CN103601864A - Cationic electric field sensitive sugar-based intelligent hydrogel with dumbbell structure and preparation method thereof - Google Patents
Cationic electric field sensitive sugar-based intelligent hydrogel with dumbbell structure and preparation method thereof Download PDFInfo
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- CN103601864A CN103601864A CN201310560325.0A CN201310560325A CN103601864A CN 103601864 A CN103601864 A CN 103601864A CN 201310560325 A CN201310560325 A CN 201310560325A CN 103601864 A CN103601864 A CN 103601864A
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Abstract
The invention relates to cationic electric field sensitive sugar-based intelligent hydrogel with a dumbbell structure and a preparation method thereof. The overall structure of the cationic electric field sensitive sugar-based intelligent hydrogel is dumbbell-shaped. In the preparation, firstly, a polymerizable double bonds-containing sugar-based monomer is synthesized by performing an esterification reaction on micromolecular glucose serving as a raw material; then, the cationic sugar-based intelligent hydrogel with the dumbbell structure is prepared by taking trithiocarbonate as a chain transfer agent by virtue of a reversible addition fragmentation chain transfer agent free radical polymerization method and cationic electric field sensitive monomer 2-(dimethylamino)ethyl methacrylate polymerization.
Description
technical field:
The present invention relates to the cationic electric field-sensitive glycosyl of a kind of dumbbell structure intelligent aqueous gel capable and preparation method thereof.
background technology:
Hydrogel refers to that a kind of main chain or side chain contain a large amount of hydrophilic radicals and adsorb the cross-linked polymer with tridimensional network that has large quantity of moisture.Hydrogel swelling but do not dissolve in water contains large quantity of moisture when keeping definite shape.According to environmental stimulus being replied to difference, can be divided into stimulating insensitive traditional hydrogel and producing to stimulating the environmental sensitive hydrogels responding, the latter claims again intelligent aqueous gel capable.So-called Intelligent Hydrogels, refers in extraneous physics and chemistry factor, as reversible change hydrogel can occur for own vol and shape under the stimulation of temperature, pH, optical, electrical, magnetic, sound, power and chemical substance etc.Due to unique responsiveness of progress in Intelligent Hydrogel, at aspects such as fixing, the organizational project of chemical transformation device, memory cell switch, sensor, artificial muscle, chemical storage device, molecular separation system, organized enzyme, pharmaceutical carriers, there is good application prospect.
In various external stimulus conditions, electric field is easy to apply and is easy to regulation and control, and this feature makes electric field-sensitive hydrogel become the problem that intelligent aqueous gel capable research field receives much concern.Hamlen etc. have reported the distortion of polyelectrolyte hydrogel under electric field induction the earliest in nineteen sixty-five, and from the nineties in 20th century, electric field-sensitive hydrogel becomes one of study hotspot.Electric field-sensitive hydrogel generally consists of polyelectrolyte, is placed in electrolyte solution, and under electrical field stimulation effect, volume or change in shape can occur gel, and then realizes by electric energy to mechanical transformation of energy.About the Response Mechanism of electric field-sensitive hydrogel, opinions vary, and Tanaka etc. are early than explaining by mean field theory the eighties in 20th century; Other the electrolysis that also has water, electrodiffusion is theoretical, sxemiquantitative is theoretical, depolarize is theoretical, one dimension electric field kinetic model, osmotic pressure mechanism etc. are explained.Generally speaking, this type of swelling behavior or go the response characteristic of swelling to realize under electrical field stimulation effect, and ionogen in gel network is the essential condition that electric field-sensitive hydrogel has electricity irritation respondent behavior.
Due to the synthetic high molecular biocompatibility of great majority and biological degradability poor, limited its application aspect biological medicine.So there is good biocompatibility, nontoxic, environmental friendliness, and the natural polymer with more active group becomes the ideal material of preparing hydrogel in recent years gradually.Corresponding, to compare with synthetic polymer, natural polymer hydrogel has hypotoxicity, good biocompatibility, to environment sensitive and the cheap advantages such as price, however bad mechanical strength, unstable properties, the easily deficiency such as the degraded improvement that needs.See thus, hypotoxicity, good biocompatibility and biological degradability, good mechanical property and this some perfect adaptation of environmental sensitivity are got up, prepare the research direction that novel, green intelligent aqueous gel capable is effort from now on.Saccharide compound is as a class natural reproducible biomass resource, there is the not available good biocompatibility of petrochemical materials, biological degradability, the advantage such as nontoxic, non-stimulated, therefore, the electric field-sensitive intelligent aqueous gel capable of introducing glycosyl has broad application prospects.
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summary of the invention:
The object of the invention is in order to obtain the cationic electric field-sensitive intelligent aqueous gel capable that a kind of biocompatibility is good, by introducing glucose small molecules, prepared the cationic electric field-sensitive intelligent aqueous gel capable of the controlled dumbbell structure of a kind of structure.
Technical solution of the present invention is:
The cationic electric field-sensitive glycosyl of a dumbbell structure intelligent aqueous gel capable is dumbbell structure in overall molecule structure; In preparation, take glucose as raw material, through carrying out esterification with unsaturated carboxylic acid halides, prepare Monomer containing sugar moiety; The polymerization process adopting is reversible addition-fragmentation chain transfer free radical polymerization, wherein, the esterifying reagent of polymerizable double bond is acrylate chloride, electric field-sensitive sense monomer is methacrylic acid N, N-dimethylaminoethyl (DMAEMA), RAFT agent is S, S '-bis-(α, α '-dimethyl-α ' '-acetic acid)-trithiocarbonate (CMP).
A preparation method for the cationic electric field-sensitive glycosyl of dumbbell structure intelligent aqueous gel capable, preparation process is as follows:
Step 1: glucose monomer is protected through OH, with the standby polymerizable Monomer containing sugar moiety that contains two keys of the unsaturated acyl stew in soy sauce that contains two keys;
Step 2: trithiocarbonate chain transfer agent CMP and the prepared polymerizable Monomer containing sugar moiety of previous step are joined in a certain amount of tetrahydrofuran (THF), under protection of inert gas, add initiator Diisopropyl azodicarboxylate, at 70 ℃, carry out the polymerization of Monomer containing sugar moiety, after Monomer containing sugar moiety polymerization completes, add electric field-sensitive monomer DMAEMA copolymerization, add again subsequently Monomer containing sugar moiety polymerization to obtain dumbbell structure glycosyl polymkeric substance;
Step 3: by the dumbbell structure glycosyl polymkeric substance of preparation, the free OH of hydrolysis, obtains the cationic electric field-sensitive glycosyl of target product dumbbell structure intelligent aqueous gel capable in diluted acid.
The present invention compared with prior art has the following advantages: 1. having prepared gel molecular skeleton is dumbbell structure, and its structure can regulate and control; 2. raw material used in the present invention is saccharide compound, has improved biocompatibility; 3. prepared glycosyl intelligent aqueous gel capable has good electric field response behavior.
accompanying drawing explanation:
Fig. 1 is the schematic diagram of the cationic electric field-sensitive glycosyl of dumbbell structure intelligent aqueous gel capable.
embodiment:
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and the following example only, for explaining the present invention, does not form limiting the scope of the present invention.
Embodiment 1:
Synthesizing of diacetoneglucose acrylate: in the four-hole boiling flask of 250mL that thermometer reflux condensing tube is housed, add dry anhydrous propanone 150 mL and pulverizing dry glucose 9.0 g (0.05 mol), add the anhydrous FeCl of catalyzer
3(1.7g, 0.01mol).Back flow reaction 2h under ultrasound condition.Then add rare Na
2cO
3solution 300 ml, CHCl
3extract three times (50 ml * 3), merge organic phase and with saturated common salt water washing (50 ml * 3), use anhydrous Na
2sO
4dry, filter underpressure distillation, obtain crude product, yield is 75.8%, with hexanaphthene recrystallization, obtains white crystals diacetoneglucose DAG.In the there-necked flask of 250mL dried and clean; add DAG(10 g, 0.04mol) and 80mL dry tetrahydrofuran stirring and dissolving, under nitrogen protection; by 60% sodium hydride (2.4g; 0.052 mol), then under 40 ℃ of conditions, stirring reaction 1h; slowly drip acrylate chloride (5.45g; 0.045mol), after dropping finishes, continue reaction 3h.Remove by filter insolubles, removal of solvent under reduced pressure, obtains diacetoneglucose acrylate, and yield is 92.1%.
Embodiment 2:
Trithiocarbonate CMP's is synthetic: by dithiocarbonic anhydride (0.1 mol, 7.613 g), trichloromethane (0.25 mol, 29.85 g), acetone (0.25 mol, 14.52 g) and tetrabutylammonium iodide (0.002 mol, 0.74 g), normal hexane (50ml) joins in the there-necked flask of 500 ml, in there-necked flask, plug respectively constant pressure funnel, thermometer, spherical condensation tube (with threeway), 50% sodium hydroxide (0.7 mol, 56 g) is added in constant pressure funnel simultaneously.Cooling with ice-water bath, keep temperature lower than 25 ℃.By threeway, balloon (interior inflated with nitrogen), with water circulating pump, bleed, then open threeway inflation, so 3-4 time, make device under nitrogen protection.Open constant pressure funnel, keep dripping fast 2s/ and drip left and right, control temperature lower than 25 ℃.Reaction overnight.After having reacted, add distilled water (300ml) to dissolve the solid generating, then add concentrated hydrochloric acid (35ml) to constant pressure funnel, open piston, drip concentrated hydrochloric acid, acidifying water layer, notes controlling temperature lower than 25 ℃.After dripping, then stir 30 min, responseless volatility of raw material is fallen.By the solid filtering in solution out, and wash with water, obtain khaki color crude product solid, claim to obtain thick CMP 16.8 g, thick productive rate is 89.3%.Thick CMP is carried out to recrystallization with 60% isopropanol water solution and obtain 14.6 g.
Embodiment 3:
In the four-hole boiling flask of 250 mL that thermometer is housed, add tetrahydrofuran (THF) 100 ml, then add diacetoneglucose acrylate 10.0 g and trithiocarbonate CMP0.2 g, under nitrogen protection, add initiator Diisopropyl azodicarboxylate AIBN 0.05 g, in 70 ℃ of water-baths, reaction 2h, adopts TLC to detect Monomer containing sugar moiety polymerization complete; Add subsequently comonomer DMAEMA 10.0 g, at 70 ℃, continue polyreaction 5h.TLC detection reaction to monomer disappears substantially; Diacetoneglucose acrylate 10.0 g that add 50 mL tetrahydrofuran (THF)s to dissolve by draw point transfer method, continue polymerization 5h.Add the be hydrolyzed acetone of deprotection of the hydrochloric acid of 2 mol/L, hydrolysis 2h, methanol extraction, dry, obtain " glycosyl-DMAEMA-glycosyl " cationic electric field-sensitive glycosyl of dumbbell structure hydrogel 15.5 g.
Embodiment 4:
In the four-hole boiling flask of 250 mL that thermometer is housed, add tetrahydrofuran (THF) 100 ml, then add diacetoneglucose acrylate 5.0 g and trithiocarbonate CMP0.1 g, under nitrogen protection, add initiator Diisopropyl azodicarboxylate AIBN 0.025 g, in 70 ℃ of water-baths, reaction 2h, adopts TLC to detect Monomer containing sugar moiety polymerization complete; Add subsequently comonomer DMAEMA 10.0 g, at 70 ℃, continue polyreaction 5h.TLC detection reaction to monomer disappears substantially; Diacetoneglucose acrylate 5.0 g that add 50 mL tetrahydrofuran (THF)s to dissolve by draw point transfer method, continue polymerization 5h.Add the be hydrolyzed acetone of deprotection of the hydrochloric acid of 2 mol/L, hydrolysis 2h, methanol extraction, dry, obtain " glycosyl-DMAEMA-glycosyl " cationic electric field-sensitive glycosyl of dumbbell structure hydrogel 12.5 g.
Embodiment 5:
In the four-hole boiling flask of 250 mL that thermometer is housed, add tetrahydrofuran (THF) 100 ml, then add diacetoneglucose acrylate 10.0 g and trithiocarbonate CMP0.2 g, under nitrogen protection, add initiator Diisopropyl azodicarboxylate AIBN 0.05 g, in 70 ℃ of water-baths, reaction 2h, adopts TLC to detect Monomer containing sugar moiety polymerization complete; Add subsequently comonomer DMAEMA 5.0 g, at 70 ℃, continue polyreaction 5h.TLC detection reaction to monomer disappears substantially; Diacetoneglucose acrylate 5.0 g that add 50 mL tetrahydrofuran (THF)s to dissolve by draw point transfer method, continue polymerization 5h.Add the be hydrolyzed acetone of deprotection of the hydrochloric acid of 2 mol/L, hydrolysis 2h, methanol extraction, dry, obtain " glycosyl-DMAEMA-glycosyl " cationic electric field-sensitive glycosyl of dumbbell structure hydrogel 14.6 g.
Claims (5)
1. the cationic electric field-sensitive glycosyl of a dumbbell structure intelligent aqueous gel capable, is characterized in that: in overall molecule structure, be dumbbell structure; In preparation, take glucose as raw material, through carrying out esterification with unsaturated carboxylic acid halides, prepare Monomer containing sugar moiety; By Monomer containing sugar moiety and cationic electric field-sensitive monomer, by reversible addition-fragmentation chain transfer free radical polymerization, prepare the cationic electric field-sensitive glycosyl of dumbbell structure intelligent aqueous gel capable.
2. the cationic electric field-sensitive glycosyl of dumbbell structure according to claim 1 intelligent aqueous gel capable, is characterized in that: described unsaturated carboxylic acid halides is acrylate chloride.
3. the cationic electric field-sensitive glycosyl of dumbbell structure according to claim 1 intelligent aqueous gel capable, is characterized in that: described cationic electric field-sensitive monomer is methacrylic acid N, N-dimethylaminoethyl (DMAEMA).
4. reversible addition-fragmentation chain transfer free radical polymerization according to claim 1 is characterized in that: the RAFT agent that adopts is S, S '-bis-(α, α '-dimethyl-α ' '-acetic acid)-trithiocarbonate (CMP).
5. a method of preparing the cationic electric field-sensitive glycosyl of the dumbbell structure intelligent aqueous gel capable described in claims 1-4, is characterized in that preparation process is as follows:
A: glucose monomer is protected through OH, with the standby polymerizable Monomer containing sugar moiety that contains two keys of unsaturated acyl stew in soy sauce;
B: trithiocarbonate (CMP) chain-transfer agent and the prepared polymerizable Monomer containing sugar moiety of previous step are joined in a certain amount of tetrahydrofuran (THF), under protection of inert gas, add initiator Diisopropyl azodicarboxylate, at 70 ℃, carry out the polymerization of Monomer containing sugar moiety, after Monomer containing sugar moiety polymerization completes, add cation electrodeposition field sensitive monomer DMAEMA copolymerization, add again subsequently Monomer containing sugar moiety polymerization to obtain dumbbell structure glycosyl polymkeric substance;
C: by the dumbbell structure glycosyl polymkeric substance of preparation, the free OH of hydrolysis, obtains the cationic electric field-sensitive glycosyl of target product dumbbell structure intelligent aqueous gel capable in diluted acid.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942661A (en) * | 2012-11-26 | 2013-02-27 | 南通大学 | Intelligent thermo-sensitive glycosyl hydrogel with dumbbell structure and preparation method of hydrogel |
| CN102964547A (en) * | 2012-12-05 | 2013-03-13 | 南通大学 | PH response glycosyl intelligent hydrogel with segmented structure and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942661A (en) * | 2012-11-26 | 2013-02-27 | 南通大学 | Intelligent thermo-sensitive glycosyl hydrogel with dumbbell structure and preparation method of hydrogel |
| CN102964547A (en) * | 2012-12-05 | 2013-03-13 | 南通大学 | PH response glycosyl intelligent hydrogel with segmented structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 娄少峰: "葡萄糖基N-异丙基丙烯酰胺共聚物的合成及其温敏性", 《应用化学》 * |
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