CN107090086B - A kind of cyclic backbones azobenzene polymer self-healing gel and its preparation method and application - Google Patents
A kind of cyclic backbones azobenzene polymer self-healing gel and its preparation method and application Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 117
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920005565 cyclic polymer Polymers 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000003456 ion exchange resin Substances 0.000 claims description 7
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 7
- 239000003814 drug Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 5
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010511 deprotection reaction Methods 0.000 claims description 5
- 229940079593 drug Drugs 0.000 claims description 5
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 5
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical group NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 150000001540 azides Chemical class 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000499 gel Substances 0.000 abstract description 103
- 239000000463 material Substances 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 6
- 238000007699 photoisomerization reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- -1 electronic devices Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 108010025899 gelatin film Proteins 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000005621 boronate group Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WZEWDEAIHCUMKY-UHFFFAOYSA-N 2,2,5-trimethyl-1,3-dioxane-5-carboxylic acid Chemical compound CC1(C)OCC(C)(C(O)=O)CO1 WZEWDEAIHCUMKY-UHFFFAOYSA-N 0.000 description 1
- MSVMSXHTHSWNAU-UHFFFAOYSA-N 2-phenylcyclohexa-2,4-diene-1,1-diol Chemical group OC1(O)CC=CC=C1C1=CC=CC=C1 MSVMSXHTHSWNAU-UHFFFAOYSA-N 0.000 description 1
- XXJYLEWWCJOUNU-UHFFFAOYSA-N B(O)OBO.C(C1=CC=C(C(=O)O)C=C1)(=O)O Chemical compound B(O)OBO.C(C1=CC=C(C(=O)O)C=C1)(=O)O XXJYLEWWCJOUNU-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical compound OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011984 grubbs catalyst Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
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Abstract
The present invention provides a kind of cyclic backbones azobenzene polymer self-healing gels and its preparation method and application.The relatively narrow line polymer of molecular weight distribution is obtained by thermocatalytic nitrine-Terminal Acetylenes step-reaction polymerization of no metal, and its head and the tail cyclization is prepared for cyclic polymer；Linear and cyclic polymer is further prepared into self-healing gel rubber material.Compared with linear main chain azobenzene polymer self-healing gel, cyclic backbones azobenzene polymer self-healing gel has slower photo-isomerisable rate and self-healing rate, lower crosslink density, biggish solvent absorption ability, higher loss modulus and creep resisting ability；Show that cyclic polymer gel possesses bigger performance advantage in the application aspect for carrying medicinal gel.
Description
Technical Field
The invention belongs to the field of high molecular polymers, and particularly relates to a preparation method of a main chain azobenzene polymer self-healing gel, and important properties of the main chain azobenzene polymer self-healing gel, such as rheological property, tensile property, self-healing property and the like.
Background
The life is continued and is difficult to avoid unexpected damage and injury, fortunately, the skin, the tissue and the bone of the organism are endowed with certain repair and healing capabilities, and the diversity of organisms and species in the nature is also ensured. The research on the self-healing material is in a sense like giving the material "life", detecting the self-occurring damage through the material-and effectively repairing, and the high molecular material is used as a soft material, and the good extensibility and elasticity are more suitable for preparing the self-healing material.
Because of no terminal effect, the cyclic polymer has unique performance in the aspects of certain physical properties such as hydrodynamic volume, intrinsic viscosity, refractive index, glass transition temperature and the like compared with the linear polymer, so that the topological structure material prepared from the cyclic polymer has more excellent performance after being designed and has wider application prospect in the fields of information storage, biology, medicine and the like. The unique property of the topological structure of the cyclic polymer is utilized to prepare the material and explore the special properties brought by the structure of the material, and the work has important significance to the scientific theoretical innovation of macromolecules and lays a solid foundation for the invention of new materials.
The polymer gel is a three-dimensional network structure capable of absorbing a large amount of solvent through polymer crosslinking, and has been widely used in the fields of daily chemical products, electronic devices, petroleum industry, food engineering, medical devices, and the like. Conventional gels can be classified as chemical gels and physical gels due to the different ways of cross-linking. The chemical gel usually has firm chemical bonds to achieve the crosslinking effect, and has the advantages of good stability and high strength. The physical gel achieves the crosslinking effect by physical entanglement or weak interaction among molecules, and has the advantages of rapid solution-gel conversion and self-repairing. In recent years, as scientists have made intensive studies on gels, new gels crosslinked by dynamic covalent bonds have gained more and more attention. The dynamic covalent bond refers to a covalent bond which can perform reversible reaction under different external environments such as pH value, temperature, illumination and the like. Due to the unique property of cross-linked chemical bonds of the dynamic covalent gel, the prepared dynamic covalent gel has the advantages of both chemical gel and physical gel, has higher physical stability, and can quickly respond to the change of external environment to realize solution-gel conversion and self-repair.
Boron is a non-toxic inactive element, boron is an electron-deficient atom and is oxygen-philic, readily in sp form2The hybrid orbit is combined with oxygen atoms, and boron still lacks electrons at the moment, so that the boron and hydroxyl are easy to generate coordination reaction and dehydration to generate boric acid ester. Boric acid ester is widely used as a surfactant in the industry due to excellent antistatic, neutron radiation resistant, antibacterial, anticorrosion, lubricating, wear resistant, dispersing and emulsifying properties. Although the advantages are great, because of sp in the borate ester structure2The hybridized boron atom still has an empty p orbital which is easily hydrolyzed by water molecules containing lone pair electrons. Hydrolytic stability of boronates has been a problem in the industry, and reversible equilibration of boronates is being required for dynamic covalent bonds.
The topology of the polymer also has a unique impact on gel properties, Zhang et al have synthesized linear and cyclic polymers with a tailored Grubbs catalyst and separately prepared gels, and by comparison have found that cyclic polymer gels possess a greater swelling ratio, a greater mesh size and a lower crosslink density than their linear polymer gels when the solids content reaches a certain level (see Ke Zhang, Melissa a. lackey, Jun Cui, gregoryn. tew. j. am. chem. soc.2011,133, 4140-4148).
However, the use of cyclic polymers containing azobenzene as self-healing gel materials has not been reported so far.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method and application of a self-healing gel of a cyclic main chain azobenzene polymer. Compared with the linear main chain azobenzene polymer self-healing gel, the obtained cyclic main chain azobenzene polymer self-healing gel has higher swelling capacity, and meanwhile, under the condition of almost same energy storage modulus, the loss modulus is higher, and the creep resistance is stronger.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the structural formula of the self-healing gel of the cyclic main chain azobenzene polymer is shown as the formula (I):
wherein,representsR represents
A preparation method of a cyclic azobenzene polymer self-healing gel comprises the following steps:
(I) use of a compoundEtherifying with 1, 6-dibromohexane and nitridizing with sodium azide to obtain the compound(3) Through the coupling reaction with diazo salt of m-aminophenylacetylene to obtain the compoundThrough compound (4) and compound (5)The etherification reaction of (2) to obtain a main chain azobenzene polymer monomer, the structural formula of which is shown as the formula (6):
(II) carrying out stepwise polymerization reaction on the monomer (6) by adopting a stepwise heating method, and after the reaction is finished, carrying out fractional precipitation on the obtained linear polymer to obtain the linear polymer with narrow molecular weight distribution and normal GPC curve distribution, wherein the structural formula is shown as a formula (7):
(III) obtaining a cyclic polymer through azide/alkynyl CuAAC ring-closing reaction, and then carrying out deprotection reaction on the cyclic polymer to obtain a deprotected cyclic polymer, wherein the structural formula of the deprotected cyclic polymer is shown as a formula (8):
and (IV) dissolving the deprotected cyclic polymer by using tetrahydrofuran, adding p-phenylboronic acid, and uniformly mixing by using a vortex mixer at the speed of 800-2000r/min to obtain the cyclic main chain azobenzene polymer self-healing gel within 10 s.
Further, the specific reaction conditions of the step-by-step polymerization reaction in the step (two) are as follows: the reaction temperature and the reaction time are 70-85 ℃ for 8-9h, 98-105 ℃ for 5.5-6.5h and 110-125 ℃ for 1.5-2h in sequence.
Further, the specific operation of fractional precipitation in the step (two) is to dissolve the obtained linear polymer with a tetrahydrofuran solution, and then add n-hexane to perform fractional precipitation, and the above operations are repeated at least five times.
Further, the specific preparation process of the cyclic polymer obtained by the azide/alkynyl CuAAC ring-closing reaction in the step (iii) is as follows: 20mL of 0.0012mol/L linear polymer solution is continuously added into the N, N-dimethylformamide solution of CuBr/PMDETA at the speed of 0.5mL/h under the protection of inert gas; wherein the molar ratio of the linear polymer to the cuprous bromide to the pentamethyldiethylenetriamine is 1:100: 150.
Further, the specific method of the deprotection reaction in the step (three) is as follows: the mass ratio of the cyclic polymer: and (3) adding the cyclic polymer and the acidic ion exchange resin into dichloromethane and methanol solvent in the same volume ratio, stirring at room temperature, filtering after stirring for 5h, and performing rotary evaporation on the filtrate to remove the solvent to obtain the deprotected cyclic polymer, wherein the acidic ion exchange resin is 1: 2.5-4.
Further, the acidic ion exchange resin is Dowex50 x 8.
Further, the crosslinking group diol in the step (iv): the molar ratio of boric acid is 1-2: 1.
An application of a self-healing gel of a cyclic polymer as a drug-loaded gel.
The invention has the beneficial effects that:
(1) the cyclic main chain azobenzene polymer self-healing gel provided by the invention has wound self-healing capacity, larger solvent absorption capacity relative to linear polymers, lower crosslinking density and higher creep resistance, and has larger performance advantages in the application aspect of drug-loaded gel, for example, more drugs can be loaded, and the stability of the internal structure of the gel is better when the gel is applied to a wound;
(2) according to the self-healing gel of the ring-shaped main chain azobenzene polymer, the azobenzene response speed is slower, and the drug-loaded release time is longer after photo-deformation, so that the use value of the self-healing gel is increased.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of the compound (6) in the first example.
FIG. 2 is a GPC outflow graph of linear and cyclic polymers in one example.
FIG. 3 shows the hydrogen nuclear magnetic spectra of linear and cyclic polymers in example.
FIG. 4 shows the IR spectra of linear and cyclic polymers in example A.
FIG. 5 is a hydrogen nuclear magnetic spectrum of the deprotected linear polymer of example one.
FIG. 6 is a hydrogen nuclear magnetic spectrum of the deprotected cyclic polymer of example one.
FIG. 7 is a diagram showing how to prepare a linear-backbone azobenzene polymer self-healing gel and a cyclic-backbone azobenzene polymer self-healing gel according to one embodiment.
FIG. 8 is the rheological curves of the self-healing gel of linear-backbone azobenzene polymer and the self-healing gel of cyclic-backbone azobenzene polymer in different solvent contents in the second embodiment.
Fig. 9 is a picture of the self-healing of the cuts of the linear-backbone azobenzene polymer self-healing gel and the cyclic-backbone azobenzene polymer self-healing gel in the third example.
FIG. 10 is a self-healing tensile curve of the linear-backbone azobenzene polymer self-healing gel and the cyclic-backbone azobenzene polymer self-healing gel in the three examples.
Fig. 11 is a schematic view of the topological structures of the linear-backbone azobenzene polymer self-healing gel and the cyclic-backbone azobenzene polymer self-healing gel in the third embodiment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description is further provided with reference to the accompanying drawings and embodiments.
The first embodiment is as follows: polymer synthesis and gel preparation process
(1) Into a 1000mL three-necked flask were charged 2.85g of 2, 2-dihydroxybiphenyl and 2.1g K2CO3500mL of acetone, and heated to reflux in an oil bath at 70 ℃. 3.95g of 1, 6-dibromohexane in acetone was added dropwise to the reaction system. After the addition was completed, the reaction was carried out for half an hour. And (3) carrying out suction filtration on the reaction solution, carrying out rotary evaporation on the filtrate to remove the solvent, and carrying out column chromatography purification to obtain the compound (2).
(2) Into a 50mL round-bottomed flask were added 4.0g of Compound (2), 1.13g of NaN3And 30ml of DMF in a 50 ℃ oil bath for 24 hours. After the reaction, water and ethyl acetate were used for extraction, the organic layer was dried to remove water, and the solvent was removed by rotary evaporation to obtain compound (3).
(3) To a 100mL beaker was added 4.25g of m-aminophenylacetylene, and to this was added 16.6mL of concentrated hydrochloric acid and 40mL of deionized water with stirring in an ice-water bath. When the temperature is reduced to 0 ℃, dropwise adding sodium nitrite aqueous solution (2.75g of NaNO) into the system2Dissolved in 30mL of deionized water). Keeping the reaction temperature at 0-5 ℃, and continuing to react for 30 minutes after the dropwise addition is finished to obtain the diazonium salt solution of the m-aminophenylacetylene. To a 500mL beaker were added 12.0g of Compound (3), 300mL of deionized water, and 2.9g of sodium nitrite, and the beaker was placed in an ice-water bath. The above diazonium salt solution was added dropwise to the system, and the reaction was continued for 2 hours after the addition. And after the reaction is finished, pouring out water to obtain a crude product, drying the crude product, and purifying by column chromatography to obtain the compound (4).
(4) Adding 10g of tetraethylene glycol and 2g of triethylamine into a 100mL beaker, dropwise adding 6-bromine-hexanoyl chloride under the condition of stirring in an ice bath at the temperature of 0 ℃,after the dropwise addition, the reaction was carried out at room temperature for two hours. After the reaction, extraction was performed with water and ethyl acetate, the organic layer was dried to remove water, the solvent was removed by rotary evaporation, and 5g of intermediate compound (5) was obtained by column chromatography5g of compound (5) was dissolved in 50mL of methylene chloride and poured into a 100mL three-necked flask, and then 0.83g of 4-dimethylaminopyridine and 1.55g of 2,2, 5-trimethyl-1, 3-dioxane-5-carboxylic acid were added to the flask and dissolved with stirring. After 3.34g of dicyclohexylcarbodiimide was dissolved in 15mL of dichloromethane, the solution was added dropwise to a three-necked flask, stirred at room temperature for 12 hours, extracted with water and ethyl acetate, the organic layer was dried to remove water, the solvent was removed by rotary evaporation, and the compound (5) was obtained by column chromatography.
(5) 5g of the compound (4), 4.2g of the compound (5), 1.35g of potassium carbonate and a catalytic amount of potassium iodide are dissolved in 100mL of dimethylformamide, the mixture is stirred in a pot at 70 ℃ for reaction for 4 hours, after the reaction is finished, water and ethyl acetate are used for extraction, an organic layer is dried and dehydrated, a solvent is removed by rotary evaporation, and the compound (6) is obtained by a column chromatography method, wherein a nuclear magnetic spectrum is shown in FIG. 1, so that the successful synthesis of the compound (6) is proved.
(6) The compound (6) is subjected to stepwise polymerization by a stepwise temperature rise method. The reaction temperature and the reaction time are respectively 80 ℃ for 8h, 100 ℃ for 6h and 120 ℃ for 2 h. Then the obtained linear polymer is dissolved by a tetrahydrofuran solution, then n-hexane is added for fractional precipitation, and the fractional precipitation is repeated for five times to obtain the linear polymer with narrow molecular weight distribution and normal distribution of GPC curve. The number average molecular weight of the polymer was 8100 and the molecular weight distribution was 1.23.
(7) 700mL of DMF was added to a 1000mL three-necked flask, and the mixture was put in an oil bath pan at 80 ℃ and purged with argon for 4 hours while stirring. 0.35g of cuprous bromide and 1.04g of pentamethyldiethylenetriamine are added into the system, then 0.2g of DMF solution compound of the linear polymer is dissolved in 20mL of DMF, and is slowly injected into the reaction system at the speed of 0.5mL/h through a micro-injection pump, and the reaction is continued for 10 hours after the injection is finished. And after the reaction is finished, distilling the reaction liquid under reduced pressure to remove the solvent, extracting with water and ethyl acetate, drying the organic layer to remove water, removing the solvent by rotary evaporation, and obtaining the cyclic polymer by a column chromatography method. The GPC outflow curve chart of the linear polymer and the cyclic polymer is shown in figure 2, the nuclear magnetic spectrum is shown in figure 3, and the infrared spectrum is shown in figure 4, which proves the success of the cyclization reaction.
(8) 1g of linear polymer was dissolved in 50mL of dichloromethane and methanol in a volume ratio of 1:1 in a 100mL single-neck flask, 3g dowex50 x 8 acidic ion exchange resin was added to the flask with stirring at room temperature. Stirring for 5h, filtering, and performing rotary evaporation on the filtrate to remove the solvent. The same procedure was used to obtain a deprotected cyclic polymer. The nuclear magnetic spectra of the obtained deprotected linear polymer and cyclic polymer are shown in FIGS. 5 and 6, which prove the successful deprotection.
(9) The preparation of the gel is that 0.2g of deprotected linear polymer and cyclic polymer are respectively dissolved in 2mL of tetrahydrofuran and filled in a 10mL ampere bottle, then 19.4mg of terephthalic diboronic acid is respectively added and evenly mixed on a mixing stirrer, and the linear main chain azobenzene polymer self-healing gel and the cyclic main chain azobenzene polymer self-healing gel can be respectively obtained within one minute. As shown in fig. 7, the successful preparation of the self-healing gel of linear-backbone azobenzene polymer and the self-healing gel of cyclic-backbone azobenzene polymer was demonstrated.
(10) And (3) naturally volatilizing tetrahydrofuran in the prepared linear main chain azobenzene polymer self-healing gel and cyclic main chain azobenzene polymer self-healing gel in a dry dryer. And after two days, respectively adding 0.51g of tetrahydrofuran swollen gel into an ampere bottle filled with the linear main chain azobenzene polymer dry glue and the cyclic main chain azobenzene polymer dry glue to obtain the linear main chain azobenzene polymer self-healing gel and the cyclic main chain azobenzene polymer self-healing gel with the solvent mass percentage of 70%. The same method can prepare the linear main chain azobenzene polymer self-healing gel and the cyclic main chain azobenzene polymer self-healing gel with the solvent mass percent of 30 percent.
Example two: method for testing gel rheological properties of different solvents in mass percentage
(1) Firstly, strain scanning tests are respectively carried out on the prepared linear and cyclic polymer gels in a region with the strain gamma being 0.1% -10% by using a turntable with the diameter of 2cm, and the storage modulus G ' is larger than the loss modulus G ' and the G ' are not obviously changed along with the increase of the gamma. Thus, the region was identified as the linear viscoelastic region of the gel, and the test contents were the modulus-time, apparent viscosity-time rheological property tests under the conditions of 25 ℃ temperature, 1.0Hz frequency f, and 1.0% strain γ. The test result is shown in fig. 8, the storage modulus G' of the linear-backbone azobenzene polymer self-healing gel and the cyclic-backbone azobenzene polymer self-healing gel are not much different, but the loss modulus G ″ of the linear-backbone azobenzene polymer self-healing gel is obviously smaller than that of the cyclic-backbone azobenzene polymer self-healing gel. The phenomenon shows that the special topological structure of the cyclic polymer influences the macroscopic performance of the gel material, the self-healing gel of the linear main chain azobenzene polymer has better plasticity, and the self-healing gel of the cyclic main chain azobenzene polymer has better shape stability.
Example three: method for testing gel stretching self-healing performance with solvent mass percent of 30%
Respectively testing the tensile properties of 30 mass percent of linear main chain azobenzene polymer self-healing gel and cyclic main chain azobenzene polymer self-healing gel under the conditions that a polytetrafluoroethylene splint and a hydraulic press are used for pressing the gel into a 0.7mm thin sheet, then the thin sheet is cut into a plurality of strips with the length of 2cm and the width of 1cm by a blade, and the linear and cyclic gel strips are respectively tested for the tensile properties by a tensile instrument at the speed of 10 cm/min. In the control group, we cut the previously prepared strip by 0.5cm in the middle with a blade, leave the sample stand for 2min and then perform a tensile test at 10cm/min with a tensile tester. The comparison of the change of the maximum tensile stress before and after the incision shows that the stretching capacity of the self-healing gel of the linear main chain azobenzene polymer after the incision is recovered to about 75 percent, and the stretching capacity of the self-healing gel of the cyclic main chain azobenzene polymer is only recovered to 60 percent of the maximum tensile stress before. This phenomenon is due to the fact that the cyclic polymer has a special topology, so that the internal segment motion capability of the cyclic polymer is inferior to that of the self-healing gel of the linear-backbone azobenzene polymer. The test patterns are shown in fig. 9 and 10. The topological structures of the linear-backbone azobenzene polymer self-healing gel and the cyclic-backbone azobenzene polymer self-healing gel are schematically shown in fig. 11.
Example four: self-healing gel of linear main chain azobenzene polymer and cross-linking density test of self-healing gel of cyclic main chain azobenzene polymer
And respectively soaking the linear main chain azobenzene polymer dry glue and the cyclic main chain azobenzene polymer dry glue in a tetrahydrofuran solution for 10min, and then taking out the gel every other minute and weighing until the weighed gel mass does not change for three times. We note the volume change of the gel and the mass of solvent absorbed, where we assume the linear polymer density to be 1mg/mL and the cyclic polymer density to be converted from the hydrodynamic volume to 1.2mg/mL, and we calculate the crosslink density of the linear and cyclic polymer gels, respectively, by the Flory equilibrium swell equation, which is as follows.
Note:
the test results are shown in table 1. The result shows that the crosslinking density of the self-healing gel of the linear main chain azobenzene polymer is higher than that of the self-healing gel of the cyclic main chain azobenzene polymer, and the tetrahydrofuran solution absorption capacity of the self-healing gel of the cyclic main chain azobenzene polymer is lower than that of the self-healing gel of the cyclic main chain azobenzene polymer.
Table 1: example two theoretical calculation comparison of crosslinking density of linear-backbone azobenzene polymer self-healing gel and cyclic-backbone azobenzene polymer self-healing gel
Example five: photoisomerization test of linear polymer and cyclic polymer in solution and film state, and of self-healing gel of linear main chain azobenzene polymer and cyclic main chain azobenzene polymer in film state
The linear polymer and the cyclic polymer were prepared into 0.04mg/mL tetrahydrofuran solutions at a concentration of 0.55mW/cm2Irradiating the azobenzene group by using ultraviolet light with the wavelength of 365nm to enable the azobenzene group to generate trans-cis isomerism, and obtaining an ultraviolet-visible light absorption spectrum of the solution by using an ultraviolet spectrophotometer; after the solution reaches trans-cis isomerization equilibrium, cis-trans isomerization is carried out by using visible light with the wavelength of 425 nm. By processing and analyzing the spectrogram, the primary kinetic curves of trans-cis and cis-trans photoisomerization of the solution can be obtained.
The difference between the linear and cyclic polymer film and the linear and cyclic main chain azobenzene polymer self-healing gel film is that the gel film contains the corresponding cross-linking agent terephthalic acid diboronic acid. The preparation method of the film adopts 5mg of solid components to be dissolved in 5mL of tetrahydrofuran, and 100 mu L of the solid components is fully dissolved and spin-coated on a quartz glass sheet to form the film. The following light induced isomerism test conditions are the same as above, and the test machine is changed into an external integrating sphere.
The results obtained are shown in table 2, and it was found by comparison that the rate of photoisomerization of azobenzene in the linear polymer is slower than that of azobenzene in the cyclic polymer when in solution, while the rate of photoisomerization of azobenzene in the linear polymer is faster than that of azobenzene in the cyclic polymer in the state of the linear, cyclic polymer film and the self-healing gel film of the linear, cyclic main chain azobenzene polymer, which illustrates the influence of different topographies and packing tightness of the polymers on the photoisomerization rate.
Table 2: example two photo-isomerization rate comparison of Linear and Cyclic Polymer solutions and films to Linear and Cyclic backbone Azobenzene Polymer self-healing gel films
In conclusion, the linear polymer with narrow molecular weight distribution is obtained by metal-free thermal catalysis azide-terminal alkyne stepwise polymerization reaction, and the cyclic polymer is prepared by closing the ends of the linear polymer; the linear and cyclic polymers are further prepared into self-healing gel materials. Compared with the linear main chain azobenzene polymer self-healing gel, the cyclic main chain azobenzene polymer self-healing gel has slower photoinduced isomerization rate and self-healing rate, lower crosslinking density, larger solvent absorption capacity and higher loss modulus and creep resistance, and the research lays a theoretical foundation for the preparation and the application of the cyclic azobenzene polymer gel material.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. The self-healing gel of the cyclic main chain azobenzene polymer is characterized in that the structural formula of the self-healing gel of the cyclic main chain azobenzene polymer is shown as the formula (I):
wherein,representsR represents
2. A method for preparing the cyclic backbone azobenzene polymer self-healing gel according to claim 1, comprising the steps of:
(I) use of a compoundEtherifying with 1, 6-dibromohexane to obtain a compoundAzidation of sodium azide to give compounds(3) Through the coupling reaction with diazo salt of m-aminophenylacetylene to obtain the compoundThrough compound (4) and compound (5)The etherification reaction of (2) to obtain a main chain azobenzene polymer monomer, the structural formula of which is shown as the formula (6):
(II) carrying out stepwise polymerization reaction on the monomer (6) by adopting a stepwise heating method, and after the reaction is finished, carrying out fractional precipitation on the obtained linear polymer to obtain the linear polymer with narrow molecular weight distribution and normal GPC curve distribution, wherein the structural formula is shown as a formula (7):
(III) obtaining a cyclic polymer through azide/alkynyl CuAAC ring-closing reaction, and then carrying out deprotection reaction on the cyclic polymer to obtain a deprotected cyclic polymer, wherein the structural formula of the deprotected cyclic polymer is shown as a formula (8):
and (IV) dissolving the deprotected cyclic polymer by using tetrahydrofuran, adding p-phenylboronic acid, and uniformly mixing by using a vortex mixer at the speed of 800-2000r/min to obtain the cyclic main chain azobenzene polymer self-healing gel within 10 s.
3. The method for preparing the self-healing gel of the cyclic-backbone azobenzene polymer according to claim 2, wherein the specific reaction conditions of the step-by-step polymerization reaction in the second step are as follows: the reaction temperature and the reaction time are 70-85 ℃ for 8-9h, 98-105 ℃ for 5.5-6.5h and 110-125 ℃ for 1.5-2h in sequence.
4. The method for preparing a self-healing gel of a cyclic-backbone azobenzene polymer according to claim 2, wherein the step (ii) of fractional precipitation is carried out by dissolving the obtained linear polymer with tetrahydrofuran solution, and then adding n-hexane to carry out fractional precipitation, wherein the above steps are repeated at least five times.
5. The method for preparing the self-healing gel of the cyclic-backbone azobenzene polymer according to claim 2, wherein the specific preparation process of the cyclic polymer obtained by the azide/alkynyl CuAAC ring-closing reaction in the step (iii) is as follows: 20mL of 0.0012mol/L linear polymer solution is continuously added into the N, N-dimethylformamide solution of CuBr/PMDETA at the speed of 0.5mL/h under the protection of inert gas; wherein the molar ratio of the linear polymer to the cuprous bromide to the pentamethyldiethylenetriamine is 1:100: 150.
6. The method for preparing the self-healing gel of the cyclic-backbone azobenzene polymer according to claim 2, wherein the deprotection reaction in the step (three) is specifically performed by: the mass ratio of the cyclic polymer: and (3) adding the cyclic polymer and the acidic ion exchange resin into dichloromethane and methanol solvent in the same volume ratio, stirring at room temperature, filtering after stirring for 5h, and performing rotary evaporation on the filtrate to remove the solvent to obtain the deprotected cyclic polymer, wherein the acidic ion exchange resin is 1: 2.5-4.
7. The method for preparing the self-healing gel of cyclic backbone azobenzene polymer according to claim 6, wherein the acidic ion exchange resin is Dowex50 x 8.
8. The method for preparing a self-healing gel of cyclic-backbone azobenzene polymer according to claim 2, wherein the crosslinking group diol in the step (iv): the molar ratio of boric acid is 1-2: 1.
9. The use of the cyclic backbone azobenzene polymer self-healing gel of claim 1 as a drug loaded gel.
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