CN1746199A - Direct synthesis of temperate sensitive aquogel by ultraviolet radiant polymerization - Google Patents
Direct synthesis of temperate sensitive aquogel by ultraviolet radiant polymerization Download PDFInfo
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- CN1746199A CN1746199A CN 200510086551 CN200510086551A CN1746199A CN 1746199 A CN1746199 A CN 1746199A CN 200510086551 CN200510086551 CN 200510086551 CN 200510086551 A CN200510086551 A CN 200510086551A CN 1746199 A CN1746199 A CN 1746199A
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Abstract
Synthesis of warm sensitive aquagel from ultraviolet light radiation polymerization is carried out by adding reacting raw materials into deionized water to prepare preformed solution, laying aside under ultraviolet light radiation, exposing, polymerizing directly to prepare cross-linking polymer, putting the polymer into sorbitic extractor, extracting from boiled deionized water for 24hrs, taking it out, and drying in vacuum drier to obtain warm sensitive aquagel. Its low critical temperature varies between 30-40 Deg C. with raw material formula. It can be used for various aquagels, medicine control-releasing system, memory element switch, artificial muscle and chemical industrial separation. It achieves low cost, simple process, high efficiency and normal-temperature operation.
Description
Technical field
Method with temperature-sensitive hydrogel is directly synthesized in the ultraviolet radiation polymerization belongs to macromolecule material preparation area.
Background technology
The stimulating responsive hydrogel be a class for external environment small physics or chemical stimulation, the hydrogel of considerable change can take place in himself character.It is a kind of water insoluble, can be in water swollen hydrophilic cross-linking polymkeric substance.External environment factors vary such as the stimulating responsive hydrogel can response temperature, pH, light, electric field and magnetic field.Utilize the deformation behavior of stimulating responsive hydrogel under environmental stimulus, people dream up various chemical energy-mechanical energy conversion system, as artificial muscle model, chemical valve, shape-memory material, medicine controlled releasing, sewage disposal etc.
Because the stimulating responsive hydrogel has potential using value in fields such as controlled drug delivery system, memory cell switch, artificial muscle, chemical separating, thereby has caused domestic and international many scholars' extensive concern.The stimulating responsive hydrogel is increasing in the application of bio-science fields such as the activity control of cell culture substrate, enzyme, target administration in recent years.
The basis of stimulating responsive macromolecule hydrogel researchdevelopment is the gel swelling theory of Flory P J, utilizes factors such as the intermolecular interaction field of force, ion electric field and photochemical effect to make the volume of hydrogel produce response.From the selection of hydrogel matrix, mostly adopt synthetic polymer both at home and abroad, by system in response such as homopolymer, grafting or segmented copolymer, blend, interpenetrating polymer networks (IPN), polymer microsphere (PMS).In view of the huge applications of stimulating responsive hydrogel at biological field is worth, obtained suitable attention to have the good and biodegradable chitosan (chitosan) of the natural macromolecular material of gel phase transformation characteristic, particularly biocompatibility for the research of the hydrogel on basis.Current have the throwing oneself into research of synthetic, structure, performance and Response Mechanism of hydrogel of many scholars, believes that in the near future we can realize the huge convenience that work that the stimulating responsive hydrogel is given us and life bring.
Temperature-sensitive hydrogel: have a certain proportion of hydrophilic and hydrophobic grouping in this class hydrogel structure, variation of temperature can influence the hydrophobic interaction and the macromole interchain hydrogen bond action of these groups, thereby changes the network structure of hydrogel, produces volume phase transition.Temperature-sensitive hydrogel has high-temperature shrinkage and low temperature to shrink two types.Traditional method synthetic hydrogel mostly has the slow shortcoming of response speed, and the synthetic hydrogel of response fast is an important topic of intelligent aqueous gel capable research always.Poly N-isopropyl acrylamide (PNIPA) is a typical high temperature shrinkage type hydrogel, to the general explanation of its Response Mechanism is, the hydrophobic interaction mutually strengthens when temperature raises, and gel is shunk.Beijing Institute of Technology change in vain equality adopt chemically crosslinked and circulation freezing-the order approximatioss that thaws and combine, prepared polyvinyl alcohol/polyacrylic acid IPN temperature-sensitive hydrogel.They find can control by the content of regulating linking agent in the gel size of sudden change volume.The Kimiko Makino of Tokyo Univ Japan etc. has studied swelling and the shrinkage of PNIPA hydrogel in water under the differing temps.They think that water molecules has three kinds of existence forms in hydrogel: (a) be adsorbed near the hydration layer the polymer hydrophobic chain; (b) water molecules that in looser polymer network, moves freely; (c) be connected water molecules on the hydrophilic radical by hydrogen bond.Polyacrylic acid and poly-N,N-DMAA IPN hydrogel are the low temperature shrinkage types, form hydrogen bond, volumetric shrinkage under the low temperature in the gel network; Hydrogen bond dissociates under the high temperature, gel swelling.
The research report of relevant low temperature shrinkage type gel is less relatively.
At present, the method for preparing temperature-sensitive hydrogel both at home and abroad is based on traditional thermopolymerization and gamma-radiation radio polymerization, and it is new method that the ultraviolet radiation polymerization prepares temperature-sensitive hydrogel, present domestic any patent report that still do not have.
Summary of the invention
Purpose of the present invention: utilize UV-light as source of radiation, the directly synthetic temperature-sensitive hydrogel of light polymerization method is a kind of new technology.It has that polymerization velocity is fast, efficient is high and but normal temperature such as reacts at characteristics, has greatly simplified polymerization technique, has avoided in the traditional preparation process method multistep rapid, long-time and shortcoming such as pollution is arranged, for the industrial production temperature-sensitive hydrogel is opened up new approach.The raw material of this polymerization process comprises monomer, polymkeric substance, light trigger and linking agent etc., can form stable homogeneous system in the aqueous solution, and the polymerization process three-waste free pollution is a kind of method for preparing hydrogel of environmental protection.
A kind of with the directly synthetic temperature-sensitive hydrogel method of ultraviolet radiation polymerization, this preparation method may further comprise the steps:
(1) the configuration pre-gathering solutions mixes reaction raw materials according to following mass content (not comprising deionized water), is solvent with the deionized water, obtains pre-gathering solutions:
Polymerization single polymerization monomer [75～99.5wt%], light trigger [1～10wt%],
Linking agent [0.1～1wt%], polymeric additive [0.1～25wt%];
Described polymerization single polymerization monomer is an any or multiple mixture in vinylformic acid and the following five kinds of monomers: N-N-isopropylacrylamide, N,N-DMAA, (2-methylacryoyloxyethyl) trimethyl ammonium chloride, N-isobutyl-acrylamide, methacrylic acid; Wherein, vinylformic acid physique amount content is [1～90wt%], and other monomer mass content are [1～95wt%];
Described light trigger is benzoin dimethylether, Alpha-hydroxy cyclohexyl-phenyl ketone, 2-methyl isophthalic acid-[4-(methyl thio-phenyl)-2-morpholino acetone], Alpha-hydroxy, any one or more in α-phenyl Propiophenone, 1-hydroxy cyclohexyl phenylketone, the 2-hydroxy-2-methyl-1-phenyl-acetone;
(2) pre-gathering solutions with step (1) gained places under the ultraviolet radiation, and exposing, direct polymerization becomes cross-linked polymer after 5-30 minute;
(3) cross-linked polymer of step (2) gained is put into apparatus,Soxhlet's with the deionized water extracting 24 hours of boiling, put into the vacuum drying oven drying after the taking-up, can arrive temperature-sensitive hydrogel.
Described linking agent is N, any one or more in N '-methylene-bisacrylamide, diethylene glycol diacrylate, three polyethyleneglycol diacrylates, four polyethyleneglycol diacrylates, Hydroxyethyl acrylate, Propylene glycol monoacrylate, the n-methylolacrylamide;
Described polymeric additive is any one or more in polyvinyl alcohol, chitosan, the polyacrylamide;
Its photopolymerization reaction path (as Fig. 1) is: monomer and linking agent and polymeric additive and light trigger are blended in that the direct synthesizing cross-linked polyalcohol hydrogel of polymerization is a temperature-sensitive hydrogel under the ultraviolet radiation.
Utilize the directly synthetic temperature-sensitive hydrogel method of above-mentioned ultraviolet radiation polymerization, can prepare the hydrogel of multiple different performance.Its low critical transition temperature LCST (the lower critical solution temperature) changes between 30 ℃-40 ℃ with the variation of composition of raw materials.The equilibrium swelling multiple of various synthetic hydrogels and physical strength be the difference to some extent with the different of raw material also.The hydrogel that these performances are different can be used for a plurality of fields such as controlled drug delivery system, memory cell switch, artificial muscle, chemical separating.But this preparation method has that technology is simple, polymerization efficiency is high, pollution is little, cost is low and characteristics such as normal-temperature operation.
Description of drawings
Fig. 1 directly synthesizes the method polyreaction path synoptic diagram of temperature-sensitive hydrogel with the ultraviolet radiation polymerization.
Embodiment
Below with specific embodiment the present invention is described.Embodiment is for the present invention being described rather than limiting of the present invention.
Embodiment 1
3g monomer (N-N-isopropylacrylamide), 0.5g monomer (vinylformic acid), 0.015g light trigger (benzoin dimethylether), 0.01g linking agent (N, N '-methylene-bisacrylamide) are dissolved in the 18mL deionized water.The solution for preparing is placed beaker, and exposure is 10 minutes under high voltage mercury lamp, obtains cross-linked polymer.Cross-linked polymer is put into apparatus,Soxhlet's with the deionized water extracting 24 hours of boiling, put into the vacuum drying oven drying after the taking-up, obtain temperature-sensitive hydrogel.
Embodiment 2
3g monomer (N-N-isopropylacrylamide), 1g monomer (vinylformic acid), 0.2g polymkeric substance (polyvinyl alcohol), 0.018g light trigger (2-methyl isophthalic acid-[4-(methyl thio-phenyl)-2-morpholino acetone]), 0.1g linking agent (diethylene glycol diacrylate) are dissolved in the 23mL deionized water.The solution for preparing is placed beaker, and exposure is 12 minutes under high voltage mercury lamp, obtains cross-linked polymer.Cross-linked polymer is put into apparatus,Soxhlet's with the deionized water extracting 24 hours of boiling, put into the vacuum drying oven drying after the taking-up, obtain temperature-sensitive hydrogel.
Embodiment 3
2.5g monomer (N-N-isopropylacrylamide), 0.3g monomer (vinylformic acid), 0.1g polymkeric substance (chitosan), 0.03g light trigger (Alpha-hydroxy, α-phenyl Propiophenone), 0.2g linking agent (three polyethyleneglycol diacrylates) are dissolved in the 21mL deionized water.The solution for preparing is placed beaker, and exposure is 15 minutes under high voltage mercury lamp, obtains cross-linked polymer.Cross-linked polymer is put into apparatus,Soxhlet's with the deionized water extracting 24 hours of boiling, put into the vacuum drying oven drying after the taking-up, obtain temperature-sensitive hydrogel.
Embodiment 4
2.5g monomer (N-N-isopropylacrylamide), 0.3g monomer (vinylformic acid), 0.1g polymkeric substance (polyacrylamide), 0.03g light trigger (Alpha-hydroxy cyclohexyl-phenyl ketone), 0.25g linking agent (four polyethyleneglycol diacrylates) are dissolved in the 21mL deionized water.The solution for preparing is placed beaker, and exposure is 20 minutes under high voltage mercury lamp, obtains cross-linked polymer.Cross-linked polymer is put into apparatus,Soxhlet's with the deionized water extracting 24 hours of boiling, put into the vacuum drying oven drying after the taking-up, obtain temperature-sensitive hydrogel.
Embodiment 5
3g monomer (N-N-isopropylacrylamide), 0.5g monomer (vinylformic acid), 0.2g monomer (N, N '-DMAA), 0.03g light trigger (1-hydroxy cyclohexyl phenylketone), 0.2g linking agent (four polyethyleneglycol diacrylates) are dissolved in the 20mL deionized water.The solution for preparing is placed beaker, and exposure is 10 minutes under high voltage mercury lamp, obtains cross-linked polymer.Cross-linked polymer is put into apparatus,Soxhlet's with the deionized water extracting 24 hours of boiling, put into the vacuum drying oven drying after the taking-up, obtain temperature-sensitive hydrogel.
Embodiment 6
2.6g monomer (N-N-isopropylacrylamide), 0.5g monomer (vinylformic acid), 0.2g monomer ((2-methylacryoyloxyethyl) trimethyl ammonium chloride), 0.03g light trigger (2-hydroxy-2-methyl-1-phenyl-acetone), 0.5g linking agent (Hydroxyethyl acrylate) are dissolved in the 20mL deionized water.The solution for preparing is placed beaker, and exposure is 10 minutes under high voltage mercury lamp, obtains cross-linked polymer.Cross-linked polymer is put into apparatus,Soxhlet's with the deionized water extracting 24 hours of boiling, put into the vacuum drying oven drying after the taking-up, obtain temperature-sensitive hydrogel.
Embodiment 7
3g monomer (N-N-isopropylacrylamide), 0.3g monomer (vinylformic acid), 0.2g monomer (N-isobutyl-acrylamide), 0.02g light trigger (benzoin dimethylether), 0.5g linking agent (Propylene glycol monoacrylate) are dissolved in the 22mL deionized water.The solution for preparing is placed beaker, and exposure is 15 minutes under high voltage mercury lamp, obtains cross-linked polymer.Cross-linked polymer is put into apparatus,Soxhlet's with the deionized water extracting 24 hours of boiling, put into the vacuum drying oven drying after the taking-up, obtain temperature-sensitive hydrogel.
Embodiment 8
3g monomer (N-N-isopropylacrylamide), 0.3g monomer (vinylformic acid), 0.15g monomer (methacrylic acid), 0.02g light trigger (benzoin dimethylether), 0.1g linking agent (n-methylolacrylamide) are dissolved in the 22mL deionized water.The solution for preparing is placed beaker, and exposure is 15 minutes under high voltage mercury lamp, obtains cross-linked polymer.Cross-linked polymer is put into apparatus,Soxhlet's with the deionized water extracting 24 hours of boiling, put into the vacuum drying oven drying after the taking-up, obtain temperature-sensitive hydrogel.
Embodiment 9
3g monomer (N-N-isopropylacrylamide), 0.3g monomer (vinylformic acid), 0.15g monomer (methacrylic acid), 0.1g polymkeric substance (polyvinyl alcohol), 0.02g light trigger (benzoin dimethylether), 0.1g linking agent (N, N '-methylene-bisacrylamide) are dissolved in the 20mL deionized water.The solution for preparing is placed beaker, and exposure is 15 minutes under high voltage mercury lamp, obtains cross-linked polymer.Cross-linked polymer is put into apparatus,Soxhlet's with the deionized water extracting 24 hours of boiling, put into the vacuum drying oven drying after the taking-up, obtain temperature-sensitive hydrogel.
Claims (4)
1, a kind of with the directly synthetic temperature-sensitive hydrogel method of ultraviolet radiation polymerization, it is characterized in that this preparation method may further comprise the steps:
(1) the configuration pre-gathering solutions according to following mass content, does not comprise deionized water with reaction raw materials, mix, and be solvent with the deionized water, obtain pre-gathering solutions:
Polymerization single polymerization monomer [75～99.5wt%], light trigger [1～10wt%],
Linking agent [0.1～1wt%], polymeric additive [0.1～25wt%];
Described polymerization single polymerization monomer is an any or multiple mixture in vinylformic acid and the following five kinds of monomers: N-N-isopropylacrylamide, N,N-DMAA, (2-methylacryoyloxyethyl) trimethyl ammonium chloride, N-isobutyl-acrylamide, methacrylic acid;
Described light trigger is benzoin dimethylether, Alpha-hydroxy cyclohexyl-phenyl ketone, 2-methyl isophthalic acid-[4-(methyl thio-phenyl)-2-morpholino acetone], Alpha-hydroxy, any one or more in α-phenyl Propiophenone, 1-hydroxy cyclohexyl phenylketone, the 2-hydroxy-2-methyl-1-phenyl-acetone;
(2) pre-gathering solutions with step (1) gained places under the ultraviolet radiation, and exposing, direct polymerization becomes cross-linked polymer after 5-30 minute;
(3) cross-linked polymer of step (2) gained is put into apparatus,Soxhlet's with the deionized water extracting 24 hours of boiling, put into the vacuum drying oven drying after the taking-up, can arrive temperature-sensitive hydrogel.
2, a kind of directly synthetic temperature-sensitive hydrogel method of ultraviolet radiation polymerization of using according to claim 1 is characterized in that the vinylformic acid mass content is [1～90wt%] in the described polymerization single polymerization monomer, and other monomeric mass content are [1～95wt%].
3, according to claim 1 a kind of with the directly synthetic temperature-sensitive hydrogel method of ultraviolet radiation polymerization, it is characterized in that, described linking agent is N, any one or more in N '-methylene-bisacrylamide, diethylene glycol diacrylate, three polyethyleneglycol diacrylates, four polyethyleneglycol diacrylates, Hydroxyethyl acrylate, Propylene glycol monoacrylate, the n-methylolacrylamide.
4, according to claim 1 a kind of with the directly synthetic temperature-sensitive hydrogel method of ultraviolet radiation polymerization, it is characterized in that described polymeric additive is any one or more in polyvinyl alcohol, chitosan, the polyacrylamide.
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