CN116874703B - Photoresponse benzoxazine material and preparation method thereof - Google Patents
Photoresponse benzoxazine material and preparation method thereof Download PDFInfo
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- CN116874703B CN116874703B CN202311155931.4A CN202311155931A CN116874703B CN 116874703 B CN116874703 B CN 116874703B CN 202311155931 A CN202311155931 A CN 202311155931A CN 116874703 B CN116874703 B CN 116874703B
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- benzoxazine
- azobenzene
- diamine
- azobenzene structure
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 26
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 72
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 57
- 150000004985 diamines Chemical class 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 8
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000004298 light response Effects 0.000 claims abstract description 7
- 238000001029 thermal curing Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- -1 polysiloxane Polymers 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 229920001451 polypropylene glycol Polymers 0.000 claims description 20
- 238000001723 curing Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 abstract 1
- 230000007334 memory performance Effects 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 29
- 239000000203 mixture Substances 0.000 description 22
- 238000007711 solidification Methods 0.000 description 18
- 230000008023 solidification Effects 0.000 description 18
- 238000004090 dissolution Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- IPHJVOCATFFPSZ-UHFFFAOYSA-N 3-bromo-2-tert-butylimidazo[1,2-a]pyridine Chemical compound C1=CC=CN2C(Br)=C(C(C)(C)C)N=C21 IPHJVOCATFFPSZ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012467 final product Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000002329 infrared spectrum Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000005130 benzoxazines Chemical class 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 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
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000012771 pancakes Nutrition 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- GEQWCUVIQMRCAZ-UHFFFAOYSA-N 2-(4-hydroxyphenyl)butanoic acid Chemical compound CCC(C(O)=O)C1=CC=C(O)C=C1 GEQWCUVIQMRCAZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a photoresponsive benzoxazine material and a preparation method thereof, which belong to the technical field of photoresponsive materials, and are obtained by thermal curing reaction of benzoxazine prepolymer containing azobenzene structures at the temperature of 120-200 ℃; the benzoxazine prepolymer containing the azobenzene structure is prepared by refluxing and stirring diamine containing the azobenzene structure, diphenol and paraformaldehyde in a mixed solvent of toluene and ethanol according to a certain molar ratio; the diamine containing the azobenzene structure is obtained by reacting azobenzene diacid chloride with long-chain diamine. The benzoxazine material provided by the invention is introduced with an optically active azobenzene structure, and the quick photoresponse deformation of the benzoxazine material is realized through the photoreversible isomerization of the azobenzene structure. The prepared benzoxazine material has rapid light response capability and excellent shape memory performance under the irradiation of ultraviolet light with the wavelength of 340-380 nm. Can be applied to the fields of biosensors, intelligent biological switches, soft robots and the like.
Description
Technical Field
The invention relates to the technical field of light response materials, in particular to a light response benzoxazine material and a preparation method thereof.
Background
The light response polymer material is one of the polymer-based intelligent materials, and is a functional polymer material which contains a structure capable of absorbing light energy in the molecule and can generate specific physical or chemical change under the action of light. Such physical or chemical changes may cause structural or morphological changes in the polymer, resulting in macroscopic changes in the material. For example, the material undergoes a change in shape, color, transparency, or refractive index under illumination, etc. The light used as a stimulus source has the advantages of quick response, remote regulation and control, no byproduct generation, safety, reliability and the like, and the advantages lead the light response polymer material to have wide application prospect in the fields of biosensors, intelligent biological switches, micro-fluid conduction soft robots, artificial muscles and the like.
The benzoxazine resin is a thermosetting resin with high heat resistance, high mechanical property, low water absorption, low dielectric property and flexible molecular design, so that the benzoxazine resin has very wide application prospect in the field of functional materials. At present, research on benzoxazines containing azo structures is mainly focused on benzoxazines (CN 108997547A, CN 108997548A) synthesized by phenol compounds containing azo structures and aromatic amine compounds and benzoxazines (CN 108997546A) synthesized by aniline compounds containing azo structures and phenol compounds, and the synthesized benzoxazines have relatively large rigidity due to relatively large crosslinking density of resin, so that the benzoxazines have relatively poor toughness and relatively low elongation at break, cannot realize orientation of azo groups, and do not have photo-deformability. In order to improve the flexibility of benzoxazine resins, we have also prepared flexible azo-containing benzoxazine elastomers (CN 110105517A) by reacting azo-containing phenols with long chain diamines. Although the toughness of the benzoxazine is improved, the benzoxazine has a lower glass transition temperature, and the shape after stretching cannot be fixed. Meanwhile, as the azo group is connected to the phenol, after cross-linking and curing, the azo group is close to the cross-linking center. For both reasons, azo groups in the synthesized azo-structure containing benzoxazine elastomer cannot be oriented, and do not have the ability to photodeformation.
According to the method, azobenzene dicarboxylic acid is used as a raw material, diamine containing azo structures is obtained through reaction with diamine with long chains, then benzoxazine prepolymer containing azo structures is obtained through reaction with common diphenol, and benzoxazine resin is obtained through ring opening and solidification. Because flexible long-chain diamine exists between the azo group and the generated oxazine ring, the cured benzoxazine can be stretched under the heating condition to successfully orient the azo structure, and the photo-induced deformation of the benzoxazine containing the azo structure is realized.
Disclosure of Invention
In order to solve the problem that the azo structure cannot be oriented and the optical deformation cannot be realized in the benzoxazine material containing the azobenzene structure at the present stage, the invention takes long-chain diamine containing the azo structure as a raw material and can be optically actuated under ultraviolet irradiation.
The quick photoresponse benzoxazine material is obtained by curing reaction of benzoxazine prepolymer containing azobenzene structure at 120-200 ℃; the benzoxazine prepolymer is prepared by refluxing and stirring diamine containing an azobenzene structure, diphenol and paraformaldehyde in a molar ratio of 1:1:4.1-4.4 in toluene for 12h. The benzoxazine prepolymer has the following structural formula:
；
wherein R is 1 Is one of the following structural formulas:
；
wherein, the value range of m is 1-14;
wherein R is 2 Is one of the following structural formulas:
。
the diamine containing the azobenzene structure is obtained by reacting azobenzene diacid chloride with long-chain diamine under the catalysis of triethylamine according to the molar ratio of 2:1:3. The long-chain diamine is one of polypropylene oxide diamine, polysiloxane diamine and alkyl diamine with the molecular weight of 100-1000; the structural formula of the diamine containing the azobenzene structure is as follows:
；
wherein R is 1 Is one of the following structural formulas:
；
wherein, the value range of m is 1-14.
The preparation method of the photoresponsive benzoxazine material comprises the following steps:
long-chain diamine was added to a round bottom flask, dissolved in methylene chloride, and then triethylamine as a catalyst was added thereto, and after cooling to 0 ℃, a methylene chloride solution of azobenzene dichloride was added thereto by means of a dropping funnel. After the completion of the dropwise addition, stirring was continued at room temperature for 24 hours. After the reaction is finished, extracting, drying and spin-evaporating to remove the solvent to obtain diamine containing an azobenzene structure;
diamine containing an azobenzene structure, diphenol and paraformaldehyde are uniformly mixed in a mixed solution of toluene and ethanol according to the molar ratio of 1:1:4.1-4.4, then fully reacted for 12 hours at 100-130 ℃, and the solvent is removed by rotary evaporation to obtain a benzoxazine prepolymer containing the azobenzene structure;
dissolving benzoxazine prepolymer in N, N-dimethylformamide, pouring into a mould, firstly drying a solvent at 60 ℃, then raising the temperature to 120-200 ℃ for curing reaction, and finally obtaining the benzoxazine material containing an azobenzene structure;
compared with the prior art, the invention has the following advantages:
firstly, the photoresponsive benzoxazine material is prepared by using long-chain diamine containing an azobenzene structure, so that the problems that the azo structure is close to a crosslinking point after thermocuring and photo-actuation is difficult to orient due to the fact that the benzoxazine is prepared by using aromatic amine containing an azo structure or phenol containing an azo structure in the past are solved;
secondly, the diamine with moderate length is used as the raw material for synthesizing the photo-braking benzoxazine resin, so that the glass transition temperature of the synthesized benzoxazine resin is 20-80 ℃, the high elongation at break is realized, the problems of poor toughness and low glass transition temperature of the existing benzoxazine with azo structure are solved, and the photo-braking of the benzoxazine material with azo structure can be realized;
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, nuclear magnetic spectrum of sodium azobenzene dicarboxylate;
FIG. 2, infrared spectra of azobenzene dicarboxylic acid;
FIG. 3, nuclear magnetic spectrum of azobenzene diamine;
FIG. 4, infrared spectrum of azobenzene diamine;
FIG. 5, infrared spectra of azobenzoxazine pre-polymers;
FIG. 6, infrared spectrum after azobenzoxazine self-curing;
FIG. 7, DSC image of azobenzoxazine prepolymer before curing;
FIG. 8, DSC image of azobenzoxazine prepolymer after curing;
FIG. 9 is a graph of tensile properties of a photo-responsive azobenzene benzoxazine material;
FIG. 10, photo-responsive azobenzoxazine material shape memory test chart, (a) is a photograph of spline original length, (b) is a photograph of spline tensile orientation fixing, (c) is a photograph of spline photopic deformation, and (d) is a photograph of spline thermal shape recovery;
FIG. 11, photo-response photo-braking graph of azobenzene benzoxazine material.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
Example 1
A quick light response benzoxazine material and a preparation method thereof, comprising the following steps:
(1) Preparation of azobenzene-4, 4-dicarboxylic acid
The first step of synthesizing azobenzene-4, 4-dicarboxylic acid requires p-nitrobenzoic acid, sodium hydroxide solid, glucose, glacial acetic acid and other medicines. 8g of p-nitrobenzoic acid and 26.8g of sodium hydroxide were mixed in 120 mL deionized water into a 2000 mL round bottom bottle. The solution was heated in a water bath until the solids dissolved, and then the temperature of the water bath was maintained at 50 ℃. 53.32g of glucose was dissolved in 80ml of deionized water to prepare an aqueous solution and the aqueous solution was added dropwise to obtain a yellow precipitate, and the solution immediately became a brown solution after further addition of glucose. The mixture solution was then stored in a water bath at 50 ℃ and bubbling was continued for 8h to give a light brown precipitate. The precipitate was collected by filtration and dissolved in deionized water. The solution was then acidified by adding large amounts of glacial acetic acid, resulting in a pale pink precipitate. Finally, the precipitate was rinsed with copious amounts of deionized water, filtered and purified. The final product was dried in vacuo to give a pink powder. The reaction equation is as follows:
；
FIG. 1 is a nuclear magnetic resonance spectrum of sodium azobenzene dicarboxylate. Since the dicarboxylic acid obtained was not soluble in water, it was reacted with sodium hydroxide to convert it to sodium salt and then tested. The displacement in the figure is respectively: 7.78-7.85 ppm,7.91-7.99 ppm of characteristic hydrogen corresponding to the a and b positions on azobenzene dicarboxylic acid respectively;
FIG. 2 is an infrared spectrum of azobenzene dicarboxylic acid. In the figure: 1283 cm -1 The position is a telescopic vibration peak of carboxyl; 1425 cm -1 Is a telescopic vibration peak of a benzene ring framework; 1605cm -1 A vibrational peak of-n=n-; 1684cm -1 Is the stretching vibration peak of carboxyl carbonyl; 2661cm -1 Is the stretching vibration peak of hydrogen in carboxyl;
(2) Preparing azobenzene-4, 4-diacyl chloride;
the azobenzene dicarboxylic acid ground into powder was weighed out 5g and poured into a flask, the flask was set on a reaction table, and the flask was set on N 2 Under the atmosphere, 75 mL thionyl chloride was slowly added dropwise to the flask, followed by stirring. Setting the temperature of an oil bath at 78 ℃ after the dripping is finished, setting the temperature of a reaction table top at 120 ℃, then mounting a condensing tube, refluxing for 12 hours, and finishing the reaction the next day to obtain the product of the mixture of the azobenzene diacid chloride. And then filtering the mixture by using a Buchner funnel to obtain red clear liquid, and evaporating the solvent from the obtained liquid by using a rotary distillation instrument to obtain pure azobenzene-4, 4-diacyl chloride. The reaction equation is as follows:
；
(3) Preparation of azobenzene polypropylene oxide diamine
The product of the previous reaction, azobenzene-4, 4-diacid chloride, was weighed out to give a mass of 5.5g and dissolved in 150 mL of dichloromethane. With azophthaloylThe molar ratio of chlorine to polypropylene oxide diamine D400 was 1:2. The polypropylene oxide diamine D400 was weighed into a round bottom pancake, 15mL methylene chloride was added to the flask, and 10mL triethylamine (eliminating hydrogen chloride gas generated in the subsequent reaction) was added. Pouring the mixed solution of the azobenzene diacid chloride and the methylene dichloride into a constant pressure funnel, placing a flask containing the polypropylene oxide diamine D400 solution on an operation table, then slowly dropwise adding the azobenzene diacid chloride solution into the polypropylene oxide diamine D400 solution by using the constant pressure funnel at the temperature of 0 ℃, and introducing N in the process 2 Slowly stirring, closing a nitrogen valve after the dripping is finished, and reacting for 24 hours at normal temperature. The next day a mixture of azobenzene diamine was obtained. And (3) spin-evaporating the solvent in the obtained initial product of the azobenzene diamine by using a rotary evaporator, washing and extracting by using ethyl acetate and water, and spin-evaporating again after washing to obtain pure azobenzene diamine. The reaction equation is as follows:
；
FIG. 3 is a nuclear magnetic spectrum of azobenzene diamine; wherein 8.20-7.77 ppm is hydrogen atom on benzene ring of azobenzene structure; 4.46 to 4.27 ppm hydrogen on amide; 3.85 to 3.02 ppm is hydrogen on the methylene group of the polypropylene oxide diamine; 1.44 to 1.12 ppm is hydrogen on polypropylene oxide diamine methine; 1.19 to 0.90ppm of hydrogen on the branched methyl group of the polypropylene oxide diamine;
FIG. 4 is an infrared spectrum of azobenzene diamine. In the figure, 3300 and 3300 cm -1 Is at the position of-NH 2 Stretching vibration peak with-NH-, 2960 cm -1 And 2868 cm -1 Stretching vibration peaks of methyl and methylene respectively 1633 and 1633 cm -1 Carbonyl peak at amide group 1096 cm -1 The part is the telescopic vibration of ether bond; the characteristic vibration bands of the amide in the azobenzene diamine are respectively positioned at 1633 and 1633 cm -1 、1279 cm -1 、670 cm -1 Nearby, the formation of amide bonds was demonstrated;
(4) Preparation of azo-containing benzoxazine prepolymer
The raw materials are mixed according to the mol ratio of azobenzene diamine, bisphenol A and paraformaldehyde of 1:1:4.3. The mixture was mixed with 15: 15mL toluene/ethanol mixture (toluene/ethanol volume ratio 2:1) per gram of azobenzene diamine, and after thorough mixing in the flask, the flask was set up to stir with a magnetic stirrer and the reaction was refluxed at 120 ℃ for 12h. The next day to obtain the initial product, filtering the initial product with cotton, filtering to remove solidified solid impurities, and then spin-evaporating the liquid part with a rotary evaporator to remove the solvent to obtain the final product benzoxazine. The reaction equation is as follows:
；
FIG. 5 is an infrared spectrum of an azobenzoxazine prepolymer; in the figure, 3296 and 3296 cm -1 Is at the position of-NH 2 Stretching vibration peak with-NH-, 2985 cm -1 And 2866cm -1 Stretching vibration peaks of methyl and methylene respectively 1636 and 1636 cm -1 Carbonyl peak at amide group 1099cm -1 Stretching vibration of ether bond 958cm -1 The characteristic peak of the oxazine ring is shown;
FIG. 6 is an infrared spectrum of an azobenzoxazine cured; in the figure, 3301 and 3301 cm -1 Is at the position of-NH 2 Stretching vibration peak with-NH-, 2974cm -1 And 2866cm -1 Stretching vibration peaks of methyl and methylene respectively, 1641 and 1641 cm -1 Carbonyl peak at amide group, 1099cm -1 The part is the telescopic vibration of ether bond; because the stretching vibration of the ether bond is stronger, the characteristic peak of the oxazine ring is less obvious. However, the infrared comparison before and after curing can find out that the peak value strength has obvious change, and the benzoxazine curing can also be proved;
FIG. 7 is a DSC image of an azobenzoxazine prepolymer prior to curing. The information in the graph demonstrates that the self-curing temperature of the benzoxazine prepolymer falls within a large range, and the peak temperature is 232 ℃. Subsequent demonstration of successful curing of the benzoxazine prepolymer by long-term curing at 200 ℃;
(5) Preparation of photoresponsive benzoxazine film
Adding 0.5g benzoxazine into 4mL N, N-dimethylformamide for dissolving, pouring into a polytetrafluoroethylene film, drying, and starting to solidify after complete drying. After dissolution, the solution is evenly poured into a film forming mold, and the mold is put into a baking oven at 60 ℃ for first drying, but after complete drying, solidification is started. DSC, tested before curing, indicated that the curing temperature was approximately 200 ℃ -250 ℃ (which can be cured for a long time at 200 ℃), the film was placed in an oven, dried at 80 ℃ for 1 hour, dried at 120 ℃ for 1 hour, then cured at 180 ℃ for 2 hours, and cured at 200 ℃ for 6 hours. And taking out the die after the completion, and cooling to room temperature to finish solidification. After the mold is completely cooled, removing the mold (which can be properly heated and is convenient for demolding) to obtain the benzoxazine film;
fig. 8 is a DSC image of an azobenzoxazine prepolymer after curing. The information in the graph proves that the glass transition temperature of a film formed by self-curing of the pre-polymer containing azobenzoxazine is 28 ℃;
fig. 9 is a graph of tensile properties of a photoresponsive benzoxazine material. Elongation at break, tensile strength of the three sets of data were read from the strain-tensile strength plot, and the modulus of elasticity was calculated. Obtaining the average elongation at break of the material to be 294% and the average breaking strength to be 15.54 MPa according to the average value of the three groups of data;
FIG. 10 is a graph of a thermal shape memory test of a photoresponsive benzoxazine material, tested: in the drawing, (a) a film sample bar having an original length of 2.1cm was stretched to a position of 3.2cm by applying stress at a predetermined temperature, as shown in the drawing (b). After the stress was removed, the film was fixed at 3cm, bent at an angle as shown in (c) after illumination, and then the sample was heated again to recover to 2.3cm as shown in (d). Thus, it is calculated that: the shape fixation ratio of the film spline was 93.8%, and the shape recovery ratio was 90.5%. The sample achieves the effect of photo-actuation and thermal shape recovery;
fig. 11 is a photo-actuation diagram of a photo-responsive benzoxazine material. Stretching and orienting the obtained photoresponse azobenzoxazine film above the glass transition temperature, cooling and shaping, and irradiating the oriented position under the condition of 365nm point light source, so that the material is bent, and the braking effect is achieved. It can be seen from the figure that the optical braking effect of the material is more obvious: a 67 deg. bend can be achieved within 6s of irradiation from a 365nm light source.
Example 2
The process for producing azobenzene-4, 4-dicarboxylic acid is the same as in step (1) in embodiment 1;
the process for preparing azobenzene-4, 4-diacid chloride is the same as in step (2) of embodiment 1;
(3) Preparation of Azobenzene polysiloxane diamine
3.07g of azobenzene-4, 4-diacyl chloride was weighed, dissolved in 100 mL methylene chloride and then purged with nitrogen for use. 20g of aminopropyl-terminated polysiloxane (Mn=1000 g/mol) were weighed in a molar ratio of 1:2 and poured into a round-bottomed pancake, 12 mL dichloromethane was added to the flask, followed by 10mL of triethylamine (elimination of hydrogen chloride generated in the subsequent reaction). Pouring the mixed solution of the azobenzene diacid chloride and the methylene dichloride into a constant pressure funnel, putting a flask containing the polysiloxane 1000 solution on an operation table, then slowly adding the azobenzene diacid chloride solution into the polysiloxane 1000 solution by using the constant pressure funnel at the temperature of 0 ℃, and introducing N in the process 2 Slowly stirring, closing a nitrogen valve after the dripping is finished, and reacting for 24 hours at normal temperature. The next day a mixture of azobenzene diamine was obtained. And (3) spin-evaporating the solvent in the obtained initial product of the azobenzene diamine by using a rotary evaporator, washing and extracting by using ethyl acetate and water, and spin-evaporating again after washing to obtain pure azobenzene diamine. The reaction equation is as follows:
；
(4) Preparation of azo-containing benzoxazine prepolymer
The raw materials are according to azobenzene polysiloxane diamine, bisphenol A and paraformaldehyde 1:1: 4.4. The mixture was mixed with 15: 15mL toluene/ethanol mixture (toluene/ethanol volume ratio 2:1) per gram of azobenzene diamine, and after thorough mixing in the flask, the flask was set up to stir with a magnetic stirrer and the reaction was refluxed at 120 ℃ for 12h. The next day to obtain the initial product, filtering the initial product with cotton, filtering to remove solidified solid impurities, and then spin-evaporating the liquid part with a rotary evaporator to remove the solvent to obtain the final product benzoxazine. The reaction equation is as follows:
；
(5) Preparation of photoresponsive benzoxazine film
And adding 4mL of benzoxazine into 0.5g to obtain DMF (dimethyl formamide) for dissolution, pouring into a polytetrafluoroethylene film, drying, and starting to solidify after the benzoxazine is completely dried. After dissolution, the solution is evenly poured into a film forming mold, and the film is put into a baking oven at 60 ℃ for first drying, but after complete drying, solidification is started. The film was placed in an oven and dried at 80 c for 1 hour, at 120 c for 1 hour, then at 180 c for 2 hours, and at 200 c for 6 hours. And taking out the die after the completion, and cooling to room temperature to finish solidification. And after the mold is completely cooled, removing the mold to obtain the benzoxazine film.
Example 3
(1) The process for producing azobenzene-4, 4-dicarboxylic acid is the same as in step (1) in embodiment 1;
(2) The process for preparing azobenzene-4, 4-diacid chloride is the same as in step (2) of embodiment 1;
(3) Preparation of azobenzene dodecyl diamine
3.07g of azobenzene-4, 4-diacyl chloride was weighed, dissolved in 50. 50 mL of water-removed N, N-dimethylformamide, and then purged with nitrogen for use. According to the mole ratio of 1:2 to the flask, 4g of dodecyldiamine was weighed into a round bottom cake, 30mL of N, N-dimethylformamide was added to the flask, and 10mL of triethylamine (elimination of hydrogen chloride generated in the subsequent reaction) was added. Pouring the mixed solution of the azobenzene diacid chloride and the N, N-dimethylformamide into a constant pressure funnel, placing a flask containing the dodecyl diamine solution on an operation table, then slowly dropwise adding the azobenzene diacid chloride solution into the solution of the dodecyl diamine solution by using the constant pressure funnel at 60 ℃, and introducing N in the process 2 Slowly stirring, closing a nitrogen valve after the dripping is finished, and refluxing for 24h at 60 ℃. The next day a mixture of azobenzene diamine was obtained. Directly adding water into the mixture, stirring to remove impurities, and vacuum filteringDrying water in a vacuum oven at 60 ℃ to obtain dodecyldiamine containing azobenzene. The reaction equation is as follows:
；
(4) Preparation of azo-containing benzoxazine prepolymer
The raw materials are mixed according to the mole ratio of azobenzene dodecyl diamine, bisphenol A and paraformaldehyde of 1:1:4.3. The mixture was mixed with 10mL of chloroform per gram of azobenzene diamine, and after thorough mixing in a flask, the flask was set up with stirring on a magnetic stirrer, and the reaction was refluxed for 24 hours. The next day, the initial product is obtained, then the liquid part is steamed by a rotary evaporator, and the final product benzoxazine is obtained after the solvent is removed. The reaction equation is as follows:
；
(5) Preparation of photoresponsive benzoxazine film
And adding 4mL of N, N-dimethylformamide into 0.5g of benzoxazine for dissolution, pouring into a polytetrafluoroethylene film, drying, and starting to solidify after complete drying. After dissolution, the solution is evenly poured into a film forming mold, and the film is put into a baking oven at 60 ℃ for first drying, but after complete drying, solidification is started. The film was placed in an oven and dried at 80 c for 1 hour, at 120 c for 1 hour, then at 180 c for 2 hours, and at 200 c for 6 hours. And taking out the die after the completion, and cooling to room temperature to finish solidification. And after the mold is completely cooled, removing the mold to obtain the benzoxazine film.
Example 4
The process for producing azobenzene-4, 4-dicarboxylic acid is the same as in step (1) in embodiment 1;
the process for preparing azobenzene-4, 4-diacid chloride is the same as in step (2) of embodiment 1;
the process for preparing azobenzene polyether diamine is the same as in step (3) of embodiment 1;
(4) Preparation of azo-containing benzoxazine prepolymer
The raw materials comprise azobenzene polypropylene oxide diamine, bisphenol F and paraformaldehyde 1:1: 4.4. The mixture was mixed with 15mL of a mixture of toluene and ethanol (toluene to ethanol volume ratio 2:1) per gram of azobenzene polyether diamine, and after thorough mixing in the flask, the flask was set up to stir with a magnetic stirrer, and the reaction was refluxed at 120 ℃ for 12h. The next day, the initial product is obtained, then the liquid part is steamed by a rotary evaporator, and the final product benzoxazine is obtained after the solvent is removed. The reaction equation is as follows:
；
(5) Preparation of photoresponsive benzoxazine film
And adding 4mL of N, N-dimethylformamide into 0.5g of benzoxazine for dissolution, pouring into a polytetrafluoroethylene film, drying, and starting to solidify after complete drying. After dissolution, the solution is evenly poured into a film forming mold, and the film is put into a baking oven at 60 ℃ for first drying, but after complete drying, solidification is started. The film was placed in an oven and dried at 80 c for 1 hour, at 120 c for 1 hour, then at 180 c for 2 hours, and at 200 c for 6 hours. And taking out the die after the completion, and cooling to room temperature to finish solidification. And after the mold is completely cooled, removing the mold to obtain the benzoxazine film.
Example 5
The process for producing azobenzene-4, 4-dicarboxylic acid is the same as in step (1) in embodiment 1;
the process for preparing azobenzene-4, 4-diacid chloride is the same as in step (2) of embodiment 1;
the process for preparing azobenzene polypropylene oxide diamine is the same as in step (3) in embodiment 1;
(4) Preparation of azo-containing benzoxazine prepolymer
The raw materials are prepared from azobenzene polypropylene oxide diamine, bisphenol AF and paraformaldehyde 1:1: 4.3. The mixture was mixed with 15mL of a mixture of toluene and ethanol (toluene to ethanol volume ratio 2:1) per gram of azobenzene polypropylene oxide diamine, and after thorough mixing in the flask, the flask was stirred on a magnetic stirrer and reacted at 120 ℃ under reflux for 12h. The next day, the initial product is obtained, then the liquid part is steamed by a rotary evaporator, and the final product benzoxazine is obtained after the solvent is removed. The reaction equation is as follows:
；
(5) Preparation of photoresponsive benzoxazine film
And adding 4mL of N, N-dimethylformamide into 0.5g of benzoxazine for dissolution, pouring into a polytetrafluoroethylene film, drying, and starting to solidify after complete drying. After dissolution, the solution is evenly poured into a film forming mold, and the film is put into a baking oven at 60 ℃ for first drying, but after complete drying, solidification is started. The film was placed in an oven and dried at 80 c for 1 hour, at 120 c for 1 hour, then at 180 c for 2 hours, and at 200 c for 6 hours. And taking out the die after the completion, and cooling to room temperature to finish solidification. And after the mold is completely cooled, removing the mold to obtain the benzoxazine film.
Example 6
The process for producing azobenzene-4, 4-dicarboxylic acid is the same as in step (1) in embodiment 1;
the process for preparing azobenzene-4, 4-diacid chloride is the same as in step (2) of embodiment 1;
the process for preparing azobenzene polypropylene oxide diamine is the same as in step (3) in embodiment 1;
(4) Preparation of azo-containing benzoxazine prepolymer
The raw materials are mixed according to the mole ratio of azobenzene polypropylene oxide diamine, 3-bis (4-hydroxyphenyl) butyric acid and paraformaldehyde of 1:1:4.3. The mixture was mixed with 15mL of a mixture of toluene and ethanol (toluene to ethanol volume ratio 2:1) per gram of azobenzene polypropylene oxide diamine, and after thorough mixing in the flask, the flask was stirred on a magnetic stirrer and reacted at 120 ℃ under reflux for 12h. The next day, the initial product is obtained, then the liquid part is steamed by a rotary evaporator, and the final product benzoxazine is obtained after the solvent is removed. The reaction equation is as follows:
；
(5) Preparation of photoresponsive benzoxazine film
And adding 4mL of N, N-dimethylformamide into 0.5g of benzoxazine for dissolution, pouring into a polytetrafluoroethylene film, drying, and starting to solidify after complete drying. After dissolution, the solution is evenly poured into a film forming mold, and the film is put into a baking oven at 60 ℃ for first drying, but after complete drying, solidification is started. The film was placed in an oven and dried at 80 c for 1 hour, at 120 c for 1 hour, then at 180 c for 2 hours, and at 200 c for 6 hours. And taking out the die after the completion, and cooling to room temperature to finish solidification.
Example 7
The process for producing azobenzene-4, 4-dicarboxylic acid is the same as in step (1) in embodiment 1;
the process for preparing azobenzene-4, 4-diacid chloride is the same as in step (2) of embodiment 1;
the process for preparing azobenzene polypropylene oxide diamine is the same as in step (3) in embodiment 1;
(4) Preparation of azo-containing benzoxazine prepolymer
The raw materials are prepared from azobenzene polypropylene oxide diamine, 4' -dihydroxybenzophenone and paraformaldehyde 1:1: 4.3. The mixture was mixed with 15mL of a mixture of toluene and ethanol (toluene to ethanol volume ratio 2:1) per gram of azobenzene polypropylene oxide diamine, and after thorough mixing in the flask, the flask was stirred on a magnetic stirrer and reacted at 120 ℃ under reflux for 12h. The next day, the initial product is obtained, then the liquid part is steamed by a rotary evaporator, and the final product benzoxazine is obtained after the solvent is removed. The reaction equation is as follows:
；
(5) Preparation of photoresponsive benzoxazine film
And adding 4mL of N, N-dimethylformamide into 0.5g of benzoxazine for dissolution, pouring into a polytetrafluoroethylene film, drying, and starting to solidify after complete drying. After dissolution, the solution is evenly poured into a film forming mold, and the film is put into a baking oven at 60 ℃ for first drying, but after complete drying, solidification is started. The film was placed in an oven and dried at 80 c for 1 hour, at 120 c for 1 hour, then at 180 c for 2 hours, and at 200 c for 6 hours. And taking out the die after the completion, and cooling to room temperature to finish solidification. And after the mold is completely cooled, removing the mold to obtain the benzoxazine film.
Example 8
The process for producing azobenzene-4, 4-dicarboxylic acid is the same as in step (1) in embodiment 1;
the process for preparing azobenzene-4, 4-diacid chloride is the same as in step (2) of embodiment 1;
the process for preparing azobenzene polysiloxane diamine is the same as in step (3) of embodiment 2;
(4) Preparation of azo-containing benzoxazine prepolymer
The raw materials are mixed according to the mole ratio of azobenzene polysiloxane diamine, 4' -dihydroxydiphenyl thioketone and paraformaldehyde of 1:1:4.3. The mixture was mixed with 15mL toluene/ethanol mixture (toluene/ethanol volume ratio 2:1) per gram of azobenzene polysiloxane diamine, and after thorough mixing in the flask, the flask was stirred on a magnetic stirrer and refluxed at 120 ℃ for reaction 12h. The next day, the initial product is obtained, then the liquid part is steamed by a rotary evaporator, and the final product benzoxazine is obtained after the solvent is removed. The reaction equation is as follows:
；
(5) Preparation of photoresponsive benzoxazine film
0.5g of benzoxazine is taken and added into 4mL of N, N-dimethylformamide for dissolution, poured into a polytetrafluoroethylene film for drying, and after the complete drying, solidification is started. After dissolution, the solution is evenly poured into a film forming mold, and the film is put into a baking oven at 60 ℃ for first drying, but after complete drying, solidification is started. The film was placed in an oven and dried at 80 c for 1 hour, at 120 c for 1 hour, then at 180 c for 2 hours, and at 200 c for 6 hours. And taking out the die after the completion, and cooling to room temperature to finish solidification. And after the mold is completely cooled, removing the mold to obtain the benzoxazine film.
In summary, the invention solves the problem that the traditional azobenzene-containing benzoxazine resin is difficult to generate orientation and does not have optical braking by utilizing the way of synthesizing the azobenzene-containing benzoxazine by using azobenzene diamine instead of traditional azobenzene monophenol or azobenzene diphenol.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalents and modifications can be made to the above-mentioned embodiments without departing from the scope of the invention.
Claims (3)
1. A photoresponsive benzoxazine material is characterized in that the photoresponsive benzoxazine material is obtained by thermal curing reaction of a benzoxazine prepolymer containing an azobenzene structure at the temperature of 120-200 ℃; the benzoxazine prepolymer is prepared by refluxing and stirring diamine containing an azobenzene structure, diphenol and paraformaldehyde in a molar ratio of 1:1:4.1-4.4 in toluene for 12 hours; the benzoxazine prepolymer has the following structural formula:
；
wherein R is 1 Is one of the following structural formulas:
；
wherein, the value range of m is 1-14;
wherein R is 2 Is one of the following structural formulas:
。
2. the photoresponsive benzoxazine material according to claim 1, wherein the diamine containing an azobenzene structure is obtained by reacting azobenzene diacid chloride with long-chain diamine under the catalysis of triethylamine according to a molar ratio of 2:1:3; the long-chain diamine is one of polypropylene oxide diamine, polysiloxane diamine and alkyl diamine with the molecular weight of 100-1000; the structural formula of the diamine containing the azobenzene structure is as follows:
；
wherein R is 1 Is one of the following structural formulas:
；
wherein, the value range of m is 1-14.
3. A method of preparing a photoresponsive benzoxazine material according to any one of claims 1 to 2, comprising the steps of:
s1, preparing diamine containing an azobenzene structure: adding long-chain diamine into a round bottom flask, dissolving with dichloromethane, adding triethylamine as a catalyst, cooling to 0 ℃, and adding dichloromethane solution of azobenzene diacid chloride with a dropping funnel; after the dripping is finished, stirring is continued for 24 hours at room temperature; after the reaction is finished, extracting, drying and spin-evaporating to remove the solvent to obtain diamine containing an azobenzene structure;
s2, preparing a benzoxazine prepolymer containing an azobenzene structure: diamine containing an azobenzene structure, diphenol and paraformaldehyde are uniformly mixed in a mixed solution of toluene and ethanol according to the molar ratio of 1:1:4.1-4.4, then fully reacted for 12 hours at 100-130 ℃, and the solvent is removed by rotary evaporation to obtain a benzoxazine prepolymer;
s3, preparing a light-response benzoxazine material: and dissolving the benzoxazine prepolymer in N, N-dimethylformamide, pouring the N, N-dimethylformamide into a mold, drying the solvent at 60 ℃, and then raising the temperature to 120-200 ℃ for curing reaction to obtain the benzoxazine material containing the azobenzene structure.
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| 可见光促进的偶氮苯的转移氢化及氢酰化反应研究;宋梦辉;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第12期);B014-126 * |
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