CN109705366B - Preparation method of gel with strong shear thinning and shear thickening behaviors - Google Patents
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- 239000000243 solution Substances 0.000 claims description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
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Abstract
The invention relates to a method for preparing gel with strong shear thinning and shear thickening behaviors, which takes a polymer with certain ionic characteristics as a framework, polyethylene glycol aqueous solution with certain concentration is swelled in a matrix, and carboxyl on the surface is dispersed in the aqueous solution to modify nano SiO2Microspheres, the pH value in the gel system is adjusted to acidity. The gels exhibit significant thinning behavior at low shear rates due to depolymerization between the components at a particular pH, and exhibit strong shear thickening characteristics due to the formation of a network with a high coefficient of friction in the microspheres and dispersion medium.
Description
Technical Field
The invention belongs to a preparation method of intelligent hydrogel, and particularly relates to an intelligent hydrogel which can generate shear thickening characteristics, has obvious shear thinning behavior at a low shear rate and has strong shear thickening behavior at a high shear rate.
Background
The polymer gel is a system composed of a polymer compound with a three-dimensional network structure and a solvent, wherein the polymers are connected by van der waals force, chemical bond force, physical winding force, hydrogen bond force and the like. Since it is a three-dimensional network three-dimensional structure, it cannot be dissolved by a solvent while being dispersed in the solvent and maintaining a certain shape. Although the solvent cannot dissolve the polymer having a three-dimensional network structure, the solvent may act on the group portion of the solvent-philic component of the polymer compound to swell the polymer, which is also a cause of forming a polymer gel.
Shear thickening refers to the "setting" behavior of a material from soft to hard, with an increase in viscosity occurring when the material is subjected to an increase in shear stress (strain). Shear thickening was first discovered in particle suspension systems, such as slurries, starch dispersions, and the like, including dispersion media such as viscous liquids and dispersions such as micro-nanoparticles, and has now been found in both solid composites and gel materials. In recent 20 years, the shear thickening phenomenon has been widely noticed, and various dispersed particles and dispersion media thereof are combined to form a suspension with the shear thickening phenomenon, typicallyThe particles include inorganic particles such as SiO2、CaCO3、Fe2O3Glass fiber, etc., organic particles such as starch, synthetic particles including polymethyl methacrylate (PMMA) microspheres, Polystyrene (PS) microspheres, polystyrene graft acrylic acid (PS-g-AA) microspheres, poly dimethyl propionamide-acrylic acid (P (DMAA-AA)) microspheres, etc., and dispersion media including water, polyethylene glycol, glycerol, aliphatic hydrocarbons of different chain lengths, etc. When the particles in the suspension reach a certain volume fraction, shear thickening occurs immediately.
The existing shear thickening gel is generally prepared by realizing sol-gelation through shear thickening characteristic thickening, the shear thickening gel does not have stable gel form, and the gel prepared by a synthetic crosslinking mode is relatively mild in shear thinning and shear thickening stages and cannot achieve smooth deformation in low shear and rapid solidification in high shear so as to achieve the effects of energy absorption and protection. If a gel material could be prepared, combining the high softness properties of low shear and the high hardening effect of high shear, it would undoubtedly have great application prospects.
Disclosure of Invention
The invention aims to provide a preparation method of a shear thickening hydrogel, in particular to a preparation method of a gel which has the characteristic of quick softening at a low shear rate and can be quickly solidified at a high shear rate.
The purpose of the invention is realized by the following technical scheme:
a preparation method of temperature-sensitive hydrogel with shear thickening property comprises the following steps:
(1) preparing aqueous solution of N, N-dimethylacrylamide, acrylic acid and polyacrylic acid with a certain concentration, and modifying a certain amount of surface carboxyl groups with nano SiO2Adding the microspheres into the solution, adding a small amount of alkaline aqueous solution, adjusting the pH value of the system to 8-10, and ultrasonically oscillating the system in an ice-water bath for 20 minutes to enable the surface carboxyl modified nano SiO to be2Uniformly dispersing the microspheres in the solution, adding a small amount of aqueous solution in which an initiator KPS and a catalyst TEMED are dissolved, continuing ultrasonic oscillation in an ice-water bath for 20 minutes,the above processes are all carried out under the protection of nitrogen. The reaction vessel was then sealed and placed in an ice-water bath to react for 24 hours to form a gel. Taking out the gel, and repeatedly soaking the gel in deionized water to change water to remove unreacted monomers and solvents;
(2) preparing a PEG aqueous solution with a certain concentration and an acidic aqueous solution with a pH value between 2 and 3, injecting the PEG aqueous solution and the acidic aqueous solution into the swollen gel through an injector in sequence to ensure that the swollen polyethylene glycol in the gel reaches a certain concentration, adjusting the pH value of a swelling solution in the gel to be between 4 and 5, and placing the gel in an ultrasonic oscillator to vibrate at a high frequency for 30 minutes to obtain a final gel product.
The preparation process is characterized in that: adding surface carboxyl modified nano SiO in the aqueous solution of N, N-dimethylacrylamide, acrylic acid and polyacrylic acid, wherein the mass concentration of N, N-dimethylacrylamide is between 8 and 12 percent, the mass concentration of acrylic acid is between 5 and 8 percent, and the mass concentration of polyacrylic acid is between 1.5 and 3 percent in the aqueous solution of N, N-dimethylacrylamide and acrylic acid, and adding surface carboxyl modified nano SiO2The volume fraction of the microspheres is between 19 and 32 percent of the volume of the aqueous solution pre-polymerization solution, the initiator KPS is added, the volume of the aqueous solution of the catalyst TEMED is between 2 and 4 percent of the pre-polymerization solution, wherein the mass fraction of the dissolved KPS is 0.3 to 0.8 percent of the mass fraction of N, N-dimethylacrylamide, the mass fraction of the TEMED is 0.5 to 1 percent of the mass fraction of N, N-dimethylacrylamide, and the mass concentration of polyethylene glycol in the gel is between 28 and 42 percent.
Further, monomers used for gel synthesis were N, N-Dimethylacrylamide (DMAA) and acrylic acid (AAc). The structural formulas are respectively as follows:
DMAA=
AAc= 
DMAA has good hydrophilicity and synthesis, can be copolymerized with AAc, and can be dissociated into positive ions in aqueous solution after polymerization because AAc has COOH groups.
Furthermore, the molecular weight of the polyacrylic acid is between 1000-5000, polyacrylic acid macromolecules exist as chain segments of a semi-interpenetrating network, and macromolecular polyacrylic acid is added to strengthen the strength of a gel network during synthesis, facilitate molding and further provide a certain movable cationic group.
Further, the surface carboxyl modified nano SiO2The molecular structure of the microspheres is as follows:
further, the amount of surface graft chains is equal to SiO2The mass ratio of the microspheres is between 0.45 and 0.65 mmol/g.
Further, the surface carboxyl is modified with nano SiO2The preparation method of the microsphere comprises the following steps: uniformly dispersing equal mols of KH-550 and succinic anhydride in a certain amount of N, N-dimethylformamide, wherein the concentration of the N, N-dimethylformamide is 5-10mol/L and 80 mol/LoAnd C, magnetically stirring for 3 hours, adding the ultrasonically dispersed N, N-dimethylformamide suspension of the silicon dioxide into the system, and simultaneously adding a certain amount of deionized water, wherein the amount of the silicon dioxide and the succinic anhydride can be adjusted according to the required molar weight of the access chain segment. At 80oAnd C, continuing magnetically stirring for 5 hours, separating the nano-silica by using an ultrahigh-speed centrifuge, and carrying out alcohol washing and centrifugal separation for multiple times to obtain the carboxylated modified nano-silica.
Further, the surface carboxyl modified nano SiO2The particle size of the microspheres is between 30 and 80 nm.
Further, the molecular weight of the polyethylene glycol is between 200 and 600.
Further, the alkaline aqueous solution is a small molecular ionic alkaline aqueous solution such as NaOH and KOH.
Further, the acidic aqueous solution is a small molecular ionic acidic aqueous solution such as an acetic acid aqueous solution, a hydrochloric acid aqueous solution and the like.
Furthermore, the alkaline aqueous solution is added in the early stage to ensure the system to be stable and ensure the synthesis to be carried out smoothly, and the acid solution is injected in the later stage to improve the shear thinning effect of the material.
The invention has the technical characteristics that: in the invention, hydrophilic N, N-dimethylacrylamide and acrylic acid are used as monomers to form a gel network, and macromolecular linear polyacrylic acid is added to form a semi-interpenetrating network gel, so that the synthesis and the basic strength of the gel are effectively ensured. The gel has obvious shear thickening property due to the existence of PEG solution with certain viscosity and suspended and dispersed grafting microspheres. The main network of the gel has cations, the carboxylic acid groups on the surfaces of the added modified silica particles also have cations, after the acid liquid and the PEG solution are added, the acid liquid is more combined with the weakly acidic PEG to play a role of a small molecular lubricant so as to be beneficial to the reduction of viscosity, and meanwhile, the microspheres with organic chain segments grafted on the surfaces are aggregated to a certain extent and then are depolymerized, so that the rapid thinning process at a low shear rate is realized. And when the shear is high, the friction coefficient between particles is improved due to the chain segment grafted on the surface of the silica microsphere, so that the thickening degree of the silica microsphere is enhanced.
The performance characteristics are as follows: the shear rate range of the gel for shear thinning is (0.01-1 s)-1) When the viscosity is reduced from 20-30Pa.s to 5-10Pa.s, the shear rate of the gel is in the range of (1-100 s)-1) The maximum viscosity of the gel is 300-600Pa.s.
Drawings
FIG. 1 is a plot of shear rate versus viscosity at 20 degrees for the hydrogel prepared in example 1.
Figure 2 is a cut rate-viscosity curve at 20 degrees for the hydrogel prepared in example 2.
Detailed Description
The foregoing and other aspects of the present invention will become more apparent from the following detailed description, taken in conjunction with the accompanying drawings, illustrating by way of example the principles of the invention, and are not to be construed as limiting the scope of the invention in any way which is based on the above teachings.
Example 1
A method for preparing gel with strong shear thinning and shear thickening behaviors comprises the following steps:
(1) preparing a certain concentration of N, N-dimethylacrylamide, acrylic acid and polyacrylic acid aqueous solution pre-polymerization solution, wherein the mass concentration of the N, N-dimethylacrylamide is 10%, the mass concentration of the acrylic acid is 6%, and the mass concentration of the polyacrylic acid is 2%. Adding surface carboxyl modified nano SiO with volume fraction of 25% of aqueous solution pre-polymerization liquid2Adding a small amount of NaOH aqueous solution into microspheres, adjusting the pH value of the system to 9, and ultrasonically oscillating the microspheres in ice-water bath for 20 minutes to enable the surface carboxyl groups to be modified by the nano SiO2Uniformly dispersing microspheres in the solution, adding an aqueous solution which is dissolved with an initiator KPS and a catalyst TEMED and accounts for 3% of the volume of the aqueous solution pre-polymerization solution, wherein the mass of the dissolved KPS is 0.45% of that of the N, N-dimethylacrylamide, and the mass fraction of the TEMED is 0.85% of that of the N, N-dimethylacrylamide, and continuing ultrasonic oscillation in an ice-water bath for 20 minutes, wherein the processes are all carried out under the protection of nitrogen. The reaction vessel was then sealed and placed in an ice-water bath to react for 24 hours to form a gel. Taking out the gel, and repeatedly soaking the gel in deionized water to change water to remove unreacted monomers and solvents;
(2) preparing a PEG aqueous solution with the mass fraction of 58% and a hydrochloric acid aqueous solution with the pH value of 2.5, injecting the PEG aqueous solution and the hydrochloric acid aqueous solution into the swollen gel through an injector to ensure that the mass concentration of the polyethylene glycol in the gel reaches 31%, the pH value of a swelling solution in the gel reaches 4.5, and placing the gel in an ultrasonic oscillator to vibrate at high frequency for 30 minutes to obtain a final gel product.
The molecular weight of the polyacrylic acid is 3000-4000.
The surface carboxyl modified nano SiO2The particle size of the microspheres is between 50 and 60 nm.
Amount and SiO2The mass ratio of the microspheres is 0.52 mmol/g.
The molecular weight of the polyethylene glycol is 400.
The shear rate-viscosity curve of the prepared gel is shown in FIG. 1.
Example 2
A method for preparing gel with strong shear thinning and shear thickening behaviors comprises the following steps:
(1) preparing N, N-dimethylacrylamide, acrylic acid and polyacrylic acid water with certain concentrationThe solution pre-polymerization solution comprises 8.5% of N, N-dimethylacrylamide, 7.5% of acrylic acid and 2% of polyacrylic acid. Adding surface carboxyl modified nano SiO with the volume fraction of 30 percent of aqueous solution pre-polymerization liquid2Adding a small amount of NaOH aqueous solution into microspheres, adjusting the pH value of the system to 9, carrying out ultrasonic oscillation in an ice-water bath for 20 minutes to uniformly disperse the surface carboxyl modified nano SiO2 microspheres in the aqueous solution, adding an aqueous solution which is dissolved with an initiator KPS and a catalyst TEMED and contains 3% of the volume of the aqueous solution pre-polymerization solution, wherein the mass of the dissolved KPS is 0.45% of that of the N, N-dimethylacrylamide, the mass fraction of the TEMED is 0.8% of that of the N, N-dimethylacrylamide, and carrying out the ultrasonic oscillation in the ice-water bath for 20 minutes continuously, wherein the processes are carried out under the protection of nitrogen. The reaction vessel was then sealed and placed in an ice-water bath to react for 24 hours to form a gel. Taking out the gel, and repeatedly soaking the gel in deionized water to change water to remove unreacted monomers and solvents;
(2) preparing a PEG aqueous solution with the mass fraction of 62% and an acetic acid aqueous solution with the pH value of 2.5, injecting the PEG aqueous solution and the acetic acid aqueous solution into the swollen gel through an injector to ensure that the mass concentration of the polyethylene glycol in the gel reaches 38%, the pH value of a swelling solution in the gel reaches 4.8, and placing the gel in an ultrasonic oscillator to vibrate at high frequency for 30 minutes to obtain a final gel product.
The molecular weight of the polyacrylic acid is 3000-4000.
The surface carboxyl modified nano SiO2The particle size of the microspheres is between 50 and 60 nm.
The amount of the surface graft chain is equal to SiO2The mass ratio of the microspheres is 0.52 mmol/g.
The molecular weight of the polyethylene glycol is 400.
The shear rate-viscosity curve of the prepared gel is shown in FIG. 2.
Claims (3)
1. A method for preparing gel with strong shear thinning and shear thickening behaviors comprises the following steps:
(1) preparing aqueous solution of N, N-dimethylacrylamide, acrylic acid and polyacrylic acid with a certain concentration, and modifying a certain amount of surface carboxyl groups with nano SiO2Adding the microspheres into the solution, adding a small amount of alkaline aqueous solution, adjusting the pH value of the system to 8-10, and ultrasonically oscillating the system in an ice-water bath for 20 minutes to enable the surface carboxyl modified nano SiO to be2Uniformly dispersing microspheres in the solution, adding a small amount of aqueous solution in which an initiator KPS and a catalyst TEMED are dissolved, continuing ultrasonic oscillation in an ice-water bath for 20 minutes, sealing the reaction container, placing the reaction container in the ice-water bath for reaction for 24 hours to form gel, taking out the gel, repeatedly soaking the gel in deionized water, and changing water to remove unreacted monomers and solvents;
(2) preparing a PEG aqueous solution with the mass fraction of between 58 and 62 percent and an acidic aqueous solution with the pH value of between 2 and 3, injecting the PEG aqueous solution and the acidic aqueous solution into the swollen gel through an injector in sequence to ensure that the swollen polyethylene glycol in the gel reaches a certain concentration, adjusting the pH value of a swelling solution in the gel to between 4 and 5, and placing the gel in an ultrasonic oscillator for high-frequency oscillation for 30 minutes to obtain a final gel product; the preparation process is characterized in that: adding surface carboxyl modified nano SiO in the aqueous solution of N, N-dimethylacrylamide, acrylic acid and polyacrylic acid, wherein the mass concentration of N, N-dimethylacrylamide is between 8 and 12 percent, the mass concentration of acrylic acid is between 5 and 8 percent, and the mass concentration of polyacrylic acid is between 1.5 and 3 percent in the aqueous solution of N, N-dimethylacrylamide and acrylic acid, and adding surface carboxyl modified nano SiO2The volume fraction of the microspheres is between 19 and 32 percent of the volume of the aqueous solution pre-polymerization solution, the initiator KPS is added, the volume of the aqueous solution of the catalyst TEMED is between 2 and 4 percent of the pre-polymerization solution, wherein the mass fraction of the dissolved KPS is 0.3 to 0.8 percent of N, N-dimethylacrylamide, the mass fraction of the TEMED is 0.5 to 1 percent of N, N-dimethylacrylamide, and the mass concentration of polyethylene glycol in the gel is between 28 and 42 percent;
it is also characterized in that the surface carboxyl modified nano SiO2The molecular structure of the microspheres is as follows:
surface carboxyl modified nano SiO2The particle size of the microsphere is between 30 and 80nm, and the surface is graftedAmount of chain and SiO2The mass ratio of the microspheres is between 0.45 and 0.65 mmol/g.
2. A method of preparing a gel having strong shear-thinning and shear-thickening behavior according to claim 1, characterized in that: the molecular weight of the polyacrylic acid is between 1000-5000.
3. A method of preparing a gel having strong shear-thinning and shear-thickening behavior according to claim 1, characterized in that: the molecular weight of the polyethylene glycol is between 200 and 600.
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| "羧基化改性聚苯乙烯微球的制备及对其聚乙二醇悬液的剪切增稠特性";宋凯杰等;《高分子材料科学与工程》;20180530;第34卷(第5期);170-176 * |
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