CN105295078A - Dual network multifunctional gel and preparation method thereof - Google Patents
Dual network multifunctional gel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses dual network multifunctional gel and a preparation method thereof, relates to the field of high polymer materials, and in particular to high mechanical property gel with temperature responsiveness, pH responsiveness and conductivity and a preparation method thereof. The dual network multifunctional gel can be prepared in the following method: modifying glycine by crylic acid to obtain vinyl glycine, performing a neutral reaction with choline to prepare a vinyl choline-glycine ionic liquid monomer, by free radical polymerization, preparing polyionic liquid gel as a first gel network by taking N,N-methylenebisacrylamide (MBAA) as a crosslinking agent and potassium persulfate (KPS) as an initiator; taking a thermosensitive material N-isopropyl acrylamide (NIPAAm) and a pH response material acrylic acid (AAc) as a reaction monomer of a second gel network, and by taking the N,N-methylenebisacrylamide (MBAA) as the crosslinking agent and potassium persulfate (KPS) as the initiator, forming the dual network gel together with the polyionic liquid first gel network. The gel has the multiple functions of temperature responsiveness, pH responsiveness, conductivity and high mechanical strength and has a broad application prospect.
Description
Technical field
The present invention relates to polymeric material field, particularly multi-functional gel of a kind of dual network and preparation method thereof.
Background technology
Gel is the novel high molecular polymer material with three-dimensional net structure, large quantity of moisture is there is in its network structure, it is high molecular strong solution, it is again elastomeric solid, small-molecule substance can permeate wherein or spread, this special stuctures and properties, makes it there is application prospect widely at industry, agricultural, biomedical sector.But general hydrogel bad mechanical property, poor stability are its common feature, therefore improve gel mechanical property and become one of field of gel study hotspot.
For improving the mechanical property of gel, scientists have developed movable pulley gel, nano-composite gel and dual network gel (DN in succession, double-networkgels) etc., wherein dual network gel gets most of the attention due to the mechanical property of its high strength, and its toughness can compare favourably with industrial rubber.Dual network gel is by two kinds of separate crosslinked polymer network integrations together, two polymer network performances are completely different, the first gel network mostly is polyelectrolyte network, and concentration is low, degree of crosslinking is high, fragility rigidity large, for whole gel structure provides skeletal support; Second layer gel network is neutral polymer network, concentration is high, degree of crosslinking is low, molecular weight is large, soft and tensile property is good, local stress is reached between the two lax by the slip of the distortion of loose cross-linked network and molecular entanglement point, utilize the combination of this " tempering toughness with gentleness ", can obtain firmly and not crisp, tough and not soft gel, makes gel mechanical strength increase substantially.As PAMPS/PAAm (poly-2-acrylamide-2-methyl propane sulfonic/polyacrylamide) dual network gel, its mechanical property be not simply adding of PAMPS gel and PAAm gel mechanical property and, the compressive strength of dual network gel is 20 times and 40 times of the mono-network gel of PAMPS and PAAm respectively, and energy-to-break is 100 ~ 1000 times of single network gel energy-to-break.
Along with the development of science and technology, the material of simple function can not adapt to the needs of scientific-technical progress, and exploitation multifunctional composite becomes the inexorable trend of materialogy development.The present invention by having the ionic liquid of conducting function, the NIPA (NIPAAm) with temperature-responsive, the vinylformic acid (AAc) with pH responsiveness organically combines, have the multi-functional gel of good mechanical strength with the preparation of dual network form, this gel is at medicine controlled releasing, species adsorbs and be separated, the field such as organizational project exists wide application prospect.
Summary of the invention
The object of the present invention is to provide the multi-functional gel of a kind of dual network, this gel has temperature-responsive, and pH responsiveness, electroconductibility, high-strength mechanical properties can be applicable to the aspects such as cell culturing rack material, medicine controlled release carrier, wound dressings.The multi-functional gel of dual network provided by the present invention can be obtained by following methods:
(1) preparation of vinyl glycine (Gly-AAc)
Take vinylformic acid (AAc), be dissolved in 10ml distilled water, add N-hydroxy-succinamide (NHS) and 1-ethyl-3-(3-dimethylamine propyl) carbodiimide (EDC), after room temperature lower magnetic force stirs 2h, add glycine (Gly) again and continue reaction 24h, AAc: Gly: EDC: NHS=5mol: 5mol: 5mol: 1mol; Pour excess ethyl alcohol into after question response terminates, leave standstill and separate out white crystal, by product centrifugation, abandoning supernatant, gets and to be deposited in baking oven through 50 DEG C of dryings, obtain vinyl glycine (Gly-AAc).
(2) preparation of vinyl ionic liquid monomer
Take vinyl glycine (Gly-AAc), choline (Ch) respectively, respectively be dissolved in 5ml distilled water, Gly-AAc: Ch=2mol: 1mol ~ 1mol: 1mol, with constant pressure funnel, choline solution is slowly dripped in vinyl glycine (Gly-AAc) solution, at 3 DEG C ~ 25 DEG C lower magnetic force stirring reaction 48h; Reaction terminates rear 60 DEG C of backspins steaming and dewaters, then above-mentioned reaction system is poured into excess ethyl alcohol, leave standstill and occur viscous solid material, centrifugation, product is dry at 50 DEG C, to remove residual second alcohol and water, obtain pure vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc).
(3) preparation of the multi-functional gel of dual network
Take vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc) and linking agent N, N-methylene-bisacrylamide (MBAA) is dissolved in 10ml distilled water, Ch-Gly-AAc concentration is made to be 0.1mol/L ~ 1.0mol/L, n (MBAA)/n (Ch-Gly-AAc) is 1mol% ~ 10mol%, stirred at ambient temperature, logical nitrogen 15min, add Potassium Persulphate (KPS), n (KPS)/n (Ch-Gly-AAc) is made to be 0.1mol% ~ 0.5mol%, pour reaction solution into glass mold, two 2%N are instilled with glue head dropper, N, N ', N '-Tetramethyl Ethylene Diamine (TEMED), 24h is reacted under room temperature, obtained poly ion liquid gel P (Ch-Gly-AAc), by gained soak in distilled water, every day changes water, removing unreacted small molecules.Take NIPA (NIPAAm) monomer, vinylformic acid (AAc) monomer, linking agent N, N-methylene-bisacrylamide (MBAA), be dissolved in 8mL distilled water, form second network reaction solution, after fully swelling in the second reaction solution for the poly ion liquid gel P (Ch-Gly-AAc) of drying, reaction system is transferred in ice-water bath, logical nitrogen, add the aqueous solution that 2mL contains Potassium Persulphate (KPS), the volumetric molar concentration of NIPAAm and AAc is made to be 1mol/L ~ 5mol/L, NIPAAm: AAc=95mol: 5mol, 90mol: 10mol, 80mol: 20mol, 70mol: 30mol, 60mol: 40mol, 50mol: 50mol, n (MBAA)/n (NIPAAm+AAc)=0mol% ~ 1mol%, n (KPS)/n (NIPAAm+AAc)=0.1mol% ~ 0.5mol%, after 4h, reaction system is transferred to 25 DEG C, two 2%TEMED are instilled with glue head dropper, dual network gel is obtained after reaction 24h, by gained soak in distilled water, every day changes water, removing unreacted small molecules.
Another object of the present invention is to the preparation method providing the multi-functional gel of a kind of dual network, preparation method comprises the following steps:
(1) preparation of vinyl glycine (Gly-AAc)
Take vinylformic acid (AAc), be dissolved in 10ml distilled water, add N-hydroxy-succinamide (NHS) and 1-ethyl-3-(3-dimethylamine propyl) carbodiimide (EDC), after room temperature lower magnetic force stirs 2h, add glycine (Gly) again and continue reaction 24h, AAc: Gly: EDC: NHS=5mol: 5mol: 5mol: 1mol; Pour excess ethyl alcohol into after question response terminates, leave standstill and separate out white crystal, by product centrifugation, abandoning supernatant, gets and to be deposited in baking oven through 50 DEG C of dryings, obtain vinyl glycine (Gly-AAc).
(2) preparation of vinyl ionic liquid monomer
Take vinyl glycine (Gly-AAc), choline (Ch) respectively, respectively be dissolved in 5ml distilled water, Gly-AAc: Ch=2mol: 1mol ~ 1mol: 1mol, with constant pressure funnel, choline solution is slowly dripped in vinyl glycine (Gly-AAc) solution, at 3 DEG C ~ 25 DEG C lower magnetic force stirring reaction 48h; Reaction terminates rear 60 DEG C of backspins steaming and dewaters, then above-mentioned reaction system is poured into excess ethyl alcohol, leave standstill and occur viscous solid material, centrifugation, product is dry at 50 DEG C, to remove residual second alcohol and water, obtain pure vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc).
(3) preparation of the multi-functional gel of dual network
Take vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc) and linking agent N, N-methylene-bisacrylamide (MBAA) is dissolved in 10ml distilled water, Ch-Gly-AAc concentration is made to be 0.1mol/L ~ 1.0mol/L, n (MBAA)/n (Ch-Gly-AAc) is 1mol% ~ 10mol%, stirred at ambient temperature, logical nitrogen 15min, add Potassium Persulphate (KPS), n (KPS)/n (Ch-Gly-AAc) is made to be 0.1mol% ~ 0.5mol%, pour reaction solution into glass mold, two 2%N are instilled with glue head dropper, N, N ', N '-Tetramethyl Ethylene Diamine (TEMED), 24h is reacted under room temperature, obtained poly ion liquid gel P (Ch-Gly-AAc), by gained soak in distilled water, every day changes water, removing unreacted small molecules.Take NIPA (NIPAAm) monomer, vinylformic acid (AAc) monomer, linking agent N, N-methylene-bisacrylamide (MBAA), be dissolved in 8mL distilled water, form second network reaction solution, after fully swelling in the second reaction solution for the poly ion liquid gel P (Ch-Gly-AAc) of drying, reaction system is transferred in ice-water bath, logical nitrogen, add the aqueous solution that 2mL contains Potassium Persulphate (KPS), the volumetric molar concentration of NIPAAm and AAc is made to be 1mol/L ~ 5mol/L, NIPAAm: AAc=95mol: 5mol, 90mol: 10mol, 80mol: 20mol, 70mol: 30mol, 60mol: 40mol, 50mol: 50mol, n (MBAA)/n (NIPAAm+AAc)=0mol% ~ 1mol%, n (KPS)/n (NIPAAm+AAc)=0.1mol% ~ 0.5mol%, after 4h, reaction system is transferred to 25 DEG C, two 2%TEMED are instilled with glue head dropper, dual network gel is obtained after reaction 24h, by gained soak in distilled water, every day changes water, removing unreacted small molecules.
Beneficial effect
The multi-functional gel of dual network designed by the present invention, due to the formation of dual network, make it have excellent mechanical property, the introducing of ionic liquid makes it have conductivity, the introducing of NIPAAm makes it have temperature-responsive, the introducing of AAc makes it have pH responsiveness, is a kind of high strength gel having several functions concurrently of exploitation, there is application prospect widely at multiple fields.
Specific embodiments
Embodiment 1.
(1) preparation of vinyl glycine (Gly-AAc)
Take vinylformic acid (AAc), be dissolved in 10ml distilled water, add N-hydroxy-succinamide (NHS) and 1-ethyl-3-(3-dimethylamine propyl) carbodiimide (EDC), after room temperature lower magnetic force stirs 2h, add glycine (Gly) again and continue reaction 24h, AAc: Gly: EDC: NHS=5mol: 5mol: 5mol: 1mol; Pour excess ethyl alcohol into after question response terminates, leave standstill and separate out white crystal, by product centrifugation, abandoning supernatant, gets and to be deposited in baking oven through 50 DEG C of dryings, obtain vinyl glycine (Gly-AAc).
(2) preparation of vinyl ionic liquid monomer
Take vinyl glycine (Gly-AAc), choline (Ch) respectively, respectively be dissolved in 5ml distilled water, Gly-AAc: Ch=1.05mol: 1mol, with constant pressure funnel, choline solution is slowly dripped in vinyl glycine (Gly-AAc) solution, at 3 DEG C of lower magnetic force stirring reaction 48h; Reaction terminates rear 60 DEG C of backspins steaming and dewaters, then above-mentioned reaction system is poured into excess ethyl alcohol, leave standstill and occur viscous solid material, centrifugation, product is dry at 50 DEG C, to remove residual second alcohol and water, obtain pure vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc).
(3) preparation of the multi-functional gel of dual network
Take vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc) and linking agent N, N-methylene-bisacrylamide (MBAA) is dissolved in 10ml distilled water, Ch-Gly-AAc concentration is made to be 0.2mol/L, n (MBAA)/n (Ch-Gly-AAc) is 2mol%, stirred at ambient temperature, logical nitrogen 15min, add Potassium Persulphate (KPS), n (KPS)/n (Ch-Gly-AAc) is made to be 0.1mol%, pour reaction solution into glass mold, two 2%N are instilled with glue head dropper, N, N ', N '-Tetramethyl Ethylene Diamine (TEMED), 24h is reacted under room temperature, obtained poly ion liquid gel P (Ch-Gly-AAc), by gained soak in distilled water, every day changes water, removing unreacted small molecules.Take NIPA (NIPAAm) monomer, vinylformic acid (AAc) monomer, linking agent N, N-methylene-bisacrylamide (MBAA), be dissolved in 8mL distilled water, form second network reaction solution, after fully swelling in the second reaction solution for the poly ion liquid gel P (Ch-Gly-AAc) of drying, reaction system is transferred in ice-water bath, logical nitrogen, add the aqueous solution that 2mL contains Potassium Persulphate (KPS), the volumetric molar concentration of NIPAAm and AAc is made to be 4mol/L, NIPAAm: AAc=95mol: 5mol, n (MBAA)/n (NIPAAm+AAc)=0mol%, n (KPS)/n (NIPAAm+AAc)=0.1mol%, after 4h, reaction system is transferred to 25 DEG C, two 2%TEMED are instilled with glue head dropper, dual network gel is obtained after reaction 24h, by gained soak in distilled water, every day changes water, removing unreacted small molecules.
Embodiment 2.
(1) preparation of vinyl glycine (Gly-AAc)
Take vinylformic acid (AAc), be dissolved in 10ml distilled water, add N-hydroxy-succinamide (NHS) and 1-ethyl-3-(3-dimethylamine propyl) carbodiimide (EDC), after room temperature lower magnetic force stirs 2h, add glycine (Gly) again and continue reaction 24h, AAc: Gly: EDC: NHS=5mol: 5mol: 5mol: 1mol; Pour excess ethyl alcohol into after question response terminates, leave standstill and separate out white crystal, by product centrifugation, abandoning supernatant, gets and to be deposited in baking oven through 50 DEG C of dryings, obtain vinyl glycine (Gly-AAc).
(2) preparation of vinyl ionic liquid monomer
Take vinyl glycine (Gly-AAc), choline (Ch) respectively, respectively be dissolved in 5ml distilled water, Gly-AAc: Ch=2mol: 1mol, with constant pressure funnel, choline solution is slowly dripped in vinyl glycine (Gly-AAc) solution, at 3 DEG C of lower magnetic force stirring reaction 48h; Reaction terminates rear 60 DEG C of backspins steaming and dewaters, then above-mentioned reaction system is poured into excess ethyl alcohol, leave standstill and occur viscous solid material, centrifugation, product is dry at 50 DEG C, to remove residual second alcohol and water, obtain pure vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc).
(3) preparation of the multi-functional gel of dual network
Take vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc) and linking agent N, N-methylene-bisacrylamide (MBAA) is dissolved in 10ml distilled water, Ch-Gly-AAc concentration is made to be 1.0mol/L, n (MBAA)/n (Ch-Gly-AAc) is 10mol%, stirred at ambient temperature, logical nitrogen 15min, add Potassium Persulphate (KPS), n (KPS)/n (Ch-Gly-AAc) is made to be 0.1mol%, pour reaction solution into glass mold, two 2%N are instilled with glue head dropper, N, N ', N '-Tetramethyl Ethylene Diamine (TEMED), 24h is reacted under room temperature, obtained poly ion liquid gel P (Ch-Gly-AAc), by gained soak in distilled water, every day changes water, removing unreacted small molecules.Take NIPA (NIPAAm) monomer, vinylformic acid (AAc) monomer, linking agent N, N-methylene-bisacrylamide (MBAA), be dissolved in 8mL distilled water, form second network reaction solution, after fully swelling in the second reaction solution for the poly ion liquid gel P (Ch-Gly-AAc) of drying, reaction system is transferred in ice-water bath, logical nitrogen, add the aqueous solution that 2mL contains Potassium Persulphate (KPS), the volumetric molar concentration of NIPAAm and AAc is made to be 4mol/L, NIPAAm: AAc=90mol: 10mol, n (MBAA)/n (NIPAAm+AAc)=0.1mol%, n (KPS)/n (NIPAAm+AAc)=0.1mol%, after 4h, reaction system is transferred to 25 DEG C, two 2%TEMED are instilled with glue head dropper, dual network gel is obtained after reaction 24h, by gained soak in distilled water, every day changes water, removing unreacted small molecules.
Embodiment 3.
(1) preparation of vinyl glycine (Gly-AAc)
Take vinylformic acid (AAc), be dissolved in 10ml distilled water, add N-hydroxy-succinamide (NHS) and 1-ethyl-3-(3-dimethylamine propyl) carbodiimide (EDC), after room temperature lower magnetic force stirs 2h, add glycine (Gly) again and continue reaction 24h, AAc: Gly: EDC: NHS=5mol: 5mol: 5mol: 1mol; Pour excess ethyl alcohol into after question response terminates, leave standstill and separate out white crystal, by product centrifugation, abandoning supernatant, gets and to be deposited in baking oven through 50 DEG C of dryings, obtain vinyl glycine (Gly-AAc).
(2) preparation of vinyl ionic liquid monomer
Take vinyl glycine (Gly-AAc), choline (Ch) respectively, respectively be dissolved in 5ml distilled water, Gly-AAc: Ch=1mol: 1mol, with constant pressure funnel, choline solution is slowly dripped in vinyl glycine (Gly-AAc) solution, at 3 DEG C of lower magnetic force stirring reaction 48h; Reaction terminates rear 60 DEG C of backspins steaming and dewaters, then above-mentioned reaction system is poured into excess ethyl alcohol, leave standstill and occur viscous solid material, centrifugation, product is dry at 50 DEG C, to remove residual second alcohol and water, obtain pure vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc).
(3) preparation of the multi-functional gel of dual network
Take vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc) and linking agent N, N-methylene-bisacrylamide (MBAA) is dissolved in 10ml distilled water, Ch-Gly-AAc concentration is made to be 0.2mol/L, n (MBAA)/n (Ch-Gly-AAc) is 4mol%, stirred at ambient temperature, logical nitrogen 15min, add Potassium Persulphate (KPS), n (KPS)/n (Ch-Gly-AAc) is made to be 0.5mol%, pour reaction solution into glass mold, two 2%N are instilled with glue head dropper, N, N ', N '-Tetramethyl Ethylene Diamine (TEMED), 24h is reacted under room temperature, obtained poly ion liquid gel P (Ch-Gly-AAc), by gained soak in distilled water, every day changes water, removing unreacted small molecules.Take NIPA (NIPAAm) monomer, vinylformic acid (AAc) monomer, linking agent N, N-methylene-bisacrylamide (MBAA), be dissolved in 8mL distilled water, form second network reaction solution, after fully swelling in the second reaction solution for the poly ion liquid gel P (Ch-Gly-AAc) of drying, reaction system is transferred in ice-water bath, logical nitrogen, add the aqueous solution that 2mL contains Potassium Persulphate (KPS), the volumetric molar concentration of NIPAAm and AAc is made to be 2mol/L, NIPAAm: AAc=50mol: 50mol, n (MBAA)/n (NIPAAm+AAc)=1mol%, n (KPS)/n (NIPAAm+AAc)=0.1mol%, after 4h, reaction system is transferred to 25 DEG C, two 2%TEMED are instilled with glue head dropper, dual network gel is obtained after reaction 24h, by gained soak in distilled water, every day changes water, removing unreacted small molecules.
Embodiment 4.
(1) preparation of vinyl glycine (Gly-AAc)
Take vinylformic acid (AAc), be dissolved in 10ml distilled water, add N-hydroxy-succinamide (NHS) and 1-ethyl-3-(3-dimethylamine propyl) carbodiimide (EDC), after room temperature lower magnetic force stirs 2h, add glycine (Gly) again and continue reaction 24h, AAc: Gly: EDC: NHS=5mol: 5mol: 5mol: 1mol; Pour excess ethyl alcohol into after question response terminates, leave standstill and separate out white crystal, by product centrifugation, abandoning supernatant, gets and to be deposited in baking oven through 50 DEG C of dryings, obtain vinyl glycine (Gly-AAc).
(2) preparation of vinyl ionic liquid monomer
Take vinyl glycine (Gly-AAc), choline (Ch) respectively, respectively be dissolved in 5ml distilled water, Gly-AAc: Ch=2mol: 1mol, with constant pressure funnel, choline solution is slowly dripped in vinyl glycine (Gly-AAc) solution, at 25 DEG C of lower magnetic force stirring reaction 48h; Reaction terminates rear 60 DEG C of backspins steaming and dewaters, then above-mentioned reaction system is poured into excess ethyl alcohol, leave standstill and occur viscous solid material, centrifugation, product is dry at 50 DEG C, to remove residual second alcohol and water, obtain pure vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc).
(3) preparation of the multi-functional gel of dual network
Take vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc) and linking agent N, N-methylene-bisacrylamide (MBAA) is dissolved in 10ml distilled water, Ch-Gly-AAc concentration is made to be 0.5mol/L, n (MBAA)/n (Ch-Gly-AAc) is 6mol%, stirred at ambient temperature, logical nitrogen 15min, add Potassium Persulphate (KPS), n (KPS)/n (Ch-Gly-AAc) is made to be 0.1mol%, pour reaction solution into glass mold, two 2%N are instilled with glue head dropper, N, N ', N '-Tetramethyl Ethylene Diamine (TEMED), 24h is reacted under room temperature, obtained poly ion liquid gel P (Ch-Gly-AAc), by gained soak in distilled water, every day changes water, removing unreacted small molecules.Take NIPA (NIPAAm) monomer, vinylformic acid (AAc) monomer, linking agent N, N-methylene-bisacrylamide (MBAA), be dissolved in 8mL distilled water, form second network reaction solution, after fully swelling in the second reaction solution for the poly ion liquid gel P (Ch-Gly-AAc) of drying, reaction system is transferred in ice-water bath, logical nitrogen, add the aqueous solution that 2mL contains Potassium Persulphate (KPS), the volumetric molar concentration of NIPAAm and AAc is made to be 4mol/L, NIPAAm: AAc=80mol: 20mol, n (MBAA)/n (NIPAAm+AAc)=0.5mol%, n (KPS)/n (NIPAAm+AAc)=0.1mol%, after 4h, reaction system is transferred to 25 DEG C, two 2%TEMED are instilled with glue head dropper, dual network gel is obtained after reaction 24h, by gained soak in distilled water, every day changes water, removing unreacted small molecules.
Embodiment 5.
(1) preparation of vinyl glycine (Gly-AAc)
Take vinylformic acid (AAc), be dissolved in 10ml distilled water, add N-hydroxy-succinamide (NHS) and 1-ethyl-3-(3-dimethylamine propyl) carbodiimide (EDC), after room temperature lower magnetic force stirs 2h, add glycine (Gly) again and continue reaction 24h, AAc: Gly: EDC: NHS=5mol: 5mol: 5mol: 1mol; Pour excess ethyl alcohol into after question response terminates, leave standstill and separate out white crystal, by product centrifugation, abandoning supernatant, gets and to be deposited in baking oven through 50 DEG C of dryings, obtain vinyl glycine (Gly-AAc).
(2) preparation of vinyl ionic liquid monomer
Take vinyl glycine (Gly-AAc), choline (Ch) respectively, respectively be dissolved in 5ml distilled water, Gly-AAc: Ch=1mol: 1mol, with constant pressure funnel, choline solution is slowly dripped in vinyl glycine (Gly-AAc) solution, at 25 DEG C of lower magnetic force stirring reaction 48h; Reaction terminates rear 60 DEG C of backspins steaming and dewaters, then above-mentioned reaction system is poured into excess ethyl alcohol, leave standstill and occur viscous solid material, centrifugation, product is dry at 50 DEG C, to remove residual second alcohol and water, obtain pure vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc).
(3) preparation of the multi-functional gel of dual network
Take vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc) and linking agent N, N-methylene-bisacrylamide (MBAA) is dissolved in 10ml distilled water, Ch-Gly-AAc concentration is made to be 0.5mol/L, n (MBAA)/n (Ch-Gly-AAc) is 10mol%, stirred at ambient temperature, logical nitrogen 15min, add Potassium Persulphate (KPS), n (KPS)/n (Ch-Gly-AAc) is made to be 0.1mol%, pour reaction solution into glass mold, two 2%N are instilled with glue head dropper, N, N ', N '-Tetramethyl Ethylene Diamine (TEMED), 24h is reacted under room temperature, obtained poly ion liquid gel P (Ch-Gly-AAc), by gained soak in distilled water, every day changes water, removing unreacted small molecules.Take NIPA (NIPAAm) monomer, vinylformic acid (AAc) monomer, linking agent N, N-methylene-bisacrylamide (MBAA), be dissolved in 8mL distilled water, form second network reaction solution, after fully swelling in the second reaction solution for the poly ion liquid gel P (Ch-Gly-AAc) of drying, reaction system is transferred in ice-water bath, logical nitrogen, add the aqueous solution that 2mL contains Potassium Persulphate (KPS), the volumetric molar concentration of NIPAAm and AAc is made to be 1mol/L, NIPAAm: AAc=70mol: 30mol, n (MBAA)/n (NIPAAm+AAc)=1mol%, n (KPS)/n (NIPAAm+AAc)=0.1mol%, after 4h, reaction system is transferred to 25 DEG C, two 2%TEMED are instilled with glue head dropper, dual network gel is obtained after reaction 24h, by gained soak in distilled water, every day changes water, removing unreacted small molecules.
Claims (9)
1. the multi-functional gel of dual network, is characterized in that described gel has temperature-responsive, pH responsiveness, electroconductibility, high-strength mechanical properties, and described gel can be obtained by following method:
(1) preparation of vinyl glycine (Gly-AAc)
Take vinylformic acid (AAc), be dissolved in 10ml distilled water, add N-hydroxy-succinamide (NHS) and 1-ethyl-3-(3-dimethylamine propyl) carbodiimide (EDC), after room temperature lower magnetic force stirs 2h, add glycine (Gly) again and continue reaction 24h, AAc: Gly: EDC: NHS=5mol: 5mol: 5mol: 1mol, excess ethyl alcohol is poured into after question response terminates, leave standstill and separate out white crystal, by product centrifugation, abandoning supernatant, gets and to be deposited in baking oven through 50 DEG C of dryings, obtain vinyl glycine (Gly-AAc);
(2) preparation of vinyl ionic liquid monomer
Take vinyl glycine (Gly-AAc) respectively, choline (Ch), respectively be dissolved in 5ml distilled water, Gly-AAc: Ch=2mol: 1mol ~ 1mol: 1mol, with constant pressure funnel, choline solution is slowly dripped in vinyl glycine (Gly-AAc) solution, at 3 DEG C ~ 25 DEG C lower magnetic force stirring reaction 48h, reaction terminates rear 60 DEG C of backspins steaming and dewaters, then above-mentioned reaction system is poured into excess ethyl alcohol, leave standstill and occur viscous solid material, centrifugation, product is dry at 50 DEG C, to remove residual second alcohol and water, obtain pure vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc),
(3) preparation of the multi-functional gel of dual network
Take vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc) and linking agent N, N-methylene-bisacrylamide (MBAA) is dissolved in 10ml distilled water, Ch-Gly-AAc concentration is made to be 0.1mol/L ~ 1.0mol/L, n (MBAA)/n (Ch-Gly-AAc) is 1mol% ~ 10mol%, stirred at ambient temperature, logical nitrogen 15min, add Potassium Persulphate (KPS), n (KPS)/n (Ch-Gly-AAc) is made to be 0.1mol% ~ 0.5mol%, pour reaction solution into glass mold, two 2%N are instilled with glue head dropper, N, N ', N '-Tetramethyl Ethylene Diamine (TEMED), 24h is reacted under room temperature, obtained poly ion liquid gel P (Ch-Gly-AAc), by gained soak in distilled water, every day changes water, removing unreacted small molecules, take NIPA (NIPAAm) monomer, vinylformic acid (AAc) monomer, linking agent N, N-methylene-bisacrylamide (MBAA), be dissolved in 8mL distilled water, form second network reaction solution, after fully swelling in the second reaction solution for the poly ion liquid gel P (Ch-Gly-AAc) of drying, reaction system is transferred in ice-water bath, logical nitrogen, add the aqueous solution that 2mL contains Potassium Persulphate (KPS), the volumetric molar concentration of NIPAAm and AAc is made to be 1mol/L ~ 5mol/L, NIPAAm: AAc=95mol: 5mol, 90mol: 10mol, 80mol: 20mol, 70mol: 30mol, 60mol: 40mol, 50mol: 50mol, n (MBAA)/n (NIPAAm+AAc)=0mol% ~ 1mol%, n (KPS)/n (NIPAAm+AAc)=0.1mol% ~ 0.5mol%, after 4h, reaction system is transferred to 25 DEG C, two 2%TEMED are instilled with glue head dropper, dual network gel is obtained after reaction 24h, by gained soak in distilled water, every day changes water, removing unreacted small molecules.
2. gel according to claim 1, is characterized in that having temperature-responsive, pH responsiveness, electroconductibility, high-strength mechanical properties.
3. the preparation method of the multi-functional gel of dual network, comprises the following steps:
(1) preparation of vinyl glycine (Gly-AAc)
Take vinylformic acid (AAc), be dissolved in 10ml distilled water, add N-hydroxy-succinamide (NHS) and 1-ethyl-3-(3-dimethylamine propyl) carbodiimide (EDC), after room temperature lower magnetic force stirs 2h, add glycine (Gly) again and continue reaction 24h, AAc: Gly: EDC: NHS=5mol: 5mol: 5mol: 1mol, excess ethyl alcohol is poured into after question response terminates, leave standstill and separate out white crystal, by product centrifugation, abandoning supernatant, gets and to be deposited in baking oven through 50 DEG C of dryings, obtain vinyl glycine (Gly-AAc);
(2) preparation of vinyl ionic liquid monomer
Take vinyl glycine (Gly-AAc) respectively, choline (Ch), respectively be dissolved in 5ml distilled water, Gly-AAc: Ch=2mol: 1mol ~ 1mol: 1mol, with constant pressure funnel, choline solution is slowly dripped in vinyl glycine (Gly-AAc) solution, at 3 DEG C ~ 25 DEG C lower magnetic force stirring reaction 48h, reaction terminates rear 60 DEG C of backspins steaming and dewaters, then above-mentioned reaction system is poured into excess ethyl alcohol, leave standstill and occur viscous solid material, centrifugation, product is dry at 50 DEG C, to remove residual second alcohol and water, obtain pure vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc),
(3) preparation of the multi-functional gel of dual network
Take vinyl choline-glycine ionic liquid monomer (Ch-Gly-AAc) and linking agent N, N-methylene-bisacrylamide (MBAA) is dissolved in 10ml distilled water, Ch-Gly-AAc concentration is made to be 0.1mol/L ~ 1.0mol/L, n (MBAA)/n (Ch-Gly-AAc) is 1mol% ~ 10mol%, stirred at ambient temperature, logical nitrogen 15min, add Potassium Persulphate (KPS), n (KPS)/n (Ch-Gly-AAc) is made to be 0.1mol% ~ 0.5mol%, pour reaction solution into glass mold, two 2%N are instilled with glue head dropper, N, N ', N '-Tetramethyl Ethylene Diamine (TEMED), 24h is reacted under room temperature, obtained poly ion liquid gel P (Ch-Gly-AAc), by gained soak in distilled water, every day changes water, removing unreacted small molecules, take NIPA (NIPAAm) monomer, vinylformic acid (AAc) monomer, linking agent N, N-methylene-bisacrylamide (MBAA), be dissolved in 8mL distilled water, form second network reaction solution, after fully swelling in the second reaction solution for the poly ion liquid gel P (Ch-Gly-AAc) of drying, reaction system is transferred in ice-water bath, logical nitrogen, add the aqueous solution that 2mL contains Potassium Persulphate (KPS), the volumetric molar concentration of NIPAAm and AAc is made to be 1mol/L ~ 5mol/L, NIPAAm: AAc=95mol: 5mol, 90mol: 10mol, 80mol: 20mol, 70mol: 30mol, 60mol: 40mol, 50mol: 50mol, n (MBAA)/n (NIPAAm+AAc)=0mol% ~ 1mol%, n (KPS)/n (NIPAAm+AAc)=0.1mol% ~ 0.5mol%, after 4h, reaction system is transferred to 25 DEG C, two 2%TEMED are instilled with glue head dropper, dual network gel is obtained after reaction 24h, by gained soak in distilled water, every day changes water, removing unreacted small molecules.
4., according to claim 1, the multi-functional gel process for preparing of a kind of dual network described in 3, is characterized in that described step (1) middle AAc: Gly: EDC: NHS=5mol: 5mol: 5mol: 1mol.
5., according to claim 1, the multi-functional gel process for preparing of a kind of dual network described in 3, is characterized in that in described step (2), temperature of reaction is 3 DEG C ~ 25 DEG C.
6., according to claim 1, the multi-functional gel process for preparing of a kind of dual network described in 3, is characterized in that in described step (3), Ch-Gly-AAc concentration is 0.1mol/L ~ 1.0mol/L.
7., according to claim 1, the multi-functional gel process for preparing of a kind of dual network described in 3, is characterized in that in described step (3), n (MBAA)/n (Ch-Gly-AAc) is 1mol% ~ 10mol%.
8., according to claim 1, the multi-functional gel process for preparing of a kind of dual network described in 3, is characterized in that the volumetric molar concentration of NIPAAm and AAc in described step (3) is 1mol/L ~ 5mol/L.
9., according to claim 1, the multi-functional gel process for preparing of a kind of dual network described in 3, is characterized in that n (MBAA)/n (NIPAAm+AAc)=0mol% ~ 1mol% in described step (3).
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