CN103087257A - Preparation method for pH and temperature dual-sensitive ion micro-hydrogel - Google Patents
Preparation method for pH and temperature dual-sensitive ion micro-hydrogel Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 81
- 230000009977 dual effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 64
- 150000002500 ions Chemical class 0.000 claims abstract description 37
- 230000035945 sensitivity Effects 0.000 claims abstract description 29
- -1 alkane compound Chemical class 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 21
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 125000001302 tertiary amino group Chemical group 0.000 claims description 6
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical compound C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 claims description 5
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical class CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 4
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 3
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 claims description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- AZLIIAMTCHKNJJ-UHFFFAOYSA-N potassium;trifluoromethanesulfonic acid Chemical compound [K].OS(=O)(=O)C(F)(F)F AZLIIAMTCHKNJJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims description 2
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 claims description 2
- LBKDGROORAKTLC-UHFFFAOYSA-N 1,5-dichloropentane Chemical compound ClCCCCCCl LBKDGROORAKTLC-UHFFFAOYSA-N 0.000 claims description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 2
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 claims description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 2
- RQMWVVBHJMUJNZ-UHFFFAOYSA-N 4-chloropyridin-2-amine Chemical group NC1=CC(Cl)=CC=N1 RQMWVVBHJMUJNZ-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 claims 1
- 241000233803 Nypa Species 0.000 claims 1
- 235000005305 Nypa fruticans Nutrition 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 10
- 238000001291 vacuum drying Methods 0.000 abstract description 9
- 229920000831 ionic polymer Polymers 0.000 abstract description 8
- 239000003814 drug Substances 0.000 abstract description 5
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- 239000000203 mixture Substances 0.000 abstract 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 29
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 26
- 238000002356 laser light scattering Methods 0.000 description 19
- 150000003839 salts Chemical class 0.000 description 16
- 150000002892 organic cations Chemical class 0.000 description 15
- 238000010792 warming Methods 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000499 gel Substances 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 239000002608 ionic liquid Substances 0.000 description 7
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- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 241000024287 Areas Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
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- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 0 *N(*)C(C=*)=O Chemical compound *N(*)C(C=*)=O 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention relates to the field of environment-sensitive type high polymer materials and aims at providing a preparation method for a pH and temperature dual-sensitive ion micro-hydrogel. The preparation method comprises the following steps of: carrying out free-radical copolymerization to N-alkyl acrylamide monomer, a double-bond compounding containing a tertiary amine radical and initiator in anhydrous solvent 1,4-dioxane or tetrahydrofuran under the oxygen-free condition; extracting binary copolymer by adopting diethyl ether or petroleum ether as a precipitant, and vacuum-drying the binary copolymer until the weight is constant after the centrifugal separating; preparing the obtained binary copolymer into aqueous solution; adding polyhalogenated alkane compound to the aqueous solution, and stirring the solution at the constant temperature of 40 DEG C to 70 DEG C; and adding an organic cation salt compound after the mixture is purified, and stirring the mixture under the room temperature to obtain the pH and temperature dual-sensitive ion micro-hydrogel. The preparation method provided by the invention is simple and easy to control, and the obtained micro-hydrogel has dual sensitivities of pH and temperature; and moreover, excellent characteristics of the polyion liquid are introduced, the purity is high, the stability is good and the swelling rate is high, so that the preparation method is suitable for the fields such as controlled slow release of the medicines, the sensors and the like.
Description
Technical field
The present invention relates to the polymeric material field of environment sensitive type, be specifically related to micro-hydrogel of ion of a kind of pH of having and temperature dual susceptibility and its preparation method and application.
Background technology
Hydrogel is cross-linked to form the hydrophilic high mol network because its inside exists physics or chemical bonds, and water can only be penetrated into the macromolecule network interchain, via swelling action, forms gel, can only swelling and can not be dissolved in the water.Due to high-moisture and biocompatibility, hydrogel has extraordinary application prospect on biomedicine, has obtained the extensive concern of researcher.Microgel (microgel) is the cross-linked latex grain of swelling in good solvent with colloid size (1nm ~ 10 μ m), and its molecular structure is between branched macromolecule and polymkeric substance macro network structure.According in molecule and surface, the non-responsiveness group is arranged, microgel can be divided into responsiveness microgel and non-responsiveness microgel two classes, wherein active with the research of responsiveness microgel, is most widely used.Typical external stimulus has temperature, pH value, solvent, salt concn, light, sound field, electric field, pressure etc.When microgel is subject to these external stimuluss, volume change can occur, utilize this stimuli responsive characteristic, can be by microgel as preparation drug delivery and control release vehicle material.The research of the microgel that wherein the water-soluble double bond compounds such as NIPA, acrylamide and vinylformic acid are made through copolymerzation with cross-linking is particularly outstanding.
Ionic liquid at room temperature (Room Temperature Ionic Liquid) is a kind of ionic compound at room temperature be in a liquid state.Only there is the yin, yang ion in ionic liquid, there is no neutral molecule.Because of its special construction, ionic liquid has many peculiar properties, and for example: stable existence is in a liquid state under normal temperature; Non-volatile, nonflammable, almost there is no vapour pressure; There is chemical stability preferably, wider electrochemical stability potential window; Can regulate the solvability that changes inorganics, water, organism and polymkeric substance; Nontoxic pollution-free, often be called as " green solvent ".Along with deepening continuously of ionic liquid research, some investigators combine ionic liquid with polymer, for example: the green solvent using ionic liquid in polymerization process, the special solvent of biomacromolecule, initiator or promotor etc., even, using it as functional monomer, obtain poly ion liquid.Typical poly ion liquid be with positively charged ion as pyrrolidone, imidazoles, pyridine and negatively charged ion as a tetrafluoro borate, phosphofluoric acid, the functional polymer of triflate.Be analogous to ionic liquid, poly ion liquid can be applicable to many different technical fields, as environmental energy, analytical chemistry, Materials science, biotechnology, catalyzer, Surface Science etc.
The present invention is devoted to microgel is combined with poly ion liquid, makes its good characteristic that simultaneously has the two, and, by the synergy between the two, brings into play the function that makes new advances, the potential using value of exploitation ion microgel.Up to the present, many reports about polyelectrolyte and intelligent aqueous gel capable and patent are arranged both at home and abroad, but substantially there is no report about the microgel that there is poly ion liquid character and intelligent response simultaneously.And most of polyelectrolyte hydrogel of reporting exists with block body gel form, and preparation process is comparatively loaded down with trivial details, affects its application prospect; On the other hand, nearly all report is all to adopt N, and N-dimethylene acrylamide, Ethylene glycol dimethacrylate etc. are that chemical cross-linking agent carries out crosslinking reaction containing the compound of a plurality of unsaturated double-bonds.At this, we have designed and developed the new preparation process with the micro-hydrogel of new features, have enriched kind and the preparation method of micro-hydrogel system.
Chinese patent CN1586706 discloses a kind of preparation method of fast temperature response semi-interpenetrating network aqueous gel.The gel of this invention preparation has fast temperature-responsive, pH responsiveness and gel-strength preferably preferably, has widened range of application, particularly biology and the field of medicaments of gel.Chinese patent CN101117392 discloses a kind of natural amphoteric polyelectrolyte electric field sensitive aqueous gel and preparation method thereof.This invention adopts natural polycation electrolyte and natural polyanion electrolyte to carry out solution blending, prepares natural polyampholyte hydrogel film.This aquagel membrane has electric field response in the electrolyte solution of different pH values, has expanded its pH value scope applicable as electric field sensitive aqueous gel.But above-mentioned gel is block or membranaceous gel, size is larger, the microsize that does not have micro-hydrogel colloidal solid, be difficult to be applicable to the various Application Areass that need reduced size, the particularly biomedicine field such as drug loading and controllable release as micro-hydrogel.
Chinese patent CN101851315A discloses a kind of preparation method of degradable polyampholyte microgel, by configuration reverse microemulsion, aqueous phase solution, oil-phase solution, the oil phase of take is made the water-in-oil reverse microemulsion as mother liquor, in electric heating, water-bath, fill under nitrogen, whipped state and add raw material to carry out polyreaction, make the polyampholyte microgel emulsion, through breakdown of emulsion precipitation, washing, suction filtration, dialysis, centrifugation, vacuum-drying, make the amphotericeledrolyte micro-gel particles.This amphotericeledrolyte microgel iso-electric point place particle flux mechanics diameter is 105.7nm, but size distribution is wider, and the preparation method is comparatively loaded down with trivial details, the purification process complexity.
Chinese patent CN101037494A discloses that a kind of to take NIPA and vinylformic acid etc. be main monomer, under the existence of chemical cross-linking agent, adopt specific dropping technology and emulsifier-free emulsion polymerization method to prepare pH and the micro-hydrogel of temperature dual susceptibility, the particle diameter of its micro-hydrogel is 40-400nm, but monomer and chemical cross-linking agent simultaneous reactions in preparation process, because the reaction spending rate of chemical cross-linking agent will be far faster than monomer reaction speed, cause micro-hydrogel internal crosslinking degree inhomogeneous, thereby affected microtexture and the physicals of micro-hydrogel; Its purge process is long simultaneously, needs dialysis 1-3 week or repeats high speed centrifugation the ultrasonic redispersion of 3-6 time.
In above-mentioned patent, the preparation method of related hydrogel is comparatively loaded down with trivial details, the purification process complexity, or the product size obtained is too large or distribution of sizes is wider, is unfavorable for suitability for industrialized production and further scientific research.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, and a kind of pH and the micro-hydrogel of temperature sensitive ion and preparation method thereof are provided.The micro-hydrogel of this ion, have the character of pH and temperature dual susceptibility and poly ion liquid, and the preparation method is simple, and size is less, is adapted at the application in medicine controllable sustained-release and sensor field.Method of the present invention is without being used linking agent and tensio-active agent, by the quaterisation of monomer, realizes crosslinkedly, and makes polymer ions, and technique is simple and have a novelty.
For the technical solution problem, technical scheme of the present invention is:
The preparation method of the micro-hydrogel of ion of a kind of pH and temperature dual sensitivity is provided, comprises the following steps:
By N-alkyl acrylamide class monomer M 1, containing the double bond compound M2 of tertiary amine group, initiator at anhydrous solvent 1, in 4-dioxane or tetrahydrofuran (THF), carry out free radicals copolymerization reaction under oxygen free condition, controlling temperature of reaction is 60-90 ° of C, and the time is 12-24 hour; Then adopting ether or sherwood oil is the copolymer generated in the precipitation agent abstraction reaction, through the centrifugation final vacuum, is dried to constant weight; The gained copolymer is mixed with to the aqueous solution that mass concentration is 0.05-0.5% at 25 ° of C, add many compound halo alkanes M3, at 40-70 ° of C constant temperature, stir 24 hours, add organic cation salt compounds M4 after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature make the micro-hydrogel of ion of purifying;
The chemical structural formula of M1, M2, M3 and M4 is respectively:
In formula, R
1for hydrogen atom and R
2for sec.-propyl, or R
1for ethyl and R
2for ethyl; R
3for the carbonatoms straight chained alkyl that is 2 ~ 6; X is pyridines or imidazoles group; Y is chlorine or bromine; A is lithium or sodium or potassium; B is dodecyl sodium sulfonate root or fluoroboric acid root or trifluoromethane sulfonic acid root;
In M1, M2 and tri-kinds of reactants of M3, shared mass percent is respectively M1:87.5-95.4% separately, M2:4.0-8.3%, M3:0.6-4.2%; M4 accounts for the 0-6% of M1, M2 and M3 total mass; The 2.0-2.7% that the consumption of described initiator is M1 and M2 total mass.
In the present invention, described N-alkyl acrylamide class monomer M 1 is NIPA or N, the two ethyl acrylamides of N-.
In the present invention, the described double bond compound M2 containing tertiary amine group is 2-vinyl pyridine, 3-vinyl pyridine, 4-vinylpridine or N-vinyl imidazole.
In the present invention, described many compound halo alkanes M3 is 1,2-ethylene dichloride, glycol dibromide, 1,3-propylene dichloride, 1,3-dibromopropane, Isosorbide-5-Nitrae-dichlorobutane, Isosorbide-5-Nitrae-dibromobutane, 1,5-dichloropentane, 1, pentamethylene bromide, 1,6-dichloro hexane or 1,6-dibromo-hexane.
In the present invention, described organic cation salt compounds M4 is dodecyl sodium sulfonate lithium, sodium laurylsulfonate, dodecyl sodium sulfonate potassium, lithium-fluoroborate, Sodium tetrafluoroborate, potassium fluoborate, trifluoromethyl sulfonic acid lithium, trifluoromethyl sulfonate or trifluoromethane sulfonic acid potassium.
In the present invention, described initiator is Diisopropyl azodicarboxylate.
Principle of the present invention is: M2 monomer resulting polymers is as responsive to the pH value of environment as poly 4 vinyl pyridine etc.; M1 monomer resulting polymers as poly N-isopropyl acrylamide etc. to the envrionment temperature sensitivity, it has a low critical transition temperature (LCST) 31-32 ° of C left and right, when temperature during lower than LCST, poly N-isopropyl acrylamide can be dissolved in deionized water fully, and when temperature during higher than LCST, the poly N-isopropyl acrylamide water fast, due to the hydrogen bond in molecular chain and between molecular chain and hydrophobic interaction, be agglomerated into bead between the poly N-isopropyl acrylamide molecular chain; On the other hand, many halogenated alkanes M3 as Isosorbide-5-Nitrae-dibromobutane etc. can with the tertiary amine group generation quaterisation of M2 as 4-vinylpridine; Obtain copolymer if first monomer M 1 and M2 are carried out to copolymerization, by this multipolymer, be dissolved in deionized water fully again, heating makes solution temperature be greater than the LCST of M1 resulting polymers, under 40-70 ° of C state of temperature, stir, quaternized crosslinking reaction occurs in the multipolymer tertiary amine structure in M2 and M3 when being agglomerated into bead, makes the shape and size of multipolymer bead be fixed; Due to the reunion degree of multipolymer, the namely size of multipolymer bead and temperature correlation, the size that can regulate bead by controlling solution temperature, obtain the microgel bead of different size.Finally by quaternary ammonium salt crosslinked in microgel and organic cation salt, carry out ion-exchange, obtain the micro-hydrogel of ion of pH and temperature dual sensitivity.
Micro-hydrogel traditional with other and preparation method thereof compared, and the invention has the beneficial effects as follows:
1, include pH sensitivity and two kinds of monomers of temperature sensitive in the micro-hydrogel structure monomer of the present invention, thereby micro-hydrogel prepared by the present invention possesses pH and temperature dual susceptibility simultaneously.
2, the present invention adopts quaterisation to make polymkeric substance occur crosslinked the time to have introduced Ionized quaternary ammonium salt, and microgel the is obtained good characteristic of poly ion liquid has enlarged the potential Application Areas of microgel.
3, preparation method of the present invention, the particle diameter of micro-hydrogel that obtains is 817-5490nm, and can, by changing temperature and the degree of crosslinking that aqueous solution constant temperature stirs in the preparation process of micro-hydrogel, obtain micro-hydrogel of different size.
4, preparation method of the present invention, micro-swelling behavior rate that obtains large, be specially adapted to the Application Areass such as drug controllable release.
5, preparation method of the present invention is simple, and reaction process is clear and definite, and does not introduce tensio-active agent, and purge process is convenient, and technique is simply controlled, is applicable to suitability for industrialized production.
The accompanying drawing explanation
The infrared spectrogram that Fig. 1 is copolymer P (NIPAm-co-4VP).
Fig. 2 is copolymer P's (NIPAm-co-4VP)
1the H nmr spectrum.
The transmission electron microscope photo of the micro-hydrogel of ion that Fig. 3 is pH and temperature dual sensitivity.
The particle diameter of the micro-hydrogel of ion that Fig. 4 is pH and temperature dual sensitivity and the graph of a relation of envrionment temperature, embodied the temperature sensitivity of micro-hydrogel.
The particle diameter of the micro-hydrogel of ion that Fig. 5 is pH and temperature dual sensitivity and the graph of a relation of pH value, embodied the pH susceptibility of micro-hydrogel.
Embodiment
Embodiment 1:
1.5g temperature sensitive monomer NIPA (NIPAm), 0.09g pH sensitive monomer 4-vinylpridine (4VP) are dissolved in anhydrous 1, in the 4-dioxane, stir it is fully dissolved under the nitrogen atmosphere condition, add again the 0.036g Diisopropyl azodicarboxylate, fully stir, under the nitrogen atmosphere condition, under 70 ° of C oil baths, isothermal reaction, after 24 hours, is taken out and is naturally cooled to room temperature, with ether, the gained reactant is precipitated out, under 4000 rpms, through 15 minutes final vacuum dryings of centrifugation, obtains copolymer P (NIPAm-co-4VP), weight-average molecular weight is 35000, and the infrared spectrogram of this multipolymer is shown in Fig. 1 (1652cm
-1, 1542cm
-1, 1458cm
-1belong to respectively in NIPA-C=O stretching vibration peak of the characteristic absorption band at place ,-N-H flexural vibration peak and-CH
3the asymmetric bending vibration peak, 1600cm
-1, 1415cm
-1, 1000cm
-1and 823cm
-1the charateristic avsorption band at place belongs to respectively the stretching vibration of CN in 4-vinylpridine, the C-H flexural vibration of the stretching vibration of C=C and pyridine ring), the nuclear magnetic resonance map of this multipolymer as shown in Figure 2, each peak be attributed to δ=1.1 (a, methyl proton on the NIPAm unit, 6H), δ=1. 4 and δ=1.9(b and c, vinyl proton on NIPAm and 4VP unit, 2H and 1H), δ=3.8(d, the proton of sec.-propyl on the NIPAm unit, 1H), δ=7.1 and δ=8.4(f and g, pyridyl proton on the 4VP unit, 2H and 2H), the success that copolymer has been described is synthetic.By above-mentioned multipolymer, in 25 ° of C are dissolved in deionized water, mass concentration is 0.3%, stirs it is fully dissolved; Then process as follows respectively:
(1) the above-mentioned aqueous solution is warming up to 70 ° of C, add 1, the 4-dibromobutane makes 1/3 pyridine generation quaterisation, constant temperature stirs 24 hours, add 0.03g organic cation salt compounds lithium-fluoroborate after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 5490.3 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained.Or,
(2) the above-mentioned aqueous solution is warming up to 60 ° of C, add 1, the 4-dibromobutane makes 1/3 pyridine generation quaterisation, constant temperature stirs 24 hours, add 0.03g organic cation salt compounds lithium-fluoroborate after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 5327.8 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained.Or,
(3) the above-mentioned aqueous solution is warming up to 50 ° of C, add 1, the 4-dibromobutane makes 1/3 pyridine generation quaterisation, constant temperature stirs 24 hours, add 0.03g organic cation salt compounds lithium-fluoroborate after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 4415.3nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained.As shown in Figure 3, be the transmission electron microscope photo of the micro-hydrogel of ion of quaternized gained pH and temperature dual sensitivity.Or,
(4) the above-mentioned aqueous solution is warming up to 40 ° of C, add 1, the 4-dibromobutane makes 1/3 pyridine generation quaterisation, constant temperature stirs 24 hours, add 0.03g organic cation salt compounds lithium-fluoroborate after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 1851.4 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained.
Known based on above-described embodiment, by changing the temperature that in micro-hydrogel preparation process, aqueous copolymers solution constant temperature stirs, can obtain micro-hydrogel of different size.
Embodiment 2:
1.5g temperature sensitive monomer NIPA (NIPAm), 0.09g pH sensitive monomer 4-vinylpridine (4VP) are dissolved in anhydrous 1, in the 4-dioxane, stir it is fully dissolved under the nitrogen atmosphere condition, add again the 0.036g Diisopropyl azodicarboxylate, fully stir, under the nitrogen atmosphere condition, under 70 ° of C oil baths, isothermal reaction, after 24 hours, is taken out and is naturally cooled to room temperature; With ether, the gained reactant is precipitated out, under 4000 rpms, through 15 minutes final vacuum dryings of centrifugation, obtains copolymer P (NIPAm-co-4VP), weight-average molecular weight is 35000; Above-mentioned multipolymer, in 25 ° of C are dissolved in deionized water, is then processed respectively as follows:
(1) be made into the aqueous solution that mass concentration is 0.05%, stirring is fully dissolved it, be warming up to 50 ° of C, add 1, the 3-propylene dichloride makes whole pyridine generation quaterisations, and constant temperature stirs 24 hours, adds 0.06g organic cation salt compounds dodecyl sodium sulfonate potassium after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 3592.1 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained.Or,
(2) be made into the aqueous solution that mass concentration is 0.1%, stirring is fully dissolved it, be warming up to 50 ° of C, add 1, the 3-propylene dichloride makes whole pyridine generation quaterisations, and constant temperature stirs 24 hours, adds 0.06g organic cation salt compounds sodium laurylsulfonate after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 3631.3 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained.Or,
(3) be made into the aqueous solution that mass concentration is 0.2%, stirring is fully dissolved it, be warming up to 50 ° of C, add 1, the 3-propylene dichloride makes whole pyridine generation quaterisations, and constant temperature stirs 24 hours, adds 0.06g organic cation salt compounds dodecyl sodium sulfonate lithium after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 3588.0 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained.Or,
(4) be made into the aqueous solution that mass concentration is 0.3%, stirring is fully dissolved it, be warming up to 50 ° of C, add 1, the 3-propylene dichloride makes whole pyridine generation quaterisations, and constant temperature stirs 24 hours, adds 0.06g organic cation salt compounds dodecyl sodium sulfonate potassium after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 3611.3 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained.Or,
(5) be made into the aqueous solution that mass concentration is 0.4%, stirring is fully dissolved it, be warming up to 50 ° of C, add 1, the 3-propylene dichloride makes whole pyridine generation quaterisations, and constant temperature stirs 24 hours, adds 0.06g organic cation salt compounds sodium laurylsulfonate after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 3644.7 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained.Or,
(6) be made into the aqueous solution that mass concentration is 0.5%, stirring is fully dissolved it, be warming up to 50 ° of C, add 1, the 3-propylene dichloride makes whole pyridine generation quaterisations, and constant temperature stirs 24 hours, adds 0.06g organic cation salt compounds dodecyl sodium sulfonate lithium after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 3582.9 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained.
Embodiment 3:
1.5g temperature sensitive monomer NIPA (NIPAm), 0.09g pH sensitive monomer 4-vinylpridine (4VP) are dissolved in anhydrous 1, in the 4-dioxane, stir it is fully dissolved under the nitrogen atmosphere condition, add again the 0.036g Diisopropyl azodicarboxylate, fully stir, under the nitrogen atmosphere condition, under 70 ° of C oil baths, isothermal reaction, after 24 hours, is taken out and is naturally cooled to room temperature; With ether, the gained reactant is precipitated out, under 4000 rpms, through 15 minutes final vacuum dryings of centrifugation, obtains copolymer P (NIPAm-co-4VP), weight-average molecular weight is 35000; By above-mentioned multipolymer in 25 ° of C are dissolved in deionized water, mass concentration is 0.3%, stirring is fully dissolved it, be warming up to 50 ° of C, add 1, the 4-dibromobutane makes 1/3 pyridine generation quaterisation, constant temperature stirs 24 hours, under 13000 rpms through centrifugation 30 minutes, lower floor adds a certain amount of organic cation salt compounds trifluoromethyl sulfonic acid lithium after adding the ultrasonic dispersion of deionized water, under 25 ° of C, isothermal reaction is 24 hours, obtains the micro-hydrogel of ion of pH and temperature dual sensitivity after centrifugal purification; To add the amount of trifluoromethyl sulfonic acid lithium be respectively several as follows, its follow-up processing mode is respectively:
(1) 0g; It is 4145.3 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records this micro-hydrogel; Or,
(2) 0.0036g; It is 2795.7 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records this micro-hydrogel; Or,
(3) 0.0072g; It is 1440.7 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records this micro-hydrogel; Or,
(4) 0.0108g; It is 817.1 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records this micro-hydrogel.
As shown in Figure 4, be the particle diameter of the micro-hydrogel of ion of embodiment 3 gained pH and temperature dual sensitivity and the graph of a relation of temperature.As seen from Figure 4, by changing envrionment temperature, the particle diameter of micro-hydrogel can change with temperature, along with the particle diameter of the micro-hydrogel of rising of envrionment temperature diminishes; Along with the increase of organic cation salt compounds add-on, micro-hydrogel hydrophobicity strengthens, and shows particle diameter and reduces.
Embodiment 4:
1.5g temperature sensitive monomer NIPA (NIPAm), 0.09g pH sensitive monomer 4-vinylpridine (4VP) are dissolved in anhydrous 1, in the 4-dioxane, stir it is fully dissolved under the nitrogen atmosphere condition, add again the 0.036g Diisopropyl azodicarboxylate, fully stir, under the nitrogen atmosphere condition, under 70 ° of C oil baths, isothermal reaction, after 24 hours, is taken out and is naturally cooled to room temperature; With ether, the gained reactant is precipitated out, under 4000 rpms, through 15 minutes final vacuum dryings of centrifugation, obtains copolymer P (NIPAm-co-4VP), weight-average molecular weight is 35000; By above-mentioned multipolymer in 25 ° of C are dissolved in deionized water, mass concentration is 0.3%, stirring is fully dissolved it, be warming up to 50 ° of C, add Isosorbide-5-Nitrae-dibromobutane to make 1/6 pyridine generation quaterisation, constant temperature stirs 24 hours, add 0.015g organic cation salt compounds potassium fluoborate after centrifuge washing, obtain the micro-hydrogel of ion of pH and temperature dual sensitivity after 25 ° of C constant temperature stir 24 hours, be centrifugal; It is 3309.2 nm at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained.Utilize HCl solution, KOH solution can regulate the pH value of micro-hydrogel solution, it is relevant to the pH value of solution at the particle diameter of 25 ° of C that the dynamic laser light scattering method records the micro-hydrogel of quaternized gained, illustrates that the micro-hydrogel of gained has pH susceptibility.The particle diameter of the micro-hydrogel of ion that Fig. 5 is the quaternized gained pH of embodiment 4 and temperature dual sensitivity and the graph of a relation of pH value.
Embodiment 5:
1.5g temperature sensitive monomer N, the two ethyl acrylamides of N-, 0.09g pH sensitive monomer 3-vinyl pyridine (3VP) are dissolved in anhydrous tetrahydro furan, stir it is fully dissolved under the nitrogen atmosphere condition, add again the 0.04g Diisopropyl azodicarboxylate, fully stir, under the nitrogen atmosphere condition, under 90 ° of C oil baths, isothermal reaction, after 12 hours, is taken out and is naturally cooled to room temperature; With sherwood oil, the gained reactant is precipitated out, under 4000 rpms, through 15 minutes final vacuum dryings of centrifugation, obtains copolymer P (NIPAm-co-3VP), weight-average molecular weight is 32800; By above-mentioned multipolymer in 25 ° of C are dissolved in deionized water, mass concentration is 0.3%, stirring is fully dissolved it, is warming up to 50 ° of C, adds 1, the 6-dichloro hexane, make pyridine that quaterisation occur fully, constant temperature stirs 24 hours, adds 0.054g organic cation salt compounds trifluoromethyl sulfonate after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; The dynamic laser light scattering method records particle diameter 2308.0 nms of the micro-hydrogel of quaternized gained at 25 ° of C.
Embodiment 6:
2.1g temperature sensitive monomer N, the two ethyl acrylamides of N-, 0.09g pH sensitive monomer 2-vinyl pyridine (3VP) are dissolved in anhydrous tetrahydro furan, stir it is fully dissolved under the nitrogen atmosphere condition, add again the 0.043g Diisopropyl azodicarboxylate, fully stir, under the nitrogen atmosphere condition, under 80 ° of C oil baths, isothermal reaction, after 18 hours, is taken out and is naturally cooled to room temperature; With sherwood oil, the gained reactant is precipitated out, under 4000 rpms, through 15 minutes final vacuum dryings of centrifugation, obtains copolymer P (NIPAm-co-3VP), weight-average molecular weight is 36300; By above-mentioned multipolymer in 25 ° of C are dissolved in deionized water, mass concentration is 0.3%, stirring is fully dissolved it, be warming up to 60 ° of C, add pentamethylene bromide to make 1/3 pyridine generation quaterisation, constant temperature stirs 24 hours, add 0.023g organic cation salt compounds trifluoromethane sulfonic acid potassium after centrifuge washing, obtain the micro-hydrogel of ion of pH and temperature dual sensitivity after 25 ° of C constant temperature stir 24 hours, be centrifugal; The dynamic laser light scattering method records particle diameter 2890.5 nms of the micro-hydrogel of quaternized gained at 25 ° of C.
Embodiment 7:
1.8g temperature sensitive monomer N, the two ethyl acrylamides of N-, 0.17g pH sensitive monomer N-vinyl imidazole are dissolved in anhydrous tetrahydro furan, stir it is fully dissolved under the nitrogen atmosphere condition, add again the 0.054g Diisopropyl azodicarboxylate, fully stir, under the nitrogen atmosphere condition, under 60 ° of C oil baths, isothermal reaction, after 24 hours, is taken out and is naturally cooled to room temperature; With sherwood oil, the gained reactant is precipitated out, under 4000 rpms, through 15 minutes final vacuum dryings of centrifugation, obtains copolymer, its weight-average molecular weight is 28300; By above-mentioned multipolymer in 25 ° of C are dissolved in deionized water, mass concentration is 0.4%, stirring is fully dissolved it, be warming up to 50 ° of C, add glycol dibromide to make imidazoles that quaterisation occur fully, constant temperature stirs 24 hours, add 0.043g organic cation salt compounds Sodium tetrafluoroborate after centrifuge washing, obtain the micro-hydrogel of ion of pH and temperature dual sensitivity after 25 ° of C constant temperature stir 24 hours, be centrifugal; The dynamic laser light scattering method records particle diameter 1876.9 nms of the micro-hydrogel of quaternized gained at 25 ° of C.
The foregoing is only several embodiments of the present invention; should be understood that; for the person of ordinary skill of the art, can also make many modification and improvement, all do not exceed the described modification of claim or improve all should be considered as protection scope of the present invention.
Claims (6)
1. the preparation method of the micro-hydrogel of ion of a pH and temperature dual sensitivity, is characterized in that, comprises the following steps:
By N-alkyl acrylamide class monomer M 1, containing the double bond compound M2 of tertiary amine group, initiator at anhydrous solvent 1, in 4-dioxane or tetrahydrofuran (THF), carry out free radicals copolymerization reaction under oxygen free condition, controlling temperature of reaction is 60-90 ° of C, and the time is 12-24 hour; Then adopting ether or sherwood oil is the copolymer generated in the precipitation agent abstraction reaction, through the centrifugation final vacuum, is dried to constant weight; The gained copolymer is mixed with to the aqueous solution that mass concentration is 0.05-0.5% at 25 ° of C, add many compound halo alkanes M3, at 40-70 ° of C constant temperature, stir 24 hours, add organic cation salt compounds M4 after centrifuge washing, after stirring 24 hours, be centrifugal, 25 ° of C constant temperature make the micro-hydrogel of ion of purifying;
The chemical structural formula of M1, M2, M3 and M4 is respectively:
In formula, R
1for hydrogen atom and R
2for sec.-propyl, or R
1for ethyl and R
2for ethyl; R
3for the carbonatoms straight chained alkyl that is 2 ~ 6; X is pyridines or imidazoles group; Y is chlorine or bromine; A is lithium or sodium or potassium; B is dodecyl sodium sulfonate root or fluoroboric acid root or trifluoromethane sulfonic acid root;
In M1, M2 and tri-kinds of reactants of M3, shared mass percent is respectively M1:87.5-95.4% separately, M2:4.0-8.3%, M3:0.6-4.2%; M4 accounts for the 0-6% of M1, M2 and M3 total mass; The 2.0-2.7% that the consumption of described initiator is M1 and M2 total mass.
2. method according to claim 1, is characterized in that, described N-alkyl acrylamide class monomer M 1 is NIPA or N, the two ethyl acrylamides of N-.
3. method according to claim 1, is characterized in that, the described double bond compound M2 containing tertiary amine group is 2-vinyl pyridine, 3-vinyl pyridine, 4-vinylpridine or N-vinyl imidazole.
4. method according to claim 1, is characterized in that, described many compound halo alkanes M3 is 1,2-ethylene dichloride, 1,2-ethylene dibromide, 1,3-propylene dichloride, 1,3-dibromopropane, 1,4-dichlorobutane, 1,4-dibromobutane, 1,5-dichloropentane, pentamethylene bromide, 1,6-dichloro hexane or 1,6-dibromo-hexane.
5. method according to claim 1, it is characterized in that, described organic cation salt compounds M4 is dodecyl sodium sulfonate lithium, sodium laurylsulfonate, dodecyl sodium sulfonate potassium, lithium-fluoroborate, Sodium tetrafluoroborate, potassium fluoborate, trifluoromethyl sulfonic acid lithium, trifluoromethyl sulfonate or trifluoromethane sulfonic acid potassium.
6. method according to claim 1, is characterized in that, described initiator is Diisopropyl azodicarboxylate.
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| CN114516939A (en) * | 2022-03-16 | 2022-05-20 | 中国科学院兰州化学物理研究所 | N-isopropyl acrylamide ionic gel and preparation method thereof |
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