CN109651545B - Azobenzene polymer material and preparation method and application thereof - Google Patents
Azobenzene polymer material and preparation method and application thereof Download PDFInfo
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- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002861 polymer material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 230000002441 reversible effect Effects 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000853 adhesive Substances 0.000 claims abstract description 12
- 230000001070 adhesive effect Effects 0.000 claims abstract description 12
- DMLAVOWQYNRWNQ-YPKPFQOOSA-N (Z)-azobenzene Chemical compound C1=CC=CC=C1\N=N/C1=CC=CC=C1 DMLAVOWQYNRWNQ-YPKPFQOOSA-N 0.000 claims abstract description 6
- 238000007699 photoisomerization reaction Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 8
- -1 arylamine compound Chemical class 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- IDSLBLWCPSAZBL-UHFFFAOYSA-N 2-cyanopropan-2-yl benzenecarbodithioate Chemical compound N#CC(C)(C)SC(=S)C1=CC=CC=C1 IDSLBLWCPSAZBL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005917 acylation reaction Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000003944 halohydrins Chemical class 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 230000007704 transition Effects 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 8
- 230000009477 glass transition Effects 0.000 abstract description 5
- 230000008439 repair process Effects 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 229920001169 thermoplastic Polymers 0.000 abstract description 4
- DMLAVOWQYNRWNQ-BUHFOSPRSA-N (E)-azobenzene Chemical compound C1=CC=CC=C1\N=N\C1=CC=CC=C1 DMLAVOWQYNRWNQ-BUHFOSPRSA-N 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000007634 remodeling Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000012043 crude product Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- DEQLTFPCJRGSHW-UHFFFAOYSA-N hexadecylbenzene Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1 DEQLTFPCJRGSHW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- JFEVWPNAOCPRHQ-UHFFFAOYSA-N chembl1316021 Chemical compound OC1=CC=CC=C1N=NC1=CC=CC=C1O JFEVWPNAOCPRHQ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- RTOLVRQCDHIQQA-UHFFFAOYSA-N hexane;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCCC RTOLVRQCDHIQQA-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LQKYCMRSWKQVBQ-UHFFFAOYSA-N n-dodecylaniline Chemical compound CCCCCCCCCCCCNC1=CC=CC=C1 LQKYCMRSWKQVBQ-UHFFFAOYSA-N 0.000 description 1
- IXEGRINNWXKNJO-UHFFFAOYSA-N n-hexadecylaniline Chemical compound CCCCCCCCCCCCCCCCNC1=CC=CC=C1 IXEGRINNWXKNJO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F120/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明提供了一种偶氮苯聚合物材料，具有式Ⅰ所示结构。所述偶氮苯聚合物能够在光诱导下异构化，玻璃化转变温度改变，可于室温下产生可逆固‑液转变，具有可重复自修复和表面修复作用。同时，反式偶氮苯聚合物为固体，具有很强的粘附性，能承受载荷，相反，顺式偶氮苯聚合物为液体，具有弱的粘附性，即光异构化可引起负载下降。因此，本发明提供的偶氮苯聚合物可作为光响应自修复材料和光控可逆粘合剂，可解决常规热塑性高分子材料在塑料，涂层的重塑、损伤修复，和胶粘剂的分离、再循环与修复粘附表面等方面存在的问题。 The present invention provides an azobenzene polymer material having the structure shown in formula I. The azobenzene polymer can be isomerized under light induction, the glass transition temperature is changed, the reversible solid-liquid transition can be generated at room temperature, and the self-healing and surface repairing effects can be repeated. At the same time, trans-azobenzene polymers are solid and have strong adhesion and can withstand loads. On the contrary, cis-azobenzene polymers are liquid and have weak adhesion, that is, photoisomerization can cause Load drops. Therefore, the azobenzene polymer provided by the present invention can be used as a light-responsive self-healing material and a light-controlled reversible adhesive, which can solve the problems of conventional thermoplastic polymer materials in plastics, coating remodeling, damage repair, and separation of adhesives, Problems with recycling and repairing adhering surfaces, etc. 
Description
Technical Field
The invention relates to the technical field of photoresponse polymer materials, in particular to an azobenzene polymer material and a preparation method and application thereof.
Background
The glass transition temperature is an inherent property of an amorphous polymer material, and is a boundary temperature interval between a glassy state and a high elastic state of the polymer material. The size of the glass transition temperature directly influences the service performance and the process performance of the material. In general, thermoplastic polymer materials, such as some plastics, paints and thermoplastic adhesives, are heated to a temperature above the glass transition temperature to a fluid state before being molded, coated and bonded, and then cooled for molding. If the plastic and the coating are damaged or the adhesive material needs to be separated, two traditional methods exist at present: firstly, the method is high in cost and large in energy consumption; and secondly, a plasticizing solvent is used at normal temperature, and the method has high treatment cost and pollutes the environment.
Therefore, it is very important to respond to external factors to realize reversible solid-liquid transition of the polymer material at room temperature.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an azobenzene polymer material, a preparation method and an application thereof, which can generate reversible solid-liquid conversion at room temperature, has a repeatable repairing function by illumination, and has a very short solid-liquid conversion time suitable for practical use.
In order to solve the technical problems, the invention provides an azobenzene polymer material which is characterized by having a structure shown in a formula I:
wherein R is1Is a decaalkyl group, herein denoted as polymer a;
or R1Hexadecyl, herein denoted as polymer B;
n is 4 to 500, and more preferably 20 to 50.
The chemical structure of the repeating structural unit has a great influence on the polymer properties. R1The length of the chain and the number of the spacer groups between the acyl-oxygen bond and the azobenzene group can directly influence whether the polymer has a photoinduced solid-liquid transformation phenomenon and the solid-liquid transformation rate, and the influence is not regular and can be circulated. For example, when the number of spacers is too small (e.g., 0, 2) or too large (e.g., 20), the polymer loses its property of photo-reversible solid-liquid transition; when R is1When the chain length is too short, the solid-liquid transition speed of the polymer is slow, which may cause inconvenience in practical use. Therefore, the invention obtains two azobenzene polymer materials with quick photorepair and reversible adhesion property through chemical structure design. The azobenzene polymer material provided by the invention has cis-form and trans-form configurations, which are respectively shown as a formula I- (Z) and a formula I- (E):
wherein, the cis-form polymer I- (Z) is liquid, the trans-form polymer I- (E) is solid, and the polymer can be isomerized under the condition of light induction, for example, under the irradiation of ultraviolet light, the trans-form can be converted into the cis-form, and the solid-liquid conversion can be carried out; under the irradiation of visible light, cis-to-trans conversion can occur, and liquid-solid conversion can occur; thereby achieving self-healing.
Meanwhile, researches show that the trans-form azobenzene polymer has strong adhesion and can bear load to realize the adhesion of the base material, the cis-form azobenzene polymer has weak adhesion, the trans-form polymer solid is irradiated by ultraviolet light to realize the separation of the base material, and the cis-form polymer liquid is irradiated by visible light to realize the re-adhesion of the base material to realize reversible adhesion.
The cis-trans transformation and the phase transformation are shown in FIG. 1.
The invention provides a preparation method of the azobenzene polymer material, which comprises the following steps:
A) carrying out azo reaction on the arylamine compound shown in the formula I-a to obtain a compound shown in the formula I-b;
B) reacting a compound shown as a formula I-b with halohydrin shown as a formula I-c to obtain a compound shown as a formula I-d;
C) carrying out acylation reaction on the compound shown in the formula I-d and acryloyl chloride to obtain a compound shown in the formula I-e;
D) carrying out polymerization reaction on the compound shown in the formula I-e to obtain a polymer shown in the formula I;
wherein R is1Is a decyl group or a hexadecyl group;
n is 4 to 500, and more preferably 20 to 50;
x is halogen; preferably, X is Cl.
In some embodiments of the present invention, the polymerization in step D) is initiated with cyanoisopropyl dithiobenzoate and azobisisobutyronitrile.
The invention provides an application of the azobenzene polymer material or the azobenzene polymer material prepared by the preparation method as a photoresponse self-repairing material or a light-operated reversible adhesive.
Specifically, the invention provides a method for realizing self-repair of the azobenzene polymer material or the azobenzene polymer material prepared by the preparation method, which comprises the following steps:
at room temperature, after the surface of the azobenzene polymer solid material shown in the formula I in the trans-configuration is damaged, ultraviolet light is firstly used for irradiating the damaged part to enable the damaged part to be subjected to photoisomerization, the damaged part is converted into the cis-configuration to generate solid-liquid conversion, the damage is repaired, then visible light is used for irradiating the damaged part to enable the cis-azobenzene polymer to return to the trans-configuration, and self-repairing is achieved.
The invention also provides a method for realizing reversible adhesion of the azobenzene polymer material or the azobenzene polymer material prepared by the preparation method, which comprises the following steps:
a) adopting a cis-configuration azobenzene polymer shown as a formula I as a bonding medium, bonding the substrates to be bonded, and converting the azobenzene polymer into a trans-configuration by irradiation of visible light to realize bonding of the substrates;
b) irradiating the bonding part by adopting ultraviolet light, converting the azobenzene polymer into a cis-configuration to generate solid-liquid conversion, and realizing the separation of the base materials;
c) repeating the steps a) and b) to realize reversible bonding.
By adopting the method, the base materials with different wettabilities and different roughness can be bonded and separated.
The azobenzene polymers described above can also be used as binders in water.
Preferably, the wavelength of the ultraviolet light is 365 nm; in some embodiments of the invention, a 365nm wavelength LED light source is used.
Preferably, the visible light wavelength is 530 nm; in some embodiments of the present invention, an LED light source with a wavelength of 530nm is used.
Compared with the prior art, the invention provides an azobenzene polymer material which has a structure shown in a formula I. The azobenzene polymer has the advantages of light repair property and light-operated reversible adhesion effect, can be isomerized under light induction, has a glass transition temperature change, can generate reversible solid-liquid transition at room temperature, and has repeatable self-repair and surface repair effects. Meanwhile, the trans-azobenzene polymer is solid, has strong adhesion and can bear load, and on the contrary, the cis-azobenzene polymer is liquid and has weak adhesion, namely, the load can be reduced due to photoisomerization. Therefore, the azobenzene polymer provided by the invention can be used as a photoresponse self-repairing material and a light-operated reversible adhesive, and can solve the problems of the conventional thermoplastic high polymer material in the aspects of plastic, coating remodeling, damage repair, adhesive separation, recycling, adhesive surface repair and the like.
Experimental results show that the azobenzene polymer material provided by the invention is used as a binder or a self-repairing material, and the binding time or the self-repairing time is shortened to be within 10S.
Drawings
FIG. 1 is a photomicrograph (20 μm scale) of the structural formula of azobenzene polymers A and B, and the liquefaction of photoisomerization and trans-solid samples thereof under the irradiation of ultraviolet light (365nm LED light source);
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of azobenzene polymer A;
FIG. 3 is a NMR hydrogen spectrum of azobenzene polymer B;
FIG. 4 is a diagram of an example of self-repair of an azobenzene polymer film;
fig. 5 is a graph showing the adhesive strength of cis-trans structure azobenzene polymer measured by a extensimeter.
Detailed Description
In order to further illustrate the present invention, the following will describe in detail the azobenzene polymer material with light repairing property and light-operated reversible adhesion, its preparation method and application.
Example 1:
the synthesis method of the azobenzene polymer A comprises the following steps:
1) dissolving 0.075mol of n-dodecylaniline in a mixture of 16mL of hydrochloric acid, 16g of ice and 110mL of acetone, slowly dropwise adding 28mL of water, a mixed solution of 28g of ice and 0.075mol of sodium nitrite into the solution, stirring the system at-5-0 ℃ for 30min, dissolving 0.075mol of phenol in 2mol/L of sodium hydroxide solution, adding the system, stirring and reacting for 2h under the condition of pH 9-10, stopping the reaction, adding hydrochloric acid for neutralization, and carrying out suction filtration and water washing on the reaction solution to obtain a crude product. Drying the crude product, and recrystallizing the crude product by using ethanol to obtain the 4- (4-n-decaalkylphenyl) azophenol.
2) 0.036mol of the final product of step 1) was dissolved in 40mL of N, N-dimethylformamide, and then 0.036mol of potassium carbonate was added and stirred at 30 ℃ for 30 min. 0.09mol of potassium iodide and 0.039mol of 6-chloro-1-hexanol were added to the system and stirred vigorously at 110 ℃ for 24 h. The reaction solution was cooled to room temperature, 900g of crushed ice was added, and then, a crude product was obtained by suction filtration. The crude product was dried and recrystallized from ethanol to give 6- [4- (4-n-undecylphenyl) azophenoxy ] -1-hexanol.
3) 0.016mol of the final product in the step 2) and 0.016mol of triethylamine are dissolved in 50mL of anhydrous dichloromethane, 0.019mol of acryloyl chloride and 10mL of anhydrous dichloromethane are mixed and dripped into the solution in ice-water bath, and the reaction is carried out for 20h at room temperature. The reaction solution was concentrated by a rotary evaporator and washed with dilute hydrochloric acid, a saturated sodium bicarbonate solution and a sodium chloride solution, respectively. Collecting oil phase, removing solvent by rotary evaporation to obtain crude product, purifying by silica gel column chromatography, eluting with dichloromethane to obtain monomer containing azobenzene: (E) -6- [4- (4-n-undecylphenyl) azophenoxy ] n-hexane acrylate.
4) The polymer is obtained by reversible addition-fragmentation chain transfer polymerization. 4.096mmol of the final product of the step 3), 0.023mmol of cyano isopropyl dithiobenzoate and 0.006mmol of azobisisobutyronitrile are dissolved in 4mL of anisole, the solution is frozen for 4 times, vacuumized, sealed by argon after the melting cycle, and polymerized for 48 hours in an oil bath at 75 ℃. After completion of the polymerization, the solution was dropped into 40mL of methanol, the precipitate was dissolved in tetrahydrofuran and then precipitated from methanol, and the reaction was repeated three times to remove unreacted monomers, collect the precipitate, and dried in a vacuum oven at 40 ℃ for 24 hours. Thus obtaining the final azobenzene polymer. The NMR spectrum is shown in FIG. 2, and the molecular weight and the polydispersity index of the molecular weight (measured by gel permeation chromatography) are shown in Table 1.
Example 2:
the synthesis method of the azobenzene polymer B comprises the following steps:
1) dissolving 0.075mol of n-hexadecylaniline in a mixture of 16mL of hydrochloric acid, 16g of ice and 110mL of acetone, slowly dropwise adding 28mL of water, a mixed solution of 28g of ice and 0.075mol of sodium nitrite into the solution, stirring the system at the temperature of minus 5-0 ℃ for 30min, dissolving 0.075mol of phenol in 2mol/L of sodium hydroxide solution, adding the system, stirring and reacting for 2h under the condition of pH 9-10, stopping the reaction, adding hydrochloric acid for neutralization, and carrying out suction filtration and water washing on the reaction solution to obtain a crude product. Drying the crude product, and recrystallizing the crude product by using ethanol to obtain the 4- (4-n-hexadecyl benzene) azophenol.
2) 0.036mol of the final product of step 1) was dissolved in 40mL of N, N-dimethylformamide, and then 0.036mol of potassium carbonate was added and stirred at 30 ℃ for 30 min. 0.09mol of potassium iodide and 0.039mol of 6-chloro-1-hexanol were added to the system and stirred vigorously at 110 ℃ for 24 h. The reaction solution was cooled to room temperature, 900g of crushed ice was added, followed by suction filtration to obtain a crude product. The crude product was dried and recrystallized from ethanol to give 6- [4- (4-n-hexadecylbenzene) azophenoxy ] -1-hexanol.
3) 0.016mol of the final product in the step 2) and 0.016mol of triethylamine are dissolved in 50mL of anhydrous dichloromethane, 0.019mol of acryloyl chloride and 10mL of anhydrous dichloromethane are mixed and dripped into the solution in ice-water bath, and the reaction is carried out for 20h at room temperature. The reaction solution was concentrated by a rotary evaporator and washed with dilute hydrochloric acid, a saturated sodium bicarbonate solution and a sodium chloride solution, respectively. Collecting oil phase, removing solvent by rotary evaporation to obtain crude product, purifying by silica gel column chromatography, eluting with dichloromethane to obtain monomer containing azobenzene: (E) -6- [4- (4-n-hexadecylbenzene) azophenoxy ] n-hexane acrylate.
4) The polymer is obtained by reversible addition-fragmentation chain transfer polymerization. 4.096mmol of the final product of the step 3), 0.023mmol of cyano isopropyl dithiobenzoate and 0.006mmol of azobisisobutyronitrile are dissolved in 4mL of anisole, the solution is frozen for 4 times, vacuumized, sealed by argon after the melting cycle, and polymerized for 48 hours in an oil bath at 75 ℃. After completion of the polymerization, the solution was dropped into 40mL of methanol. Dissolving the precipitate with tetrahydrofuran, precipitating with methanol, repeating for three times to remove unreacted monomer, collecting precipitate, and vacuum drying at 40 deg.C for 24 hr. Thus obtaining the final azobenzene polymer. The NMR spectrum is shown in FIG. 3, and the molecular weight and the polydispersity index of the molecular weight (measured by gel permeation chromatography) are shown in Table 1.
Example 3:
the method for realizing self-repair of the azobenzene polymers A and B comprises the following steps: scribing a nick on the surface of a polymer solid sample at room temperature by using 365nm (30 mW/cm)2) Irradiating the damaged part with ultraviolet light for 10s to induce photoisomerization, performing solid-liquid transformation, repairing the damage, and treating with 530nm (2 mW/cm)2) Under the irradiation of visible light, the cis-azobenzene polymer is recovered to a trans-solid, and self-repairing is realized. See in particular fig. 4.
The solid-liquid transition time is shown in Table 2.
Example 4:
the method for realizing reversible bonding of the azobenzene polymers A and B comprises the following steps: the adhesion strength measured on a tensile tester using trans-azobenzene polymer firmly bonded two quartz substrates at room temperature is shown in FIG. 5, passing 365nm (30 mW/cm)2) Ultraviolet irradiation induced trans-cis isomerization liquefied the polymer on the two separate quartz substrates, and the adhesion strength of cis-azobenzene is shown in fig. 5. The substrates are then joined by pressing, and the liquefied polymer wets the substrate surface. Subsequently, the mixture was passed through a filter at 530nm (2 mW/cm)2) Visible light induces cis-trans isomerization to solidify the polymer, thereby increasing adhesion. The light-induced reversible solid-liquid transition makes the polymer a reusable adhesive with an adhesive strength of more than 68% of its original strength.
Example 5:
the static water contact angle of the quartz substrate was 27 + -5 deg.. The trans-polymers a, B strongly bound the quartz substrate. UV irradiation induces trans-cis isomerization and the adhesion of the polymer to the substrate is reduced. This indicates that light can control the adhesion of the polymer to the substrate.
TABLE 1 molecular weights and molecular weight polydispersity indices of three azobenzene polymers measured by gel permeation chromatography
Comparative examples 1 to 7
Following the procedure of example 1, the following control compounds were prepared, of the formula:
m、R1the values, molecular weights and molecular weight polydispersity indices (measured by gel permeation chromatography) are shown in table 2, and the results of the performance tests are shown in table 2, wherein the solid-liquid transition time is the time required for irradiating 365nm (30mW/cm2) ultraviolet light on the surface of the polymer to completely disappear the scratches, according to example 3.
TABLE 2 examples and comparative examples m, R1And performance instrumentation data summarization
As can be seen from the above examples and comparative examples, the azobenzene polymer provided by the present invention can realize self-repair and reversible adhesion, and has a short solid-liquid transition time.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (7)
1. An azobenzene polymer material, characterized by having the structure shown in formula I:
wherein R is1Is a decyl group or a hexadecyl group;
n is 4 to 500.
2. The method of preparing an azobenzene polymer material of claim 1, comprising the steps of:
A) carrying out azo reaction on the arylamine compound shown in the formula I-a to obtain a compound shown in the formula I-b;
B) reacting a compound shown as a formula I-b with halohydrin shown as a formula I-c to obtain a compound shown as a formula I-d;
C) carrying out acylation reaction on the compound shown in the formula I-d and acryloyl chloride to obtain a compound shown in the formula I-e;
D) carrying out polymerization reaction on the compound shown in the formula I-e to obtain a polymer shown in the formula I;
wherein R is1Is a decyl group or a hexadecyl group;
n is 4 to 500;
x is halogen.
3. The method according to claim 2, wherein the polymerization reaction in step D) is initiated by cyanoisopropyl dithiobenzoate and azobisisobutyronitrile.
4. The azobenzene polymer material of claim 1 or the azobenzene polymer material prepared by the preparation method of any one of claims 2 to 3 is applied as a photoresponse self-repairing material or a photo-control reversible adhesive.
5. The method for realizing self-repair of the azobenzene polymer material as set forth in claim 1 or the azobenzene polymer material as set forth in any one of claims 2 to 3, which is characterized by comprising the following steps:
at room temperature, after the surface of the azobenzene polymer solid material shown in the formula I in the trans-configuration is damaged, ultraviolet light is firstly used for irradiating the damaged part to enable the damaged part to be subjected to photoisomerization, the damaged part is converted into the cis-configuration to generate solid-liquid conversion, the damage is repaired, then visible light is used for irradiating the damaged part to enable the cis-azobenzene polymer to be restored to the trans-configuration, and self-repairing is achieved.
6. The method for reversibly bonding the azobenzene polymer material according to claim 1 or the azobenzene polymer material prepared by the preparation method according to any one of claims 2 to 3, comprising the steps of:
a) adopting a cis-configuration azobenzene polymer shown as a formula I as a bonding medium, bonding the substrates to be bonded, and converting the azobenzene polymer into a trans-configuration by irradiation of visible light to realize bonding of the substrates;
b) irradiating the bonding part by adopting ultraviolet light, converting the azobenzene polymer into a cis-configuration to generate solid-liquid conversion, and realizing the separation of the base materials;
c) repeating the steps a) and b) to realize reversible bonding.
7. The method of claim 5 or 6, wherein the ultraviolet light wavelength is 365 nm; the visible light wavelength is 530 nm.
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