CN105461939B - A kind of preparation method of the temperature-sensitive hydrogel with shear thickening behavior - Google Patents
A kind of preparation method of the temperature-sensitive hydrogel with shear thickening behavior Download PDFInfo
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- CN105461939B CN105461939B CN201510138787.2A CN201510138787A CN105461939B CN 105461939 B CN105461939 B CN 105461939B CN 201510138787 A CN201510138787 A CN 201510138787A CN 105461939 B CN105461939 B CN 105461939B
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Abstract
The present invention relates to one kind to have obvious shear thickening effect, and the preparation method for the temperature-sensitive hydrogel being controlled to this characteristic can be controlled by temperature change, and the hydrogel is with poly-（N N-isopropylacrylamides）Cross-linked network is matrix, and certain density Aqueous Solutions of Polyethylene Glycol is swollen in matrix, the poly- of certain mass fraction is disperseed in aqueous solution（N N-isopropylacrylamides）Engrafted nanometer SiO2Microballoon.The hydrogel has obvious shear thickening behavior, its shear thickening effect can be by temperature control, and gel also has obvious Thermo-sensitive in itself.
Description
Technical field
The invention belongs to the preparation method of intelligent aqueous gel, can produce shear thickening behavior more particularly to one kind, and can lead to
Cross the intelligent aqueous gel that shear thickening behavior is adjusted to the Thermo-sensitive of gel.
Background technology
High-molecular gel refers to the system of the high-molecular compound and solvent composition of three-dimensional net structure, macromolecule therein
Connected with Van der Waals force, chemical bond force, physical entanglement power, hydrogen bond force etc..Since it is a kind of three-dimensional network stereochemical structure,
It cannot be dissolved by the solvent, while disperse in a solvent and can keep certain shape.Although solvent cannot be by three-dimensional netted knot
The macromolecule dissolution of structure, but the group part of solvophilic can make macromolecule molten by solvent action in high-molecular compound
Swollen, this is also the reason for forming high-molecular gel.
Shear thickening refers to when the shear stress suffered by material（Strain）Occur when increase viscosity increase, material by
Soft " curing " behavior being hardened.Shear-thickening phenomenon is found in particle suspension system earliest, such as mud, starch dispersion liquid etc.,
System includes decentralized medium such as viscous liquid and dispersion such as micro-nano particle, present solid composite material and gel rubber material
In have found shear thickening phenomenon.In the past 20 years, shear thickening phenomenon is by extensive concern, existing a variety of dispersed particles and its
Decentralized medium collocation constitutes the suspension with shear thickening phenomenon, and typical particle includes inorganic particulate such as SiO2、CaCO3、
Fe2O3, glass fibre etc., organic filler such as starch, compound particle include polymethyl methacrylate（PMMA）Microballoon, polyphenyl second
Alkene（PS）Microballoon, polystyrene graft acrylic acid（PS-g-AA）Microballoon, poly dimethyl propionamide-acrylic acid（P（DMAA-AA))
Microballoon etc., decentralized medium include water, polyethylene glycol, glycerine, different chain length aliphatic hydrocarbon etc..When particulate reaches certain in suspension system
During volume fraction, shear thickening phenomenon occurs immediately.
And current shear thickening gel generally realizes sol gel to prepare by shear thickening behavior thickening,
Only the volume fraction of microballoon is influenced this shear thickening behavior in by suspension, and has no other voltage inputs.This can such as be sheared
Thickening characteristic is combined with responsive gel, and realization passes through control of the external source response to gel shear thickening behavior, undoubtedly will tool
There is huge application prospect.
The content of the invention
The purpose of the invention is to provide a kind of preparation method of the hydrogel of achievable shear thickening, it is provided in particular in
One kind can produce shear thickening behavior, and the preparation of the intelligent aqueous gel of shear thickening behavior can be adjusted by the Thermo-sensitive of gel
Method.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of preparation method of the temperature-sensitive hydrogel with shear thickening behavior, its preparation process are：
Certain density n-isopropyl acrylamide aqueous solution is configured, by a certain amount of engrafted nanometer SiO2Microballoon adds it
In, ultrasonic vibration causes engrafted nanometer SiO in 20 minutes in ice-water bath2Microballoon is dispersed wherein, and addition is dissolved with a small quantity
Initiator KPS, the aqueous solution of catalyst TEMED continue ultrasonic vibration 20 minutes in ice-water bath, and above procedure is protected in nitrogen
Shield is lower to be carried out.Afterwards by reaction vessel seal and be positioned in ice-water bath reaction 24 it is small when to form gel.Spent after taking out gel
Ionized water soaks repeatedly changes the unreacted monomer of water removal and solvent.After configure certain density PEG aqueous solutions, passed through note
In emitter injection gel, when the polyethylene glycol being swollen in gel reaches a certain concentration, product is obtained.
Above-mentioned preparation process is characterized in that：The quality of n-isopropyl acrylamide in n-isopropyl acrylamide aqueous solution
Concentration adds engrafted nanometer SiO between 10%-20%2The volume fraction of microballoon is n-isopropyl acrylamide aqueous liquid
Between long-pending 15%-28%, addition is dissolved with initiator KPS, and the volume of the aqueous solution of catalyst TEMED is N- isopropyl acrylamides
Between the 3-5% of amine aqueous solution, wherein the quality of dissolving KPS is the 0.25-0.75% of n-isopropyl acrylamide, the matter of TEMED
The 0.5-1% that fraction is n-isopropyl acrylamide is measured, the polyethylene glycol mass concentration reached in gel is between 15-32%.
Further, monomer used in gel synthesis is n-isopropyl acrylamide.Its structural formula is respectively：
NIPA is typical temperature sensitive monomer, its minimum transition temperature（LCST）About 32 °C.When less than LCST temperature, its
Amido and water form hydrogen bond, and the enhancing of macromolecular hydrophily, so that strand be in extended position, gel absorbs water, and higher than
During LCST temperature, hydrogen bond destroys, and macromolecular hydrophily reduces, and strand is shunk, and gel is hydrophobic.
Further, the engrafted nanometer SiO2The particle diameter of microballoon is between 20-100nm.
Further, the engrafted nanometer SiO2The grafted chain of microballoon is hydrophobic segment, including polymethyl methacrylate chain,
Polybutyl methacrylate chain.Chain molecular weight is between 0.8 ten thousand -1.5 ten thousand, and molecular weight distributing index is between 1.1-1.5.
Further, the engrafted nanometer SiO2The preparation method of microballoon can be used by commercialization Nano-meter SiO_22Microballoon table
It is prepared by the method for face graft polymerization macromolecular chain.Mainly by be connected to surface of inorganic particles initiator trigger monomer polymerization from
And form the divergent method of grafted chain.Its implementation can use the atom transfer radical polymerization of living polymerization（ATRP）Polymerization,
Reversible addion-fragmentation chain transfer polymerize（RAFT）NO free radical polymerization is triggered on polymerization, surface（SI-NMP）And surface light
Chain tra nsfer is triggered to terminate radical polymerization（SI-PIMP）, click chemistry etc..Typical method is by RAFT living polymerizations, such as
Using document（Macromolecules, 2011,44(22): 8944–8953）In method, drawn by the macromolecular of synthesis
Send out agent, polymerisation in solution synthesis grafting microballoon.The structural formula of macromolecular RAFT initiators is used in wherein synthesizing：
Further, the molecular weight of the polyethylene glycol is between 200-2000.
The temperature-responsive POSS hybridized hydrogel performances of acid degradation of the present invention have following performance characteristics：
Due in the presence of the PEG solution and suspended dispersed with certain viscosity in gel
The presence of microballoon/PEG suspension is grafted, there is significant shear thickening behavior, it is when being subject to different impacts
Certain resistant property will be produced.Gel occur shear thickening range of shear rate be（0.2-1.5s-1）, the maximum of gel glues
Degree scope is 200-500Pa.s..Influence of the temperature to gel shear thickening behavior is notable, and the shear thickening of gel starts plus cuts
Speed reduces, peak viscosity increase.Simultaneously as the presence of temperature sensitive monomer, gel swellability itself has significant temperature sensitive spy
Property.
Brief description of the drawings
Fig. 1 is relation schematic diagram of the hydrogel prepared in embodiment 1 at 20 degree between shear rate and viscosity.
Fig. 2 is the temperature of the hydrogel prepared in embodiment 1 with starting shear thickening shear rate relation schematic diagram.
Fig. 3 is relation schematic diagram between the temperature of the hydrogel prepared in embodiment 1 and peak viscosity.
Fig. 4 is the relation schematic diagram between the temperature of the hydrogel prepared in embodiment 1 and Equilibrium swelling ratio.
Embodiment
With reference to the embodiment of specific embodiment form, the above of the present invention is remake further in detail
Illustrate, but should not be construed as following each embodiments is the limitation to scope involved by the above-mentioned theme of the present invention, it is all based on the present invention
The technology that the above is realized belongs to the scope of the invention.
Embodiment 1
Configuration quality concentration is 15% n-isopropyl acrylamide aqueous solution 115g, and the grafting that cumulative volume is 20ml is received
Rice SiO2Microballoon is added thereto, and ultrasonic vibration causes engrafted nanometer SiO in 20 minutes in ice-water bath2Microballoon is dispersed wherein,
The aqueous solution that 4.5ml is dissolved with 0.075g initiators KPS, 0.14g catalyst TEMED is added, continues ultrasound shake in ice-water bath
Swing 20 minutes, above procedure carries out under nitrogen protection.Reaction vessel is sealed afterwards and to be positioned in ice-water bath reaction 24 small
When.Soaked with deionized water to change water and remove unreacted monomer repeatedly after taking-up and obtain gel products with solvent.Configuration concentration afterwards
For 42% PEG aqueous solutions, it is injected in gel by syringe, the polyglycol solution quality for obtaining swelling in gel is dense
Degree reaches 24%, obtains product.
Embodiment 2
Configuration quality concentration is 12% n-isopropyl acrylamide aqueous solution 96g, and the grafting that cumulative volume is 16.8ml is received
Rice SiO2Microballoon is added thereto, and ultrasonic vibration causes engrafted nanometer SiO in 20 minutes in ice-water bath2Microballoon is dispersed wherein,
The aqueous solution that 4ml is dissolved with 0.075g initiators KPS, 0.14g catalyst TEMED is added, continues ultrasonic vibration in ice-water bath
20 minutes, above procedure carried out under nitrogen protection.Afterwards by reaction vessel seal and be positioned in ice-water bath reaction 24 it is small when.
Soaked with deionized water to change water and remove unreacted monomer repeatedly after taking-up and obtain gel products with solvent.Configuration concentration is afterwards
35.7% PEG aqueous solutions, it are injected in gel by syringe, the polyglycol solution quality for obtaining swelling in gel is dense
Degree reaches 21.4%, obtains product.
Claims (4)
1. a kind of preparation method of the temperature-sensitive hydrogel with shear thickening behavior, its preparation process are：
Certain density n-isopropyl acrylamide aqueous solution is configured, by a certain amount of engrafted nanometer SiO2Microballoon is added thereto, Yu Bing
Ultrasonic vibration causes engrafted nanometer SiO in 20 minutes in water-bath2Microballoon is dispersed wherein, and addition is dissolved with initiator on a small quantity
KPS, the aqueous solution of catalyst TEMED continue ultrasonic vibration 20 minutes in ice-water bath, above procedure under nitrogen protection into
OK, after by reaction vessel seal and be positioned in ice-water bath reaction 24 it is small when to form gel；Deionized water is used after taking out gel
Immersion changes water and removes unreacted monomer and solvent repeatedly；After configure certain density PEG aqueous solutions, it is noted by syringe
Enter in gel, when the polyethylene glycol being swollen in gel reaches a certain concentration, obtain product；
Above-mentioned preparation process is further characterized in that：The quality of n-isopropyl acrylamide is dense in n-isopropyl acrylamide aqueous solution
Degree adds engrafted nanometer SiO between 10%-20%2The volume fraction of microballoon is n-isopropyl acrylamide aqueous solution volume
15%-28% between, addition be dissolved with initiator KPS, the volume of the aqueous solution of catalyst TEMED is n-isopropyl acrylamide
Between the 3-5% of aqueous solution, wherein the quality of dissolving KPS is the 0.25-0.75% of n-isopropyl acrylamide, the quality of TEMED
Fraction is the 0.5-1% of n-isopropyl acrylamide, and the polyethylene glycol mass concentration reached in gel is between 15-32%.
2. a kind of preparation method of temperature-sensitive hydrogel with shear thickening behavior according to claim 1, its feature exist
In：The engrafted nanometer SiO2The particle diameter of microballoon is between 20-100nm.
3. a kind of preparation method of temperature-sensitive hydrogel with shear thickening behavior according to claim 1, its feature exist
In：The engrafted nanometer SiO2The grafted chain of microballoon is hydrophobic segment, including polymethyl methacrylate chain, polymethylacrylic acid
Butyl ester chain, chain molecular weight is between 0.8 ten thousand -1.5 ten thousand, and molecular weight distributing index is between 1.1-1.5.
4. a kind of preparation method of temperature-sensitive hydrogel with shear thickening behavior according to claim 1, its feature exist
In：The molecular weight of the polyethylene glycol is between 200-2000.
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| CN106674421B (en) * | 2017-01-05 | 2018-08-14 | 中国工程物理研究院化工材料研究所 | A kind of preparation method of shock resistance shear thickening liquid gel |
| CN109400916B (en) * | 2018-09-29 | 2021-01-12 | 青岛大学 | SiO (silicon dioxide)2Luminous hydrogel material of grafted polymer and preparation method thereof |
| CN109593313B (en) * | 2018-10-23 | 2020-11-27 | 湖北洋田塑料制品有限公司 | Shear thickening liquid and preparation method thereof |
| CN109705366B (en) * | 2018-11-30 | 2021-04-02 | 湖南工业大学 | Preparation method of gel with strong shear thinning and shear thickening behaviors |
| CN109627499B (en) * | 2018-11-30 | 2020-11-27 | 湖南工业大学 | Preparation method of biomass composite gel with shear thickening effect |
| CN110522951B (en) * | 2019-09-11 | 2021-08-27 | 湖南工业大学 | Gel material with anti-fatigue and anti-impact characteristics |
| CN114015182B (en) * | 2021-11-29 | 2023-05-30 | 中山大学 | Impact-resistant composite hydrogel and preparation method and application thereof |
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| CN1454924A (en) * | 2003-05-15 | 2003-11-12 | 复旦大学 | Multifunctional organic-inorganic composite polymeric microball and preparing method thereof |
| CN101838375A (en) * | 2010-04-23 | 2010-09-22 | 东华大学 | Temperature and pH stimuli-responsive intelligent polymer microcapsule and preparation thereof |
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| CN1454924A (en) * | 2003-05-15 | 2003-11-12 | 复旦大学 | Multifunctional organic-inorganic composite polymeric microball and preparing method thereof |
| CN101838375A (en) * | 2010-04-23 | 2010-09-22 | 东华大学 | Temperature and pH stimuli-responsive intelligent polymer microcapsule and preparation thereof |
| CN102617769A (en) * | 2012-02-29 | 2012-08-01 | 华南理工大学 | Nanometer composite porous gel microsphere and preparation method thereof |
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Effective date of registration: 20190819 Address after: 412000 Liyu Industrial Park, Tianyuan District, Zhuzhou City, Hunan Province Patentee after: Hunan Zhenqiu Fire Stopper Industry Co., Ltd. Address before: 412008 No. 88 West Taishan Road, Tianyuan District, Hunan, Zhuzhou Patentee before: Hunan University of Technology |