CN104829780A - Preparation method for high-strength hydrogel with rapid response to both pH value and temperature - Google Patents
Preparation method for high-strength hydrogel with rapid response to both pH value and temperature Download PDFInfo
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- CN104829780A CN104829780A CN201410044415.9A CN201410044415A CN104829780A CN 104829780 A CN104829780 A CN 104829780A CN 201410044415 A CN201410044415 A CN 201410044415A CN 104829780 A CN104829780 A CN 104829780A
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Abstract
The invention relates to a preparation method for a high-strength dual-network hydrogel capable of rapidly responding to both a pH value and temperature. The preparation method comprises the following steps: (1) dissolving temperature-sensitive monomer, pH-sensitive monomer and inorganic cross-linking agent modified nanometer clay in water together, placing the obtained solution in a container, carrying out stirring in an ice bath with a temperature of 0 DEG for 60 min under the protection of nitrogen until the solution is uniform and transparent, then adding an aqueous solution of a silica network precursor and continuing stirring for 30 min until the obtained mixture is uniform and transparent; (2) adding an aqueous solution of a redox initiator and a catalyst, carrying out uniform mixing under stirring, introducing nitrogen for 5 min and pouring the obtained mixture in a die with a certain shape; (3) subjecting the die to a reaction at 20 DEG C for 30 min and then to a reaction at -28 DEG C for 24 h; and (4) taking the product out and carrying out repeated water changing and soaking so as to obtain the finished hydrogel. The hydrogel prepared in the invention has obvious dual response to temperature and the pH value, excellence strength and an ultra-fast response rate; moreover, raw materials used in the invention are cheap; the preparation method is simple; and the hydrogel is expected to be used in fields like drug sustained release and dye absorption.
Description
Technical field
The invention belongs to the preparation method of hydrogel, particularly relate to and a kind ofly can produce fast response for residing envrionment temperature and pH value change and then produce volume transformation, there is the preparation method of the double-network hydrogel of excellent mechanical performance.
Background technology
High-molecular gel refers to the macromolecular compound of three-dimensional net structure and the system of solvent composition, polymer wherein with Van der Waals force, chemical bond force, physical entanglement power, the connections such as hydrogen bond force.Because it is a kind of three-dimensional network three-dimensional arrangement, therefore it by dissolution with solvents, can not disperse in a solvent simultaneously and can keep certain shape.Although solvent can not by the macromolecule dissolution of tridimensional network, in macromolecular compound, solvophilic radical moiety can be made polymer swelling by solvent action, and this is also the reason forming high-molecular gel.
Response polymer gel is its structure, physical properties, chemical property can change and the high-molecular gel of change with external environment.When this gel is subject to environmental stimulus, its structure and characteristics (mainly volume) can respond thereupon, as when the composition of solvent, pH value, ionic strength, temperature, the stimulus signal such as light intensity and electromagnetic field change, or when being subject to the stimulation of special chemical substance, the volume of gel can be undergone mutation, and presents Volume-phase transition behavior.Namely when gel is subject to external stimulus, segment in gel network has larger conformational change, present swelling phase or contraction phase, therefore there is corresponding deformation in gel systems: disappear once external stimulus, gel systems has the trend automatically restoring to interior steady state that can be lower.
In response type gel, the most typical be also most widely used for temperature sensitive with pH sensitive gel, especially use extensively in the field such as medicament slow release, monitoring device.The gel that temperature and pH value double-bang firecracker answer can be realized simultaneously then there is larger magnetism and application potential.But meanwhile, traditional chemically crosslinked, gel prepared by radiation crosslinking is all highly brittle, and small mechanical force also can cause the fragmentation of gel thus cause the great restriction of gel application.
In current research; the gel method that preparation has excellent mechanical performance mainly contains three kinds; be respectively dual network gel; topology gel and nano-composite gel; the nano-composite gel wherein invented with Haraguchi again because of the over-all properties of its excellence and simple preparation technology be better selection; (Macromolecules, 2002, the 35:10162 such as Haraguchi; Macromolecules2003,36,5732) adopt amphiphilic macromole such as NIPA, DMAA to be monomer, with inorganic nano clay for linking agent, prepare and there is excellent mechanical properties, the Nanometer composite hydrogel of swelling behavior and responsiveness.And adopt nanoclay as linking agent, preparing double-bang firecracker, to answer the method for gel mostly to be in gel synthesis be monomer with NIPA, add the mode of a small amount of ionic comonomer, methacrylic acid N, N-dimethylaminoethyl (DMAEMA) is a kind of typical cationic monomer.DMAEMA is Soluble acrylate's analog derivative monomer with polymerizability, is also a kind of broad-spectrum multifunctional monomer.In the structure of DMAEMA, not only containing tertiary amine groups but also containing polymerisable double bond, again due to the p of amine groups
ka is 7.5, can be protonated in acidic medium, and thus its homopolymer or multipolymer present cationic when low ph value; In its molecular structure, also there is hydrophilic radical [(CH3) 2-N-CH2CH2-] and hydrophobic grouping [CH2=C (CH3)-CO-O-] simultaneously, and two class groups match each other on space structure, formation and the destruction of hydrogen bond can be caused when the environment changes, thus cause the change of polymer phase.It has the characteristic of alkene, amine, ester compound simultaneously, can be polymerized under certain condition, addition, the chemical reaction such as quaternized and hydrolysis.Due to the characteristic that these are good, DMAEMA is used as the green intermediate of numerous fine chemicals such as sewage treatment flocculating agent, paper static inhibitor, retention aid, dye dispersant, tamanori, lubricating oil additive, ion exchange resin, medical slow release agent at present in a large number.
Although nano-composite gel is provided with multiple performance advantage, its responsiveness still has the space of improving further.Respond gel fast for preparing, existing multiple method is studied.Add different organic and inorganic perforating agents, in synthesis, adopt mixed solvent as template, freezing polymerization method, synthesis postlyophilization method, prepare graftomer method etc.And freezing polymerization thing method beyond doubt a kind of technique simply, easily realize, and do not add other materials to reduce the method affected reaction itself.As namely Xu etc. is caused by two-stage polymerization method under normal temperature 20 ° of C, after under-28 ° of C, be polymerized the method for 24 hours prepared the organic crosslinked PNIPA gel with supper-fast responsiveness, this gel can from dehydration 95% in lower 1 minute of equilibrium swelling state, and is again swelling to 70% original equilibrium swelling quality and also only needs 30 minutes.（Eur. Polym. J. 2004，40，467）。But this method is due to the freezing drilling effect on gel thus cause the decline that will cause gel mechanical property on the impact of gel network structure, thus the mechanical property of gel and the speed of response is caused to take into account.
In patent of the present invention, with NIPA and DMAMEA be temperature sensitive and pH responds monomer, by freezing polymerization legal system for supper-fast response nano plural gel, add the presoma of the second-Si-O-network in the course of the polymerization process simultaneously, synchronous polycondensation generates rigidity second network to ensure gel mechanical property in gel, thus achieve there is supper-fast responsiveness, temperature sensitive, the hydrogel preparation that pH is responsive of high strength.
Summary of the invention
The object of this invention is to provide a kind of preparation method with the hydrogel of high strength that can respond fast temperature, pH value change.The method has cheaper starting materials and is easy to get, and technique is simple, and easy handling, the feature that controllability is strong, the gel of preparation has fast temperature and pH value double responsiveness, good mechanical property, close to the LCST of human body temperature, this hydrogel is with a wide range of applications.
A kind of high strength pH of the present invention, temperature be two response water gel fast, and preparation process is:
(1) by temperature sensitive monomer; pH sensitive monomer; inorganic crosslinking agent modified Nano clay is altogether soluble in water and be placed in container, stirs 60 minutes to homogeneous transparent under nitrogen protection in 0 ° of C ice bath, after add certain mass silica network precursor water solution and continue stirring 30 minutes to homogeneous transparent solution.In solution, the mass percent concentration of temperature sensitive monomer in water is the mass percent concentration of 5%-7.5%, pH sensitive monomer in water is 1%-3%, and the quality of inorganic crosslinking agent is the 15-45% of monomer, and the mass ratio of silica network presoma and monomer is 40-100%;
(2) in (1) solution, add the initiator and aqueous catalyst solution with oxidation-reduction quality, stir and lead to nitrogen and pour in definite shape mould after 5 minutes.Wherein the volume of water is 5% of volume of water in (1) solution, wherein initiator, catalyzer and temperature sensitive monomer, and the total mass ratio of pH sensitive monomer is 1:0.75:100;
(3), after (2) solution being reacted 30 minutes under 20 ° of C, react 24 hours under being transferred to-28 ° of C;
(4) repeatedly change water soaking after being taken out by product and obtain final gel.
PH sensitive monomer of the present invention is dimethylaminoethyl methacrylate (DMAEMA), and its molecular structure is as follows,
Tertiary amine groups wherein can produce hydrogen bond with water at low temperatures, and make molecular chain in extended position in water, and under high temperature, hydrogen bond destroys, and makes molecular chain in contraction schedule in water, this hydrogel prepared by DMAEMA presents temperature-responsive.Simultaneously, as DMAEMA (pH < 7) in sour environment, protonated formation ion is become hydrophilic by tertiary amine groups, and under alkaline condition, (pH < 7) is this protonated suppressed, thus causes the pH responsiveness of this kind of gel.And there is the macromole of kinds of properties, as ethylacrylic acid dimethylaminoethyl, dimethylaminoethyl propyl ester etc. is all suitable for and the preparation method described by this patent.
Temperature sensitive monomer of the present invention is NIPA (NIPA), NIPA is typical temperature sensitive monomer, and its lowermost turn temperature (LCST) is about 32 ° of C.When lower than LCST temperature, its amido and water form hydrogen bond, and macromole wetting ability strengthens, thus makes molecular chain be extended position, and gel absorbs water, and when higher than LCST temperature, hydrogen bond destroys, and macromole wetting ability reduces, and molecular chain shrinks, and gel is hydrophobic.After adding the DMAEMA as comonomer, because DMAEMA itself has higher LCST, therefore will the LCST of gel entirety be raised.Time between the 1/4-1/3 that add-on is NIPA, LCST will close to human body temperature (37 ° of C-39 ° of C).
Initiator of the present invention and catalyzer are respectively KPS and TEMED, belong to water soluble, redox catalyst system.
The present invention's inorganic crosslinking agent modified Nano clay used is nanometer lithium algae soil and the blend of trisodium phosphate.Wherein, the thickness of nanometer lithium algae soil is 1-2nm, and diameter is 20-30nm, and chemical structure of general formula is [Mg
5.34li
0.66si
8o
20-(OH)
4] Na
0.66, the chemical general formula of trisodium phosphate is Na
4p
2o
7, massfraction is 7.68% of nanometer lithium algae soil.
The silica network presoma added in polymerization pre-polymerization liquid of the present invention is that tetramethoxy-silicane (TMOS), TMOS all hydrolysis reaction and polycondensation can occur under acid, alkaline condition.As in acid condition, the methoxyl group of TMOS has nucleophilicity, can attack H
3o
+ion causes hydroxyl to replace then, the carrying out of facilitation of hydrolysis-polycondensation; Then OH in the basic conditions
-siliciumatom on attack TMOS, due to-OCH
3-nucleophilicity more weak, hydroxyl methoxyl group displacement.In body series, TMOS realizes weakly alkaline catalyzed polycondensation in system, produces sol-gel change to form the second-Si-O-network that independence and clay are cross-linked PNIPA network.
The present invention adopts first polyase 13 0 minute under normal temperature 20 ° of C, after under-28 ° of C, be polymerized the method for 24 hours, under normal temperature polymerization be sol-gel change in order to ensure TMOS to form gel network, and ensure the initiation of PNIPA first network.Post polymerization under-28 ° of C is to produce ice crystal in the course of the polymerization process to form microporous network structure, thus provides channel for the turnover of water, and the water suction that improve gel with separate swelling rate.
Why the present invention has excellent mechanical strength and the supper-fast speed of response is simultaneously because there is the rigidity silicon-oxygen network formed with TMOS polycondensation and the second network formed by clay cross-linked polymer in gel, the existence of first network ensure that the microvoid structure that the mechanical property of gel, freezing polymerization make second network have to run through thus imparts the ultrafast speed of response of gel.
The each performance of gel of the present invention, comprises mechanical property, swelling property, separates swelling rate, and LCST etc. are all by regulating monomer concentration, and in linking agent nanoclay consumption, TMOS consumption and comonomer, the ratio of two monomers regulates.
High strength pH of the present invention, temperature fast two response water gel have following performance characteristics:
High strength pH of the present invention, temperature fast two response water gel have excellent mechanical property, and overall loading scope is 4.2-12.5N, and elongation at break ranges is 642%-982%.
High strength pH of the present invention, temperature fast two response water gel have adjustable LCST, and in described monomer ratio, the scope of LCST is 34.8-38.6 ° of C.
High strength pH of the present invention, temperature fast two response water gel have larger swelling ratio and obvious volume transformation pH, temperature response, test and assess for equilibrium state is swelling with regard to soaking two days in solvent, under 20 ° of C environment, within the scope of this patent synthetic ratio, the prepared swelling ratio of hydrogel in pure water is (with wet glue/dry glue quality than representing, lower same) be 23.4-42.7, being that in the acidic buffer of 3, swelling ratio scope is 34.4-52.4 in pH value, is that in the damping fluid of 8.7, swelling ratio is 18.1-29.6 in pH value.In 60 ° of C environment, gel swelling ratio in pure water is 5.4-10.7, is that in the acidic buffer of 3, swelling ratio scope is 10.4-21.3 in pH value, is that in the damping fluid of 8.7, swelling ratio is 4.1-6.9 in pH value.
The quick two response water gel of the high strength pH of the present invention, temperature has supper-fast solution swelling property (before measuring instant quality with hydrogel and survey, the ratio of quality represents), under in pure water, 20 ° of C reach equilibrium swelling, raised temperature is between 10s-34s as 60 ° of C, dehydration 90wt% required time.
Embodiment
Below in conjunction with the embodiment of specific embodiment form, foregoing of the present invention is further elaborated again, but should not be construed as following each embodiment is restriction to scope involved by the above-mentioned theme of the present invention, and all technology realized based on foregoing of the present invention all belong to the scope of the invention.
Embodiment 1
The quick two response water gel of the high strength pH of the present invention, temperature is prepared as follows:
(1) pre-solution is configured: by 4gNIPA, 1.6gDMAEMA, 1.16g modified clay to be dissolved in 50ml water and to be placed in container, in 0 ° of C ice bath, 60 minutes are stirred to even, transparent under nitrogen protection, after add the 20ml aqueous solution being dissolved with 3.0gTMOS, continue stirring 30 minutes to homogeneous transparent solution;
(2) in (1) solution, add 3.5ml and be dissolved with initiator KPS, the aqueous solution of catalyzer TEMED, wherein, the quality of KPS is 0.056g, and the quality of catalyzer TEMED is 0.042g.Stir and lead to nitrogen and pour into after 5 minutes in definite shape mould;
(3), after (2) solution being reacted 30 minutes under 20 ° of C, react 24 hours under being transferred to-28 ° of C;
(4) repeatedly change water soaking after being taken out by product and obtain final gel.
The performance of this gel is as follows:
The stretching overall loading of this hydrogel is 5.94 N, elongation at break is 822.3%, LCST in pure water is 36.1 ° of C, dry glue soaks measures swelling ratio in two days, under 20 ° of C, the swelling ratio of gel in pure water is 27.5, is that the swelling ratio in the acidic buffer of 3 is 41.8 in pH value, is that the swelling ratio in the ealkaline buffer of 8.7 is 24.6 in pH value.In 60 ° of C environment, the swelling ratio of gel in pure water is 6.2, is that in the acidic buffer of 3, swelling ratio is 11.4 in pH value, is that in the damping fluid of 8.7, swelling ratio is 5.3 in pH value.Under in pure water, 20 ° of C reach equilibrium swelling, raised temperature to 60 ° C, dehydration 90wt% are 14s.
Embodiment 2
The quick two response water gel of the high strength pH of the present invention, temperature is prepared as follows:
(1) pre-solution is configured: by 4gNIPA, 2gDMAEMA, 2.26g modified clay to be dissolved in 52ml water and to be placed in container, in 0 ° of C ice bath, 60 minutes are stirred to even, transparent under nitrogen protection, after add the 20ml aqueous solution being dissolved with 4.5gTMOS, continue stirring 30 minutes to homogeneous transparent solution;
(2) in (1) solution, add 3.6ml and be dissolved with initiator KPS, the aqueous solution of catalyzer TEMED, wherein, the quality of KPS is 0.06g, and the quality of catalyzer TEMED is 0.045g.Stir and lead to nitrogen and pour into after 5 minutes in definite shape mould;
(3), after (2) solution being reacted 30 minutes under 20 ° of C, react 24 hours under being transferred to-28 ° of C;
(4) repeatedly change water soaking after being taken out by product and obtain final gel.
The performance of this gel is as follows:
The stretching overall loading of this hydrogel is 9.94 N, elongation at break is 714.6%, LCST in pure water is 38.1 ° of C, dry glue soaks measures swelling ratio in two days, under 20 ° of C, the swelling ratio of gel in pure water is 26.5, is that the swelling ratio in the acidic buffer of 3 is 37.6 in pH value, is that the swelling ratio in the ealkaline buffer of 8.7 is 26.3 in pH value.In 60 ° of C environment, the swelling ratio of gel in pure water is 8.2, is that in the acidic buffer of 3, swelling ratio is 18.1 in pH value, is that in the damping fluid of 8.7, swelling ratio is 6.8 in pH value.Under in pure water, 20 ° of C reach equilibrium swelling, raised temperature to 60 ° C, dehydration 90wt% are 31s.
Claims (5)
1. high strength pH, a temperature two response water gel fast, its preparation process is:
(1) by temperature sensitive monomer, pH sensitive monomer, inorganic crosslinking agent modified Nano clay is total to soluble in water and is placed in container, in 0 ° of C ice bath, 60 minutes are stirred to homogeneous transparent under nitrogen protection, after add certain mass silica network precursor water solution and continue stirring 30 minutes to homogeneous transparent solution, in solution, the mass percent concentration of temperature sensitive monomer in water is 5%-7.5%, the mass percent concentration of pH sensitive monomer in water is 1%-3%, the quality of inorganic crosslinking agent modified Nano clay is the 15-45% of monomer, the mass ratio of silica network presoma and monomer is 40-100%,
(2) in (1) solution, add the initiator and aqueous catalyst solution with oxidation-reduction quality, stir and lead to nitrogen and pour into after 5 minutes in definite shape mould, wherein the volume of water is 5% of volume of water in (1) solution, wherein initiator, catalyzer and temperature sensitive monomer, the total mass ratio of pH sensitive monomer is 1:0.75:100;
(3), after mould in (2) being reacted 30 minutes under 20 ° of C, react 24 hours under being transferred to-28 ° of C;
(4) repeatedly change water soaking after being taken out by product and obtain final gel.
2. the preparation method of high strength pH according to claim 1, the quick two response water gel of temperature, it is characterized in that: inorganic crosslinking agent modified Nano clay used is the blend of nanometer lithium algae soil and trisodium phosphate, wherein, the thickness of nanometer lithium algae soil is 1-2nm, diameter is 20-30nm, and chemical structure of general formula is [Mg
5.34li
0.66si
8o
20-(OH)
4] Na
0.66, the chemical general formula of trisodium phosphate is Na
4p
2o
7, the massfraction added is 7.68% of nanometer lithium algae soil.
3. the preparation method of high strength pH according to claim 1, the quick two response water gel of temperature, it is characterized in that: described temperature sensitive monomer is NIPA (NIPA), pH sensitive monomer is dimethylaminoethyl methacrylate (DMAEMA).
4. the preparation method of high strength pH according to claim 1, the quick two response water gel of temperature, is characterized in that: described silica network presoma is tetramethoxy-silicane (TMOS).
5. the preparation method of high strength pH according to claim 1, the quick two response water gel of temperature, it is characterized in that: redox type initiators used comprises initiator ammonium persulfate (KPS), catalyzer is N, N, N', N'-Tetramethyl Ethylene Diamine (TEMED).
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| CN107056983A (en) * | 2017-06-06 | 2017-08-18 | 中国地质大学（北京） | Prepare orthogonal regulation and control mechanical performance and medicine-releasing performance double-network hydrogel method |
| CN107474263A (en) * | 2016-06-08 | 2017-12-15 | 中国科学院武汉物理与数学研究所 | The preparation method of temperature pH sensitivity block nano-hydrogels using polyion polysaccharide as macromolecules cross-linking agent |
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| CN107474263A (en) * | 2016-06-08 | 2017-12-15 | 中国科学院武汉物理与数学研究所 | The preparation method of temperature pH sensitivity block nano-hydrogels using polyion polysaccharide as macromolecules cross-linking agent |
| CN106810636A (en) * | 2016-12-29 | 2017-06-09 | 华中科技大学 | The nanogel and nanogel drug-loading system of tumor microenvironment intelligent response |
| CN106810636B (en) * | 2016-12-29 | 2019-11-15 | 华中科技大学 | The nanogel and nanogel drug-loading system of tumor microenvironment intelligent response |
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| CN107056983B (en) * | 2017-06-06 | 2019-08-23 | 中国地质大学（北京） | Prepare orthogonal regulation mechanical performance and medicine-releasing performance double-network hydrogel method |
| CN108341906A (en) * | 2018-03-12 | 2018-07-31 | 福州大学 | A kind of preparation method and application of dye of positive ion composite adsorbing material |
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| CN110507848A (en) * | 2019-09-25 | 2019-11-29 | 商丘师范学院 | Carry enzyme bacteria cellulose base composite antibiotic aerogel dressing and preparation method thereof |
| CN110507848B (en) * | 2019-09-25 | 2021-09-24 | 商丘师范学院 | Enzyme-loaded bacterial cellulose-based composite antibacterial hydrogel dressing and preparation method thereof |
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