CN103087258B - Method for realizing one-pot synthesis of pH and temperature double-sensitive ionic micro hydrogel - Google Patents
Method for realizing one-pot synthesis of pH and temperature double-sensitive ionic micro hydrogel Download PDFInfo
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- CN103087258B CN103087258B CN201310013903.9A CN201310013903A CN103087258B CN 103087258 B CN103087258 B CN 103087258B CN 201310013903 A CN201310013903 A CN 201310013903A CN 103087258 B CN103087258 B CN 103087258B
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 6
- 230000035945 sensitivity Effects 0.000 claims abstract description 30
- 238000005342 ion exchange Methods 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 19
- -1 alkane compound Chemical class 0.000 claims abstract description 13
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 32
- 230000009977 dual effect Effects 0.000 claims description 31
- 150000002500 ions Chemical class 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 9
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 8
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical compound C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 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
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical group Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 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
- 239000006227 byproduct Substances 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
- 239000000376 reactant Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 14
- 239000002608 ionic liquid Substances 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract description 2
- 238000013270 controlled release Methods 0.000 abstract description 2
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- 238000010526 radical polymerization reaction Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 22
- 238000000746 purification Methods 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 21
- 239000012299 nitrogen atmosphere Substances 0.000 description 20
- 238000000502 dialysis Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000002356 laser light scattering Methods 0.000 description 11
- 125000002947 alkylene group Chemical group 0.000 description 10
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229920000831 ionic polymer Polymers 0.000 description 8
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- 239000000499 gel Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LPNSCOVIJFIXTJ-UHFFFAOYSA-N 2-methylidenebutanamide Chemical compound CCC(=C)C(N)=O LPNSCOVIJFIXTJ-UHFFFAOYSA-N 0.000 description 4
- 150000002892 organic cations Chemical class 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 2
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 2
- LBKDGROORAKTLC-UHFFFAOYSA-N 1,5-dichloropentane Chemical compound ClCCCCCCl LBKDGROORAKTLC-UHFFFAOYSA-N 0.000 description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 2
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- AZLIIAMTCHKNJJ-UHFFFAOYSA-N potassium;trifluoromethanesulfonic acid Chemical compound [K].OS(=O)(=O)C(F)(F)F AZLIIAMTCHKNJJ-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 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
- 241000024287 Areas Species 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 0 CC=C(C1)[*@]1C(N(*)*)=O Chemical compound CC=C(C1)[*@]1C(N(*)*)=O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 238000005485 electric heating Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction 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
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 238000001291 vacuum drying Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of environment-sensitive high polymer materials and aims to provide a method for realizing one-pot synthesis of pH and temperature double-sensitive ionic micro hydrogel. The method comprises the following steps: performing a free radical polymerization reaction on an N-alkyl acrylamide monomer, a double bond containing tertiary amine group, a polyhalogenated alkane compound and an initiator in an aqueous solution under oxygen-free conditions, dialyzing the obtained product for three days, performing ion exchange with organic cationic salt, and centrifuging to prepare the purified ionic micro hydrogel. The preparation method is simple and easily controllable, the obtained micro hydrogel has the pH and temperature double sensitivity, the excellent characteristics of the poly(ionic liquid) are introduced, and the micro hydrogel is high in purity, high in stability, high in swelling ratio and suitable for the fields of medicine controlled release and sensors and the like.
Description
Technical field
The present invention relates to the polymeric material field of environment sensitive type, be specifically related to a kind of micro-hydrogel of ion with pH and temperature dual susceptibility and preparation method thereof.
Background technology
Microgel (microgel) is a kind of crosslinked polymer particle, swelling and do not dissolve in good solvent, has strong expansion-contraction.Different polymer gels according to solvent are divided into again hydrogel and organogel, and wherein the research of stimulating responsive hydrogel especially receives the concern of people.The external stimulus of the micro-hydrogel of environment sensitive type has temperature, pH value, solvent, salt concn, light, sound field, electric field, pressure etc., and when being subject to these external stimuluss, micro-hydrogel can show corresponding responsiveness, is embodied in expansion or the contraction change of volume.Utilize this stimuli responsive characteristic, high-molecular gel can be applied in each fields such as drug controlled release, catalyzer, chemical separation, biosensor, power element, switch.General micro-hydrogel is with water-soluble double bond compounds such as NIPA, acrylamide and vinylformic acid for polymerization single polymerization monomer, and N, N-dimethylene acrylamide, Ethylene glycol dimethacrylate etc. are chemical cross-linking agent, adopts emulsion polymerization to obtain.According to the characteristic of selected monomer, obtained micro-hydrogel can have the response characteristic to environment such as temperature, pH value and ionic strengths.
Ionic liquid (ionic liquids) is generally defined as the organic/inorganic salt of fusing point lower than 100 ° of C, has good chemistry and electrochemical stability, low combustible, low-vapor pressure and high ion conductivity.At first, ionic liquid, by the substitute as volatile organic solvent, along with going deep into of research, has been widely used in other technologies field now, as catalysis, organic and polymeric chemical, electrochemistry, analytical chemistry, the energy, nanotechnology and biotechnology etc.In chemical field, investigator is using ionic liquid as the green solvent in polymerization process, and the special solvent of biomacromolecule, initiator or promotor etc., even it can be used as functional monomer, obtains poly ion liquid.Typical poly ion liquid is with positively charged ion if pyrrolidone, imidazoles, pyridine and negatively charged ion are 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.
If be incorporated into by poly ion liquid in microgel, then it can be made to have the good characteristic of the two simultaneously, and by synergy therebetween, give play to New function, thus extended the potential Application Areas of microgel.Up to the present, there are many reports about polyelectrolyte and intelligent aqueous gel capable both at home and abroad, but but substantially do not have about the report of the microgel with poly ion liquid character and intelligent response, particularly obtained micro-hydrogel of ionic nature by crosslinking reaction.And the most polyelectrolyte hydrogel reported exists with the form of block-shaped body gel, and preparation process is comparatively loaded down with trivial details, affects its application prospect.The research making it have new features by the composition and structure designing micro-hydrogel is subject to extensively being absorbed in of domestic and international investigator in recent years always, and about the research of poly ion liquid be also a up-to-date focus.
Chinese patent CN102304231A discloses the preparation method of a class high absorbency material embedding thing, adopt linear hydrophilic polymer and high-valence cationic and the various thing that is embedded to be cross-linked by polyelectrolyte compound action, form the micromolecular material with high-hydroscopicity energy of embedding.This invention has excellent water absorbing properties, embeddability properties and sustained release performance, also has certain degradability.But this material exists with the form of block gel, and do not have the microsize of micro-hydrogel colloidal solid, be difficult to can effectively be transported to each position as micro-hydrogel, range of application is less.
Chinese patent CN101851315A discloses a kind of preparation method of degradable polyampholyte microgel, by configuration reverse microemulsion, aqueous phase solution, oil-phase solution, be that mother liquor makes water-in-oil reverse microemulsion with oil phase, electric heating, water-bath, fill nitrogen, whipped state under add raw material and carry out polyreaction, make polyampholyte microgel emulsion, through breakdown of emulsion precipitation, washing, suction filtration, dialysis, centrifugation, vacuum-drying, obtained amphotericeledrolyte micro-gel particles.This amphotericeledrolyte microgel iso-electric point place particle Hydrodynamic diameter is 105.7nm, but size distribution is wider, and preparation method is comparatively loaded down with trivial details, and purification process is complicated.
Chinese patent CN101851315A discloses one with NIPA and vinylformic acid etc. for main monomer, under chemical cross-linking agent exists, initiated polymerization prepares the method for pH and temperature dual susceptibility nano-hydrogel, the particle diameter of its nano-hydrogel is 30-200nm, but this preparation method also needs to use tensio-active agent, causes the dialysis purification time of nano-hydrogel to reach 2 weeks.
The preparation method of hydrogel involved in above-mentioned patent is comparatively loaded down with trivial details, and purification process is complicated, and 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, provides the method for the micro-hydrogel of the ion of one pot process pH and temperature dual sensitivity.The micro-hydrogel of the ion obtained by the method has the character of pH and temperature dual susceptibility and poly ion liquid, and preparation method is simple, nano-grade size and being evenly distributed, and is adapted at the application in medicine controllable sustained-release and sensor field.
The present invention is without the need to using linking agent and tensio-active agent, realize crosslinked by the quaterisation of monomer, and make polymers ionise, only adopt one kettle way to obtain the pH of even size distribution and the micro-hydrogel of ion of temperature dual sensitivity, realize Simplified flowsheet, controlled production.
The concrete solution of the present invention is: the method providing the micro-hydrogel of ion of a kind of one pot process pH and temperature dual sensitivity, comprises the following steps:
N-alkyl acryl amine monomer M 1, double bond compound M2, alkyl polyhalides hydrocarbon compound M3 and initiator containing tertiary amine group is soluble in water, free radicals copolymerization reaction is carried out under oxygen free condition, copolyreaction temperature is 60-90 ° of C, and the copolyreaction time is 6 hours; After being dialysed by products therefrom three days, add organic cation salt compounds M4 and carry out ion exchange reaction, ion-exchange reaction temperature is 25 ° of C, and the reaction times is 24 hours; Then centrifuge washing is carried out, the micro-hydrogel of ion of obtained purifying;
The chemical structural formula of M1, M2, M3 and M4 is respectively:
Wherein, R
1for hydrogen atom, R
2for sec.-propyl, or R
1for ethyl, R
2for ethyl; R
3for carbonatoms is the straight chained alkyl of 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 M3 tri-kinds of reactants, shared mass percent is respectively M1:77-92% separately, and M2:4-12%, M3:4-11%, M4 account for the 7-52% of M1, M2 and M3 total mass; The consumption of initiator is the 6-10% of M1, M2 and M3 gross weight.
In the present invention, described N-alkyl acryl amine monomer M 1 is the two ethyl acrylamide of NIPA or N, N-.
In the present invention, the described double bond compound M2 containing tertiary amine group is 2-vinyl pyridine, 3-vinyl pyridine, 4-vinylpridine, N-vinyl imidazole.
In the present invention, described alkyl polyhalides hydrocarbon compound 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 2,2 '-azo diisobutyl amidine dihydrochloride.
Principle of the present invention is:
M2 monomer resulting polymers is as the pH sensitive to environment such as poly 4 vinyl pyridine; M1 monomer resulting polymers is as responsive to envrionment temperature in poly N-isopropyl acrylamide etc., it has a low critical transition temperature (LCST) at 31-32 ° of about C, when temperature is lower than LCST, poly N-isopropyl acrylamide can be dissolved in deionized water completely, and when temperature is higher than LCST, poly N-isopropyl acrylamide water fast, due to the hydrogen bond in molecular chain and between molecular chain and hydrophobic interaction, is agglomerated into bead between poly N-isopropyl acrylamide molecular chain; On the other hand, alkyl polyhalides hydrocarbon M3 as Isosorbide-5-Nitrae-dibromobutane etc. can with the tertiary amine group generation quaterisation of M2 as 4-vinylpridine; If M1, M2 and M3 are dissolved in deionized water, heat and add initiator initiation reaction, when solution temperature is greater than the LCST of M1 resulting polymers, namely stir under 60-90 DEG C of state of temperature, then there is free radicals copolymerization reaction on the one hand, there is quaternized crosslinking reaction in the reunion bead of another aspect multipolymer simultaneously, make 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, can regulate the size of bead, obtaining the microgel bead of different size by controlling solution temperature.Carry out ion-exchange finally by quaternary ammonium salt crosslinked in microgel and organic cation salt, obtain the micro-hydrogel of ion of pH and temperature dual sensitivity.
Compared with micro-hydrogel that other are traditional and preparation method thereof, the invention has the beneficial effects as follows:
1. include pH sensitivity and temperature sensitive two kinds of monomers in the micro-hydrogel structure unit of the present invention, micro-hydrogel that thus prepared by the present invention possesses pH and temperature dual susceptibility simultaneously.
2. in the present invention, micro-hydrogel stability is high, can stablize placement 6 months under 25 ° of C.
3. the present invention introduces Ionized quaternary ammonium salt while adopting quaterisation to make monomer occur to be cross-linked, and makes microgel obtain the good characteristic of poly ion liquid, extends the potential Application Areas of microgel.
4. preparation method of the present invention, obtain micro-hydrogel particle diameter be 50-1010nm, and by changing the temperature and degree of crosslinking that aqueous solution constant temperature stirs in the preparation process of micro-hydrogel, obtain micro-hydrogel of different size.
5. preparation method of the present invention, to obtain micro-swelling behavior rate large, be specially adapted to the Application Areass such as drug controllable release.
6. preparation method of the present invention, operation is simple, does not introduce emulsifying agent, and purge process is convenient, and technique is simply controlled, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the micro-hydrogel of ion of pH and temperature dual sensitivity.
Fig. 2 is the particle diameter of the micro-hydrogel of ion and the graph of a relation of pH value of pH and temperature dual sensitivity, embodies the pH susceptibility of micro-hydrogel.
Fig. 3 is the particle diameter of the micro-hydrogel of ion and the graph of a relation of envrionment temperature of pH and temperature dual sensitivity, embodies the temperature sensitivity of micro-hydrogel.
Fig. 4 is the stereoscan photograph of the micro-hydrogel of ion of pH and temperature dual sensitivity.
Embodiment
Embodiment 1:
0.23g temperature sensitive monomer NIPA (NIPAm), 0.028g pH sensitive monomer N-vinyl imidazole (VIM) and 0.033g alkylene dihalide 1,4-dibromobutane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, under nitrogen atmosphere condition, carry out following subsequent disposal respectively:
(1) isothermal reaction 6 hours under 60 ° of C oil baths, dialysis purification is after 3 days, and add 0.06g organic cation salt compounds potassium fluoborate and carry out ion exchange reaction, ion-exchange reaction temperature is 25 ° of C, and the reaction times is 24 hours; Then carry out centrifuge washing, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; Or,
(2) isothermal reaction 6 hours under 70 ° of C oil baths, dialysis purification is after 3 days, and add 0.06g organic cation salt compounds potassium fluoborate and carry out ion exchange reaction, ion-exchange reaction temperature is 25 ° of C, and the reaction times is 24 hours; Then carry out centrifuge washing, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; The transmission electron microscope photo of micro-hydrogel of this copolyreaction gained pH and temperature dual sensitivity as shown in Figure 1.Or,
(3) isothermal reaction 6 hours under 80 ° of C oil baths, dialysis purification is after 3 days, and add 0.06g organic cation salt compounds potassium fluoborate and carry out ion exchange reaction, ion-exchange reaction temperature is 25 ° of C, and the reaction times is 24 hours; Then carry out centrifuge washing, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; Or,
(4) isothermal reaction 6 hours under 90 ° of C oil baths, dialysis purification is after 3 days, and add 0.06g organic cation salt compounds potassium fluoborate and carry out ion exchange reaction, ion-exchange reaction temperature is 25 ° of C, and the reaction times is 24 hours; Then carry out centrifuge washing, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity.
Embodiment 2:
0.23g temperature sensitive monomer NIPA (NIPAm), 0.028g pH sensitive monomer N-vinyl imidazole (VIM) and a certain amount of alkylene dihalide 1, 4-dibromobutane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, under nitrogen atmosphere condition, isothermal reaction 6 hours under 70 ° of C oil baths, dialysis purification is after 3 days, add a certain amount of organic cation salt compounds and carry out ion exchange reaction, ion-exchange reaction temperature is 25 ° of C, reaction times is 24 hours, then carry out centrifuge washing, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity, add Isosorbide-5-Nitrae-dibromobutane and organic cation salt compounds content and be respectively following several, its subsequent disposal is respectively:
(1) Isosorbide-5-Nitrae-dibromobutane 0.016g, trifluoromethyl sulfonic acid lithium 0.05g; It is 1010.1 nm that dynamic laser light scattering method records the micro-hydrogel of copolyreaction gained at the particle diameter of 25 ° of C; Or,
(2) Isosorbide-5-Nitrae-dibromobutane 0.022g, trifluoromethyl sulfonate 0.10g; It is 669.9 nm that dynamic laser light scattering method records the micro-hydrogel of copolyreaction gained at the particle diameter of 25 ° of C; Or,
(3) Isosorbide-5-Nitrae-dibromobutane 0.033g, trifluoromethane sulfonic acid potassium 0.15g; It is 596.7 nm that dynamic laser light scattering method records the micro-hydrogel of copolyreaction gained at the particle diameter of 25 ° of C.
Utilize HCl solution, KOH solution can regulate the pH value of micro-hydrogel solution, it is relevant with the pH value of solution at the particle diameter of 25 ° of C that dynamic laser light scattering method records micro-hydrogel, illustrates that the micro-hydrogel of gained has pH susceptibility.Fig. 2 is the particle diameter of micro-hydrogel and the graph of a relation of pH value of copolyreaction gained pH and temperature dual sensitivity under (1) kind situation.Fig. 3 is the particle diameter of micro-hydrogel and the graph of a relation of temperature of copolyreaction gained pH and temperature dual sensitivity under (2) kind situation.As seen from Figure 3, by changing envrionment temperature, the particle diameter of micro-hydrogel can change with temperature, and the particle diameter of the micro-hydrogel of the rising along with envrionment temperature diminishes.
Embodiment 3:
0.23g temperature sensitive monomer NIPA (NIPAm), 0.028g pH sensitive monomer N-vinyl imidazole (VIM) and 0.011g alkylene dihalide 1, 4-dibromobutane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, isothermal reaction 6 hours under 70 ° of C oil baths under nitrogen atmosphere condition, dialysis purification is after 3 days, add 0.023g lithium-fluoroborate and carry out ion exchange reaction, ion-exchange reaction temperature is 25 ° of C, reaction times is 24 hours, then carry out centrifuge washing, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity, as shown in Figure 4, particle diameter is 50 nm to the stereoscan photograph of micro-hydrogel of this copolyreaction gained pH and temperature dual sensitivity.
Embodiment 4:
0.3g temperature sensitive monomer NIPA (NIPAm), 0.014g pH sensitive monomer 4-vinylpridine (4VP) and 0.015g alkylene dihalide 1, 3-propylene dichloride is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.02g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, isothermal reaction 6 hours under 80 ° of C oil baths under nitrogen atmosphere condition, dialysis purification is after 3 days, add 0.035g dodecyl sodium sulfonate potassium and carry out ion exchange reaction, ion-exchange reaction temperature is 25 ° of C, reaction times is 24 hours, then carry out centrifuge washing, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity, it is 287.9 nm that dynamic laser light scattering method records this micro-hydrogel at the particle diameter of 25 ° of C.
Embodiment 5:
0.3g temperature sensitive monomer NIPA (NIPAm), 0.014g pH sensitive monomer 4-vinylpridine (4VP) and 0.016g alkylene dihalide 1,4-dichlorobutane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.02g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, isothermal reaction 6 hours under 80 ° of C oil baths under nitrogen atmosphere condition, dialysis purification is after 3 days; Add 0.028g Sodium tetrafluoroborate, isothermal reaction 24 hours under 25 ° of C oil baths, after centrifugal purification, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 235.8nm that dynamic laser light scattering method records this micro-hydrogel at the particle diameter of 25 ° of C.
Embodiment 6:
0.3g temperature sensitive monomer NIPA (NIPAm), 0.014g pH sensitive monomer 4-vinylpridine (4VP) and 0.017g alkylene dihalide 1,5-dichloropentane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.02g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, isothermal reaction 6 hours under 80 ° of C oil baths under nitrogen atmosphere condition, dialysis purification 3 days; Add 0.022g dodecyl sodium sulfonate lithium, isothermal reaction 24 hours under 25 ° of C oil baths, after centrifugal purification, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 198.5 nm that dynamic laser light scattering method records this micro-hydrogel at the particle diameter of 25 ° of C.
Embodiment 7:
0.3g temperature sensitive monomer NIPA (NIPAm), 0.014g pH sensitive monomer 4-vinylpridine (4VP) and 0.018g alkylene dihalide 1,6-dichloro hexane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.02g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, abundant stirring, isothermal reaction 6 hours under 80 ° of C oil baths under nitrogen atmosphere condition, dialysis purification 3 days; Add 0.036g sodium laurylsulfonate, isothermal reaction 24 hours under 25 ° of C oil baths, after centrifugal purification, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 156.9 nm that dynamic laser light scattering method records this micro-hydrogel at the particle diameter of 25 ° of C.
Embodiment 8:
0.34g temperature sensitive monomer N, N-two ethyl acrylamide, 0.034g pH sensitive monomer 3-vinyl pyridine (3VP) and 0.038g alkylene dihalide 1, pentamethylene bromide is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.04g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, fully stirs, isothermal reaction 6 hours under 60 ° of C oil baths under nitrogen atmosphere condition, dialysis purification 3 days; Add 0.045g potassium fluoborate, isothermal reaction 24 hours under 25 ° of C oil baths, after centrifugal purification, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 343.4 nm that dynamic laser light scattering method records this micro-hydrogel at the particle diameter of 25 ° of C.
Embodiment 9:
0.23g temperature sensitive monomer N, N-two ethyl acrylamide, 0.021g pH sensitive monomer 2-vinyl pyridine (2VP) and 0.024g alkylene dihalide 1,6-dibromo-hexane is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.02g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, fully stirs, isothermal reaction 6 hours under 70 ° of C oil baths under nitrogen atmosphere condition, dialysis purification 3 days; Add 0.031g sodium laurylsulfonate, isothermal reaction 24 hours under 25 ° of C oil baths, after centrifugal purification, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 157.6nm that dynamic laser light scattering method records this micro-hydrogel at the particle diameter of 25 ° of C.
Embodiment 10:
0.23g temperature sensitive monomer N, N-two ethyl acrylamide, 0.035g pH sensitive monomer 2-vinyl pyridine (2VP) and 0.03g alkylene dihalide 1,2-ethylene dichloride is dissolved in deionized water, stirring under nitrogen atmosphere condition makes it fully dissolve, add 0.025g initiator 2 again, 2 '-azo diisobutyl amidine dihydrochloride, fully stirs, isothermal reaction 6 hours under 70 ° of C oil baths under nitrogen atmosphere condition, dialysis purification 3 days; Add 0.029g trifluoromethyl sulfonic acid lithium, isothermal reaction 24 hours under 25 ° of C oil baths, after centrifugal purification, namely obtain the micro-hydrogel of ion of pH and temperature dual sensitivity; It is 107.9nm that dynamic laser light scattering method records this micro-hydrogel at the particle diameter of 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, many modification and improvement can also be made, allly not exceed modification described in claim or improve and all should be considered as protection scope of the present invention.
Claims (3)
1. the method for the micro-hydrogel of the ion of one pot process pH and temperature dual sensitivity, is characterized in that, comprise the following steps:
N-alkyl acryl amine monomer M 1, double bond compound M2, alkyl polyhalides hydrocarbon compound M3 and initiator containing tertiary amine group is soluble in water, free radicals copolymerization reaction is carried out under oxygen free condition, copolyreaction temperature is 60-90 DEG C, and the copolyreaction time is 6 hours; After being dialysed by products therefrom three days, add organic cation salt compounds M4 and carry out ion exchange reaction, ion-exchange reaction temperature is 25 DEG C, and the reaction times is 24 hours; Then centrifuge washing is carried out, the micro-hydrogel of ion of obtained purifying;
The chemical structural formula of M1, M2, M3 and M4 is respectively:
Wherein, R
1for hydrogen atom, R
2for sec.-propyl, or R
1for ethyl, R
2for ethyl; R
3for carbonatoms is the straight chained alkyl of 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 M3 tri-kinds of reactants, shared mass percent is respectively M1:77-92% separately, and M2:4-12%, M3:4-11%, M4 account for the 7-52% of M1, M2 and M3 total mass; The consumption of initiator is the 6-10% of M1, M2 and M3 gross weight.
2. 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, N-vinyl imidazole.
3. method according to claim 1, is characterized in that, described initiator is 2,2 '-azo diisobutyl amidine dihydrochloride.
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