CN104193926A - Block structure temperature/pH-sensitive glycosyl intelligent aquagel and preparation method thereof - Google Patents
Block structure temperature/pH-sensitive glycosyl intelligent aquagel and preparation method thereof Download PDFInfo
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- CN104193926A CN104193926A CN201410407843.3A CN201410407843A CN104193926A CN 104193926 A CN104193926 A CN 104193926A CN 201410407843 A CN201410407843 A CN 201410407843A CN 104193926 A CN104193926 A CN 104193926A
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Abstract
The invention discloses a block structure temperature/pH-sensitive glycosyl intelligent aquagel and a preparation method thereof. The intelligent aquagel is a glycosyl monomer/temperature-sensitive monomer/pH-sensitive monomer triblock structure. The preparation method comprises the following steps: by using glucose as the raw material, carrying out esterification reaction with unsaturated acyl halide to prepare the glycosyl monomer; and by using alpha,alpha,alpha',alpha'-tetramethyl-alpha,alpha'-dicarboxyl-trithiocarbonate as a chain-transfer agent, carrying out reversible addition fragmentation chain transfer free-radical polymerization on the glycosyl monomer, temperature-sensitive monomer and pH-sensitive monomer to prepare the block structure temperature/pH-sensitive glycosyl intelligent aquagel. The temperature/pH-sensitive glycosyl intelligent aquagel has favorable temperature and pH response behavior, and the molecular framework is a controllable block structure. The used raw material is a saccharide compound, thereby enhancing the biocompatibility.
Description
Technical field
The present invention relates to relate to the preparation of intelligent aqueous gel capable, be specifically related to a kind of block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable and preparation method thereof.
Background technology
Hydrogel refers in the aqueous solution and is interacted and kept swelling and undissolved three-dimensional macromolecule network structural polymer by hydrogen bond, molecular force or Van der Waals force etc., it is extremely some equilibrium states of swellable in the aqueous solution, its volume does not change over time, still can keep its shape.According to being divided into traditional hydrogel and environmental sensitive hydrogels to the response water gel of environment, the latter can produce response to environmental stimulus (as temperature, pH, optical, electrical, magnetic, sound, power and chemical substance), is called again intelligent aqueous gel capable.Due to unique responsiveness of progress in Intelligent Hydrogel, have a good application prospect at aspects such as material with memory, chemical valve, light control material, medicine control release, biosensor, tissue culture.
In biological correlated process, be often accompanied by the variation of environment or self pH, this point makes pH sensitive aquagel become one of emphasis of intelligent aqueous gel capable research field.With the variation of pH value, pH sensitive aquagel has swelling or to go swelling response characteristic, this type of hydrogel be all generally to form macromolecular network by crosslinked, contains a large amount of facile hydrolysiss or protonated acid, base groups, as carboxyl and amino in network.Dissociating of these groups is subject to the impact of extraneous pH: in the time that extraneous pH changes, the corresponding change of dissociation degree of these groups, causes inside and outside ionic concn to change; And cause and generation or the fracture of hydrogen bond in network cause the discontinuous volume phase transformation of gel.
Temperature-sensitive hydrogel refers to the hydrogel that volume is undergone mutation along with the change of outside temperature.Research at present the most widely temperature sensitive monomer is NIPA, its polyalcohol hydrogel lower critical solution temperature is 32 DEG C, relatively approach body temperature, and can be by regulating and controlling with other monomer copolymerizations, there is good temperature sensitive performance, make its in a lot of fields especially biological medicine engineering field be widely used.But the biocompatibility of NIPA class hydrogel own and degradability are poor, its application aspect biological medicine is restricted, the biocompatibility and the degradability that therefore improve this type of hydrogel become the problem that needs solve.
Along with the further investigation of intelligent aqueous gel capable, the progress of preparation means and synthetic technology, for improving biocompatibility and the intelligent response behavior of hydrogel, by the synthetic macromolecule hydrogel with different functional groups, the important development direction that research and development has dual or multiple response, has good biocompatibility, eco-friendly intelligent aqueous gel capable has become this field.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 double-response intelligent aqueous gel capable of introducing glycosyl has broad application prospects, and will greatly widen the range of application of intelligent aqueous gel capable.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming that overcomes prior art, with not enough, provides the block structure temperature-and pH-sensitivity glycosyl that a kind of biocompatibility is good, structure is controlled intelligent aqueous gel capable.
Another object of the present invention is to provide the preparation method of above-mentioned block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable.
Object of the present invention is achieved through the following technical solutions:
A kind of block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable is block structure in overall molecule structure, is three block structures of Monomer containing sugar moiety, temperature sensitive monomer and pH sensitive monomer.
Described temperature sensitive monomer is NIPA, and described pH sensitive monomer is acrylic or methacrylic acid.
A preparation method for block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable, comprises the steps: taking glucose as raw material, prepares Monomer containing sugar moiety through carrying out esterification with unsaturated carboxylic acid halides; By Monomer containing sugar moiety and temperature sensitive monomer and pH sensitive monomer, prepare block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable by reversible addition-fragmentation chain transfer free radical polymerization (RAFT).
Described unsaturated carboxylic acid halides is preferably acrylate chloride or propylene acylbromide.
The RAFT agent adopting is preferably α, α, α ', α '-tetramethyl--α, α '-dicarboxyl-trithiocarbonate (CMP), this RAFT agent preferably prepares by the method that comprises following steps: dithiocarbonic anhydride, trichloromethane, acetone, tetrabutylammonium iodide and normal hexane are joined in reaction vessel; Under protection of inert gas protection, react to dripping sodium hydroxide solution in reaction vessel; The solid that adds water dissolution to generate after reaction finishes, then drip hcl acidifying water layer, after unreacting material volatilization, the solid in washed reaction solution obtains α, α, α ', α '-tetramethyl--α, α '-dicarboxyl-trithiocarbonate.In the method, to keep temperature lower than 25 DEG C.
Preferably, the preparation method of described block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable, comprises the steps:
(1) 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.
(2) by RAFT agent α; α; α '; α '-tetramethyl--α; α '-dicarboxyl-trithiocarbonate (CMP), tert-butyl acrylate and initiator join in solvent, and under protection of inert gas, reaction obtains the large RAFT reagent of polyacrylic acid tert-butyl ester PtBA-CMP.
(3) PtBA-CMP preparing taking step (2) is macromolecular chain transfer agent, carries out RAFT react and obtain PtBA-PNIPAM under protection of inert gas with temperature sensitive monomer NIPA.
(4) the polymerizable Monomer containing sugar moiety that the PtBA-PNIPAM preparing by step (3) is prepared with step (1) is proceeded RAFT and is reacted and obtain block structure glycosyl polymkeric substance under protection of inert gas.
(5) the block structure glycosyl polymkeric substance of being prepared by step (4) is hydrolyzed free-OH in trifluoroacetic acid, thereby obtains target product block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable.
Initiator described in step (2) is preferably Diisopropyl azodicarboxylate, and described solvent is preferably dioxan; Temperature of reaction is preferably 65-80 DEG C.
Initiator in RAFT reaction in step (3), (4) is preferably Diisopropyl azodicarboxylate, and solvent is preferably dioxan; Temperature of reaction is preferably 65-80 DEG C.
The present invention compared with prior art has the following advantages: (1) temperature-and pH-sensitivity glycosyl of the present invention intelligent aqueous gel capable molecular skeleton is block structure, and its structure can regulate and control; (2) raw material used in the present invention is saccharide compound, has improved biocompatibility; (3) glycosyl intelligent aqueous gel capable of the present invention has good temperature and pH respondent behavior.
Brief description of the drawings
Fig. 1 is the schematic diagram of block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable of the present invention.
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.
A kind of schematic diagram of block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable as shown in Figure 1, is three block structures of Monomer containing sugar moiety, temperature sensitive monomer and pH sensitive monomer.Wherein temperature sensitive monomer is NIPA, and pH sensitive monomer is acrylic or methacrylic acid.Taking glucose as raw material, prepare Monomer containing sugar moiety through carrying out esterification with unsaturated carboxylic acid halides; By Monomer containing sugar moiety and temperature sensitive monomer and pH sensitive monomer, prepare block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable by reversible addition-fragmentation chain transfer free radical polymerization (RAFT).
Embodiment 1
(1) diacetoneglucose acrylate is synthetic: take the thick product 3g of NaH (60%, about 0.075mol) and put into the there-necked flask of 250mL, by 30mL petroleum ether 3 times, to remove mineral oil.Add dry sherwood oil 80mL and diacetoneglucose 13g (0.05mol), N
2under protection atmosphere at 65 DEG C stir about 4 hours.Reaction mixture is cooled to-10 DEG C, taking acrylate chloride 6.79g (0.075mol) is dissolved in the dry sherwood oil of 30mL, slowly be added drop-wise in reaction system by constant pressure funnel, after dropping finishes, system is warming up to 65 DEG C and continues reaction certain hour, confirm that by TCL reaction finishes, and is down to room temperature by system.Remove by filter insolubles, filtrate is used 5%NaOH solution washing twice, and then with distillation washing, finally uses anhydrous Na SO
4dried overnight.Cross and filter out solid, filtrate is put into refrigerator freezing crystallization, isolate solid vacuum-drying, obtain diacetoneglucose acrylate, yield is 75.2%.
(2) α, α, α ', α '-tetramethyl--α, synthesizing of α '-dicarboxyl-trithiocarbonate (CMP): by dithiocarbonic anhydride (0.1mol, 7.613g), trichloromethane (0.25mol, 29.85g), acetone (0.25mol, 14.52g), tetrabutylammonium iodide (0.002mol, 0.74g) and normal hexane (50mL) join in the there-necked flask of 500mL, in there-necked flask, plug respectively constant pressure funnel, thermometer, spherical condensation tube (with threeway), simultaneously by 50% sodium hydroxide (0.7mol, 56g) solution is added in constant pressure funnel.Cooling with ice-water bath, keep temperature lower than 25 DEG C.By threeway, balloon (interior inflated with nitrogen), bleed with water circulating pump, 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 DEG C.After having reacted, add distilled water (300mL) to dissolve the solid generating, then add concentrated hydrochloric acid (36%, 35mL) to constant pressure funnel, open piston, drip concentrated hydrochloric acid, acidifying water layer, notes controlling temperature lower than 25 DEG C.After dripping, then stir 30min, 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 α, α, α ', α '-tetramethyl--α, α '-dicarboxyl-trithiocarbonate (CMP) 16.81g, thick productive rate is 89.3%.Thick CMP is carried out to recrystallization with 60% isopropanol water solution.
(3) in the there-necked flask of 50mL, the CMP0.11g, the initiator Diisopropyl azodicarboxylate AIBN6.6mg that add tert-butyl acrylate 5.1g, (2) to prepare, then add dioxan 10mL, under nitrogen protection, in 70 DEG C of oil baths, reaction 4h, adopts TLC to detect monomer polymerization complete; Products therefrom precipitates with methanol aqueous solution, and vacuum-drying obtains macromolecular chain transfer agent PtBA-CMP solid 3.9g.
(4) in the there-necked flask of 50mL, PtBA-CMP3.5g, the NIPA 7g, the Diisopropyl azodicarboxylate AIBN5.1mg that add (3) to prepare, add 12mL dioxan to dissolve, under nitrogen protection, in 65 DEG C of oil baths, react 6h, adopt TLC to detect monomer polymerization complete; Reaction system is cooled to after room temperature by methanol aqueous solution precipitation, and vacuum-drying obtains solid PtBA-PNIPAM7.9g.
(5) in the there-necked flask of 50mL, the PtBA-PNIPAM2.5g, diacetoneglucose acrylate 5.0g, the Diisopropyl azodicarboxylate 1.3mg prepared by (1) that add (4) to prepare, dissolve with 12mL dioxan, under nitrogen protection, in 65 DEG C of oil baths, reaction 12h, adopts TLC to detect Monomer containing sugar moiety polymerization complete; Be cooled to after room temperature by methanol aqueous solution precipitation, vacuum-drying, obtains block structure glycosyl polymkeric substance 5.6g.
(6) in the there-necked flask of 50mL, by gained block structure glycosyl polymkeric substance 1g, be dissolved in methylene dichloride, add a certain amount of trifluoroacetic acid, under room temperature, stir 24h, rotary evaporation is removed methylene dichloride and trifluoroacetic acid, dry, obtains target product block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable 0.75g.
Embodiment 2
(1) diacetoneglucose acrylate is synthetic: with embodiment 1 (1).
(2) α, α, α ', α '-tetramethyl--α, α '-dicarboxyl-trithiocarbonate (CMP) synthetic: with embodiment 1 (2).
(3) in the there-necked flask of 50mL, the CMP0.2256g, the initiator Diisopropyl azodicarboxylate AIBN0.01312g that add tert-butyl acrylate 10.24g, (2) to prepare, then add dioxan 11mL, under nitrogen protection, in 78 DEG C of oil baths, reaction 2.5h, adopts TLC to detect monomer polymerization complete; Products therefrom precipitates with methanol aqueous solution, and vacuum-drying obtains macromolecular chain transfer agent PtBA-CMP solid 8.1g.
(4) in the there-necked flask of 50mL, PtBA-CMP7g, the NIPA 14g, the Diisopropyl azodicarboxylate AIBN0.0130g that add (3) to prepare, add 22mL dioxan to dissolve, under nitrogen protection, in 78 DEG C of oil baths, react 10h, adopt TLC to detect monomer polymerization complete; Reaction system is cooled to after room temperature by methanol aqueous solution precipitation, and vacuum-drying obtains solid PtBA-PNIPAM19g.
(5) in the there-necked flask of 50mL, the PtBA-PNIPAM5g, diacetoneglucose acrylate 10g, the Diisopropyl azodicarboxylate 0.0026g prepared by (1) that add (4) to prepare, dissolve with 25mL dioxan, under nitrogen protection, in 78 DEG C of oil baths, reaction 15.5h, adopts TLC to detect Monomer containing sugar moiety polymerization complete; Be cooled to after room temperature by methanol aqueous solution precipitation, vacuum-drying, obtains block structure glycosyl polymkeric substance 10.2g.
(6) in the there-necked flask of 50mL, by gained block structure glycosyl polymkeric substance 1.5g, be dissolved in methylene dichloride, add a certain amount of trifluoroacetic acid, under room temperature, stir 24h, rotary evaporation is removed methylene dichloride and trifluoroacetic acid, dry, obtains target product block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable 1.1g.
Claims (10)
1. a block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable, is characterized in that: be three block structures of Monomer containing sugar moiety, temperature sensitive monomer and pH sensitive monomer.
2. block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable according to claim 1, is characterized in that: described temperature sensitive monomer is NIPA.
3. block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable according to claim 1, is characterized in that: described pH sensitive monomer is acrylic or methacrylic acid.
4. the preparation method of the block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable described in claim 1-3 any one, is characterized in that comprising the steps: taking glucose as raw material, prepares Monomer containing sugar moiety through carrying out esterification with unsaturated carboxylic acid halides; By Monomer containing sugar moiety and temperature sensitive monomer and pH sensitive monomer, prepare block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable by reversible addition-fragmentation chain transfer free radical polymerization.
5. the preparation method of block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable according to claim 4, is characterized in that: described unsaturated carboxylic acid halides is acrylate chloride or propylene acylbromide.
6. the preparation method of block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable according to claim 4, it is characterized in that: the RAFT agent adopting is α, α, α ', α '-tetramethyl--α, α '-dicarboxyl-trithiocarbonate, it prepares by the method that comprises following steps: dithiocarbonic anhydride, trichloromethane, acetone, tetrabutylammonium iodide and normal hexane are joined in reaction vessel; Under protection of inert gas protection, react to dripping sodium hydroxide solution in reaction vessel; The solid that adds water dissolution to generate after reaction finishes, then drip hcl acidifying water layer, after unreacting material volatilization, the solid in washed reaction solution obtains α, α, α ', α '-tetramethyl--α, α '-dicarboxyl-trithiocarbonate.
7. the preparation method of block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable according to claim 6, it is characterized in that: α, α, α ', α '-tetramethyl--α, will keep temperature lower than 25 DEG C in the preparation of α '-dicarboxyl-trithiocarbonate.
8. the preparation method of block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable according to claim 4, is characterized in that comprising the steps:
(1) 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;
(2) by RAFT agent α, α, α ', α '-tetramethyl--α, α '-dicarboxyl-trithiocarbonate, tert-butyl acrylate and initiator join in solvent, and under protection of inert gas, reaction obtains the large RAFT reagent of polyacrylic acid tert-butyl ester PtBA-CMP;
(3) PtBA-CMP preparing taking step (2) is macromolecular chain transfer agent, carries out RAFT react and obtain PtBA-PNIPAM under protection of inert gas with temperature sensitive monomer NIPA;
(4) the polymerizable Monomer containing sugar moiety that the PtBA-PNIPAM preparing by step (3) is prepared with step (1) is proceeded RAFT and is reacted and obtain block structure glycosyl polymkeric substance under protection of inert gas;
(5) the block structure glycosyl polymkeric substance of being prepared by step (4) is hydrolyzed free-OH in trifluoroacetic acid, thereby obtains target product block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable.
9. the preparation method of block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable according to claim 8, is characterized in that: the initiator described in step (2) is Diisopropyl azodicarboxylate, described solvent is dioxan; Temperature of reaction is 65-80 DEG C.
10. the preparation method of block structure temperature-and pH-sensitivity glycosyl intelligent aqueous gel capable according to claim 8, it is characterized in that: the initiator in the RAFT reaction in step (3), (4) is Diisopropyl azodicarboxylate, and solvent is dioxan; Temperature of reaction is 65-80 DEG C.
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| CN110003486A (en) * | 2019-03-25 | 2019-07-12 | 江苏大学 | The gold nanoparticle and preparation method and purposes of Thermo-sensitive sugar-containing polymer modification |
| CN113117140A (en) * | 2021-04-07 | 2021-07-16 | 西安理工大学 | Preparation method of double-stimulus synergistic response porous hydrogel modified acrylic acid bone cement |
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Application publication date: 20141210 |