061263A (en) * | 2021-04-06 | 2021-07-02 | 华东理工大学 | Preparation method of photocrosslinking dynamic reversible supramolecular polymer adhesive based on lipoic acid micromolecular compound |
| CN113583180A (en) * | 2021-08-11 | 2021-11-02 | 浙江理工大学龙港研究院有限公司 | Polyionic liquid containing thioctic acid anions and preparation method thereof |
| CN114605960A (en) * | 2022-03-23 | 2022-06-10 | 东南大学 | Adhesive with reversible photo-thermal response and preparation method and application thereof |
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