CN115572370A - Light response epoxy resin based on azopyridine structure and preparation method and light response method thereof - Google Patents
Light response epoxy resin based on azopyridine structure and preparation method and light response method thereof Download PDFInfo
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- CN115572370A CN115572370A CN202211407916.XA CN202211407916A CN115572370A CN 115572370 A CN115572370 A CN 115572370A CN 202211407916 A CN202211407916 A CN 202211407916A CN 115572370 A CN115572370 A CN 115572370A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 75
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 75
- VJTJVFFICHLTKX-UHFFFAOYSA-N dipyridin-2-yldiazene Chemical group N1=CC=CC=C1N=NC1=CC=CC=N1 VJTJVFFICHLTKX-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000004298 light response Effects 0.000 title description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- -1 polysiloxane Polymers 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 20
- 230000004044 response Effects 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 230000001678 irradiating effect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 26
- 238000001723 curing Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 18
- 239000004593 Epoxy Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- ZCIFWRHIEBXBOY-UHFFFAOYSA-N 6-aminonicotinic acid Chemical compound NC1=CC=C(C(O)=O)C=N1 ZCIFWRHIEBXBOY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000009193 crawling Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Images
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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
Abstract
The invention discloses an optical response epoxy resin based on an azopyridine structure, which comprises the following steps: dissolving the amino derivative containing the azopyridine structure and an epoxy resin monomer in N, N-dimethylformamide, pouring into a mold, drying the solvent in an oven at 50 ℃, and heating to 120-160 ℃ for curing reaction for 4-5 hours to obtain the photoresponse epoxy resin. The photoresponse method of the photoresponse epoxy resin comprises the following steps: stretching the epoxy resin by 5-100% at 70-150 ℃, cooling to room temperature, deforming the epoxy resin under the irradiation of ultraviolet light of 340-380nm, continuously irradiating the deformed position with visible light of 420-460nm, and recovering the epoxy resin. The preparation method of the photo-response epoxy resin based on the azopyridine structure is simple, the curing temperature is low, the curing reaction time is short, and meanwhile, the material has excellent mechanical property, shape memory property and photo-response property and has wide application prospect in the field of intelligent materials.
Description
Technical Field
The invention relates to the technical field of photoresponse materials, in particular to a photoresponse epoxy resin based on an azopyridine structure, a preparation method thereof and a photoresponse method.
Background
The stimuli-responsive polymer material, as one of polymer-based intelligent materials, is very sensitive to external stimuli such as temperature, pH value, light, voltage and the like, and the stimuli can cause reversible or irreversible transformation of the structure or state of the material, so that the material has some special functions. These special functions can satisfy certain special requirements of people for materials. Compared with other response behaviors, the light response has the advantages of quick response, remote regulation and control, no by-product generation, safety, reliability and the like, and can be widely applied to the fields of light orientation, light regulation and control, surface relief gratings and the like. The light braking material simulates the movement of organisms through the reversible deformation of the material under the light stimulation, and is widely applied in the field of bionics. For example: the optical brake may also mimic human movements such as crawling/walking, rolling, grabbing objects, jumping, swimming, and the like. Therefore, the optical braking material has a wide application prospect.
Epoxy resins have excellent mechanical properties, chemical resistance and thermal stability and are widely used in the fields of construction, coatings, decoration, electronics, industrial molds and the like. Relatively few researches are carried out in the field of epoxy resin for photobraking, and the reported photobraking epoxy resin is mainly obtained by curing epoxy monomer containing an azobenzene structure and long-chain alkyl diacid generated by azobenzene diphenol and epoxy chloropropane. For example, michael r.kessler (acsappl. Mater.interacesses 2016,8, 15750-15757) and Yue Zhao (adv.mater.2017, 29,1606467 and adv.mater.2018,30, 1706597) cure at high temperature with epoxy monomers containing azobenzene structures and sebacic acid and dodecanedioic acid, respectively, to give photoresponsive epoxy resins. Because the carboxylic acid curing epoxy resin needs higher temperature, the epoxy resin is prepared by firstly reacting the epoxy monomer containing azobenzene structure with long-chain alkyl diacid at 145 ℃ for about 12 hours, and then continuously heating for 12 hours to remove the solvent. The subsequent hot pressing of the polymer particles at 180 ℃ is required. The method has high reaction temperature, long time and complex preparation process, and limits the application of materials.
Disclosure of Invention
The invention provides a preparation method of a photoresponse epoxy resin material, which is low in curing temperature, short in curing time and simple in process, and aims to solve the problems of high curing temperature, long curing time, complex curing process and the like of the existing photoinduced epoxy resin.
The photoresponse epoxy resin based on the azopyridine structure is prepared by carrying out curing reaction on an amino derivative containing the azopyridine structure and an epoxy resin monomer at the temperature of 120-160 ℃ for 4-5h according to the molar ratio of 1 (1-2).
The molecular structural formula of the amino derivative containing the azopyridine structure is as follows:
in the formula, R 1 Is one of the following structural formulas:
the value of m ranges from 1 to 11.
The molecular structure general formula of the epoxy resin monomer is as follows:
in the formula, R 2 Is one of the following structural formulas:
wherein the value range of n is 1-10.
The specific preparation method of the azo pyridine structure-based photoresponse epoxy resin comprises the following steps:
dissolving an amino derivative containing an azopyridine structure and an epoxy resin monomer in N, N-dimethylformamide according to a molar ratio of 1.
The synthesis method of the azo dipyridyl amino derivative comprises the following steps: at room temperature, azobipyridyl acyl chloride is dissolved in dry dichloromethane, flexible long-chain diamine is added, and synthesis is carried out under the catalysis of triethylamine.
Preferably, the flexible long-chain diamine is one of polysiloxane, polyether amine and polyethylene glycol diamine with the molecular weight of 100-800.
The photoresponse method of the photoresponse epoxy resin based on the azopyridine structure comprises the following steps: stretching the epoxy resin by 5-100% at 70-150 ℃, cooling to room temperature, deforming the epoxy resin under the irradiation of 340-380nm ultraviolet light, and continuously irradiating the deformed position with 420-460nm visible light to restore the original shape of the epoxy resin.
Compared with the prior art, the invention has the advantages that:
firstly, the photoreactive epoxy resin of the invention introduces an azo dipyridine structure with optical activity, and the photoinduced action of the epoxy resin material is realized through the photoresponse reversible cis-trans isomerization of the azo dipyridine structure. After the obtained epoxy resin is irradiated by ultraviolet light with the wavelength of 340-380nm, the material deforms; and continuously irradiating the deformation position by using visible light with the wavelength of 420-460nm, and recovering the material. The light is used as a stimulation source, and the device has the advantages of remote non-contact control, accurate positioning, instantaneous switch and the like.
Secondly, the photoresponse epoxy resin is obtained by curing reaction of amino derivatives containing an azobipyridine structure and epoxy resin monomers at 120-160 ℃ for 4-5 h. Compared with the reported photoresponse epoxy resin, the curing temperature is lower, the curing time is obviously shortened, and the curing process is simpler.
And thirdly, the photoresponse epoxy resin has higher crosslinking density, the tensile strength reaches 37.3MPa, and the tensile strength is improved by about 60 percent compared with the optical actuation azobenzene epoxy resin material. The material has excellent mechanical property, shape memory property and light response property, and has wide application prospect in the field of intelligent materials.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of sodium azopyridinedicarboxylate.
FIG. 2 is an infrared spectrum of an azo-pyridine diamine derivative Abpy-PEA.
FIG. 3 is a diagram showing an ultraviolet absorption spectrum of an azo-pyridyldiamine derivative Abpy-PEA.
FIG. 4, DSC of epoxy E51 and azopyridinediamine derivatives before curing.
FIG. 5 is a DSC of epoxy E51 cured with an azopyridinediamine derivative.
FIG. 6 is an infrared spectrum of a photoresponsive epoxy resin film E51/Abpy-PEA based on an azopyridine structure.
FIG. 7 is a graph showing the photoresponse of the azo-pyridine structure-based photoresponse epoxy resin thin film E51/Abpy-PEA.
FIG. 8 is a diagram showing the shape memory process of the light-responsive epoxy resin film E51/Abpy-PEA based on the azopyridine structure.
FIG. 9 is a stress-strain diagram of a photoresponsive epoxy resin thin film E51/Abpy-PEA based on an azopyridine structure.
FIG. 10 IR spectra of epoxy E51 and blocked azopyridyldiamine E51/Terminated Abpy-PEA.
FIG. 11, DSC of epoxy E51 before reaction with blocked azopyridinediamine E51/Terminated Abpy-PEA.
FIG. 12, DSC of epoxy E51 after reaction with blocked azopyridinediamine E51/Terminated Abpy-PEA.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
A preparation method of an azopyridine structure-based photoresponse epoxy resin comprises the following steps:
(1) Preparation of azopyridinedicarboxylic acids
Weighing 9g of 6-aminonicotinic acid into a round-bottom flask, preparing 10 percent sodium hydroxide aqueous solution by mass fraction, measuring 45ml of the aqueous solution, adding the aqueous solution into the round-bottom flask, and uniformly stirring by magnetic force. Under the condition of ice-water bath, 135ml of NaClO solution is dripped, and the dripping time is controlled to be about 15 min; after the dropwise addition, the mixture was stirred for 1 hour under ice-water bath conditions. After 1h, 90ml of NaClO solution is added again, and the reaction is still carried out under the ice-water bath condition for 3h.
After the reaction, the mixed solution obtained by the reaction was filtered by a funnel, and the obtained filtrate was filtered after being treated with NaOH pellets. Dissolving the solid obtained by filtering twice in 250ml of 1mol/L NaOH solution to obtain red solution, pouring the red solution into a round-bottom flask, heating to 50 ℃, and adding activated carbon for treating for 30min; cooling the obtained solution to room temperature, and then using SiO 2 Filtering the powder, acidifying the obtained solution with concentrated hydrochloric acid to make the pH of the solution be 3-4; filtering the pink precipitate obtained in the acidification process, washing to be neutral, and drying to obtain the azopyridine dicarboxylic acid.
The reaction equation is as follows:
FIG. 1 is a nuclear magnetic hydrogen spectrum of sodium azopyridinedicarboxylate. Since the dicarboxylic acid was not soluble in deuterated water, it was tested by changing it to a sodium salt with sodium carbonate and then dissolving it in deuterated water. The displacements in the figure are: δ =4.7ppm (deuterated water), 8.92-8.93ppm (2H), 8.34-8.37ppm (2H), 7.87-7.89ppm (2H).
(2) Preparation of azopyridine dicarboxylic acid dichloride
Grinding dry azodipicolinic acid into powder, weighing 1g of azodipicolinic acid in a round-bottom flask, and adding 15ml of thionyl chloride solution into the same round-bottom flask in a fume hood; setting up an experimental device, and placing a drying pipe filled with potassium carbonate particles on the upper part of a condensation pipe; the reaction temperature was set at 78 ℃ and the reaction time was 12h under magnetic stirring.
After the reaction is finished, carrying out rotary evaporation on the obtained solution to remove unreacted thionyl chloride in the system; ultrasonically dissolving the solid obtained after rotary evaporation by using a proper amount of dichloromethane, and filtering by using a sand core funnel after dissolving; pouring the obtained filtrate into a round-bottom flask with known weight for rotary evaporation to obtain a certain amount of azopyridine diacid chloride. The reaction equation is as follows:
(3) Preparation of azopyridinediamine Abpy-PEA
2.57g of polyether diamine with the relative molecular mass of 400 is weighed in a round-bottom flask, 1.43ml of triethylamine is added, and 21.4ml of dichloromethane is used for ultrasonic dissolution; 14.3ml of methylene chloride was added to 1g of the azopyridine diacylchloride obtained in the above-mentioned step to conduct ultrasonic dissolution. Placing the round-bottom flask in an ice bath under the protection of nitrogen, slowly dropwise adding the mixed solution of azopyridine diacyl chloride into the round-bottom flask by using a needle tube, and after dropwise adding, introducing nitrogen for 2min, wherein the reaction time is 24h.
After the reaction is finished, carrying out rotary evaporation on the solution, adding tetrahydrofuran into the obtained solid, and carrying out rotary evaporation twice again to remove triethylamine. At the last rotary evaporation, the solution was poured into a round bottom flask of known weight in order to obtain the quality of azopyridinediamine (Abpy-PEA). And finally, pumping for 15-20min by using an oil pump to remove the residual tetrahydrofuran. The reaction equation is as follows:
FIG. 2 is an infrared spectrum of an azo-pyridyldiamine derivative Abpy-PEA, in which: 3488cm -1 Is the stretching vibration absorption peak of-NH 2 and-NH-in amide, 1644cm -1 And 1374cm -1 The peak of absorption of stretching vibration of-C = O-and-C-N-in the amide bond, respectively, is 1544cm -1 Is a stretching vibration absorption peak of-N = N-in the azopyridine structure, 1105cm -1 Is a stretching vibration absorption peak of ether bond-C-O-C-, 2927cm -1 ,2973cm -1 ,2873cm -1 Are each-CH-, -CH 3 ，-CH 2 -a peak of absorption of stretching vibration.
FIG. 3 is a graph of the UV absorption spectrum of the azo-pyridine diamine derivative Abpy-PEA, wherein: and an azo trans-structure absorption peak is at 365nm, and an azo cis-structure absorption peak is at 450 nm.
(4) Preparation of photoresponse epoxy resin film E51/Abpy-PEA
Preparing a photoresponse epoxy resin film by using the azopyridine diamine derivative and epoxy resin: 0.128g of bisphenol A epoxy resin and 0.17g of an azopyridinediamine derivative (Abpy-PEA) (molar ratio 2; pouring the uniformly dispersed solution into a mould, and putting the mould into a drying oven at 50 ℃ for drying. After a period of time, it is cured: the oven was warmed to 120 ℃ over 10min for 2h, then the oven was warmed to 160 ℃ over 10min for 2h. After completion of curing, the film was taken out with tweezers, inspected for the presence of defects such as air bubbles, and then stored. The chemical reaction formula is as follows:
FIG. 4 is a DSC chart of epoxy E51 and azopyridinediamine derivatives before curing, and the information in the chart proves that the curing reaction temperature of epoxy E51 and azopyridinediamine derivatives is about 150 ℃.
FIG. 5 is a DSC of cured epoxy E51 and an azopyridinediamine derivative, wherein the information demonstrates that the glass transition temperature of the epoxy resin obtained by curing the epoxy E51 and the azopyridinediamine derivative is about 42 ℃.
FIG. 6 is an infrared spectrum of a photoresponsive epoxy resin film E51/Abpy-PEA based on an azopyridine structure, wherein: 3424cm -1 is-NH 2 And a stretching vibration absorption peak of-NH-in amide, 1644cm -1 And 1374cm -1 respectively-C = O and-C-N-in the amide bond, and 1509cm -1 Is a stretching vibration absorption peak of-N = N-in the azopyridine structure, 1105cm -1 Is the absorption peak of ether bond-C-O-C-stretching vibration, 1249cm -1 、921cm -1 And 829cm -1 Is a characteristic peak of the epoxy group, 2969cm -1 、2871cm -1 And 2929cm -1 Are each-CH 3 、-CH 2 -C-H-and a stretching vibration absorption peak.
FIG. 7 is a graph showing the photoresponse of an azopyridine structure-based photoresponse epoxy resin film E51/Abpy-PEA, wherein a 3.1 cm-thick sample strip is stretched at 50 ℃ and oriented, the film is held by tweezers, and the film is placed under 365nm ultraviolet light, so that the deformation of the film at the light source irradiation position is clearly observed, and the film is bent in the light source direction. This phenomenon indicates that the azopyridine structure is converted from a stable trans structure to a cis structure under 365nm ultraviolet light, and the photoresponse epoxy resin film has the capability of light-induced deformation.
FIG. 8 is a diagram showing a shape memory process of an azo-pyridine structure-based photo-responsive epoxy resin film E51/Abpy-PEA, wherein before taking, the original length of a sample strip of the photo-responsive epoxy resin film is 2.1cm; stretching and orientation are carried out at 50 ℃ through external force,the length of the film sample strip is 3.6cm; the external force is cancelled, and the sample strip after stretching is placed in ice water for cooling, and the sample strip is changed into 3.5cm; finally, after the sample is placed in an environment of 50 ℃, the sample returns to 2.3cm. By calculating the fixation ratio R of the photoresponse epoxy resin film f And a recovery rate R r To obtain R f ＝93％、R r =86%, indicating that the film has an excellent shape memory function.
FIG. 9 is a stress-strain graph of an azo-pyridine structure-based photo-responsive epoxy resin film E51/Abpy-PEA, wherein the prepared photo-responsive epoxy resin film was trimmed into a long strip for tensile property test, the width of the sample was 5mm, the thickness was 0.25mm, the original mark was 11.73mm, and the tensile rate was 20mm/min. The test is carried out for 5 times, the average value is taken, the average maximum tensile stress of the photoresponse epoxy resin film is 39.8N, the average elastic modulus is 617.96MPa, the average tensile strength is 37.3MPa, the average elongation at break is 54.4 percent, and the tensile stress at break is 0.65MPa under the tensile speed of 20mm/min. The elongation at break of a conventional epoxy resin film made of E51 was 36%.
Example 2
The preparation of azopyridinedicarboxylic acid and azopyridinedicarboxylic acid dichloride was carried out in the same manner as in steps (1) and (2) of example 1.
(3) Preparation of blocked azopyridinediamines
Dissolving 0.235g of acrylonitrile in 10ml of anhydrous methanol, and dissolving 2.3g of azopyridine diamine in 2ml of anhydrous methanol; and dropwise adding the methanol solution of azopyridine diamine into the anhydrous methanol solution of acrylonitrile for 30min, and dropwise adding in an ice bath. After the dropwise addition, the reaction conditions were changed to room temperature and stirred magnetically for 24h.
After the reaction is finished, carrying out rotary evaporation on the obtained solution, adding a proper amount of tetrahydrofuran for dissolving and carrying out rotary evaporation to remove methanol in the solution; the tetrahydrofuran which was not removed was removed by oil pumping. The reaction equation is as follows:
(4) Preparation of photoresponsive epoxy resin film
Preparing a photoresponse epoxy resin film by using the blocked azopyridine diamine and epoxy resin: taking 0.25g of bisphenol A epoxy resin and 0.085g of blocked azopyridine diamine (the molar ratio is 1; pouring the uniformly dispersed solution into a mould, and putting the mould into a 50 ℃ oven for drying. After drying, heating and curing the film, wherein the curing program is as follows: firstly heating to 200 ℃, keeping for 2h, then heating to 265 ℃ and curing for 2h. After completion of curing, the film was taken out with tweezers and stored after checking for no problem. The reaction equation is as follows:
FIG. 10 is an infrared spectrum of epoxy E51 and blocked azopyridinediamine E51/Terminated Abpy-PEA, compared to the infrared absorption spectrum of FIG. 6 of example 1, the IR absorption spectrum of the end-capped E51/Abpy-PEA is other than-NH-, -N = N-, -C = O, -C-O-C-, -C-N-, -C-H-, -CH 3 、-CH 2 -and outside the characteristic absorption peak of the epoxy group, at 2146cm -1 The peak is the stretching vibration absorption peak of-C ≡ N, which shows that the experimental process of acrylonitrile-terminated Abpy-PEA is completed.
FIG. 11 is a DSC of epoxy E51 before reaction with blocked azopyridinediamine E51/Terminated Abpy-PEA, where the peak temperature illustrates that the curing temperature of E51 with blocked Abpy-PEA is 264 ℃.
FIG. 12 is a DSC of the reaction of epoxy E51 with blocked azopyridinediamine E51/Terminated Abpy-PEA, where the glass transition temperature of the film is clearly observed to be 20 ℃ and also indicates the completion of curing.
In conclusion, the invention realizes the photoinduced effect of the photoresponse epoxy resin through the photoresponse property of the azopyridine structure by introducing the azopyridine structure into the main chain of the epoxy resin. The preparation method of the photo-response epoxy resin based on the azopyridine structure is simple, the curing temperature is low, the curing reaction time is short, and meanwhile, the material has excellent mechanical property, shape memory property and photo-response property, and has wide application prospect in the field of intelligent materials.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation method of photoresponse epoxy resin based on an azopyridine structure is characterized in that amino derivatives containing the azopyridine structure and epoxy resin monomers are dissolved in N, N-dimethylformamide, poured into a mold, heated to 120-160 ℃ after drying a solvent in an oven at 50 ℃ and cured and reacted for 4-5 hours to obtain the photoresponse epoxy resin; the molecular structural formula of the amino derivative containing the azopyridine structure is as follows:
in the formula, R 1 Is one of the following structural formulas:
the value of m ranges from 1 to 11.
2. The method for preparing the photo-responsive epoxy resin based on the azopyridine structure according to claim 1, wherein the molecular structural general formula of the epoxy resin monomer is as follows:
in the formula, R 2 Is one of the following structural formulas:
wherein the value range of n is 1-10.
3. The method for preparing an azo-pyridine structure-based photoresponsive epoxy resin according to claim 2, wherein the molar ratio of the azo-bipyridine structure-containing amine derivative to the epoxy resin monomer is 1 (1-2).
4. The method for preparing the photo-responsive epoxy resin based on the azopyridine structure according to claim 1, wherein the method for synthesizing the azobipyridine amine derivative comprises the following steps: at room temperature, azobipyridyl acyl chloride is dissolved in dry dichloromethane, flexible long-chain diamine is added, and synthesis is carried out under the catalysis of triethylamine.
5. The method for preparing the photo-responsive epoxy resin based on the azopyridine structure according to claim 4, wherein the flexible long-chain diamine is one of polysiloxane, polyether amine and polyethylene glycol diamine with a molecular weight of 100-800.
6. A photoresponsive epoxy resin based on an azopyridine structure, characterized in that it is obtained by a process according to any one of claims 1 to 5.
7. The photoresponse method of the azo-pyridine structure-based photoresponse epoxy resin according to claim 6, characterized in that the epoxy resin is stretched by 5% -100% at 70-150 ℃ and then cooled to room temperature, the epoxy resin deforms under the irradiation of 340-380nm ultraviolet light, the deformation position is continuously irradiated by 420-460nm visible light, and the epoxy resin recovers.
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