CN108659440B - Preparation method for obtaining high-strength hydrogel through secondary swelling and crosslinking - Google Patents
Preparation method for obtaining high-strength hydrogel through secondary swelling and crosslinking Download PDFInfo
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Abstract
The invention provides a preparation method of high-strength hydrogel obtained by secondary swelling and crosslinking. Firstly, dissolving sodium silicate with lower concentration, acrylamide and sodium alginate in water together to initiate acrylamide polymerization, generating calcium silicate nano particles with larger particles in situ in hydrogel through calcium ion crosslinking, then soaking the hybrid hydrogel into a sodium silicate aqueous solution again, enabling the sodium silicate to be diffused into the hydrogel through moderate swelling of the hydrogel, crosslinking the swollen hydrogel with calcium ions again, and generating more calcium silicate nano particles in situ in the hydrogel. Reacting hydrogen ions released by hydrolysis of the gluconic acid-delta-lactone with calcium silicate to generate the calcium silicate with mesoporous silica gel on the surface. The mesoporous silica gel has hydrogen bond effect with calcium alginate and polyacrylamide, thereby improving the strength and stability of the hydrogel in physiological environment. The preparation method is simple and rapid, and the material has good biocompatibility and can be used as a joint cartilage substitute.
Description
Technical Field
The invention relates to a preparation method of high-strength hydrogel obtained by secondary swelling and crosslinking, belonging to the field of functional materials.
Background
The polymer hydrogel is a multi-component system consisting of a polymer three-dimensional network and water, and is widely applied to the fields of industry, agriculture, biology and materials. However, the strength of the conventional hydrogel is low, which limits further practical application. Gong Jian Nu etc. proposes the idea of 'double-layer network' hydrogel, on the basis of forming the gel of rigid first layer network with high crosslinking degree, the inside of the hydrogel is synthesized into a flexible second layer network with lower crosslinking degree. However, the double chemical network crosslinked hydrogel requires two-step polymerization, and the preparation process is relatively complicated [ Advanced materials.2014, 26: 436, 442 ]. High-elasticity and high-toughness polyacrylamide/calcium alginate (PAM/CaAlg) double-network hydrogel is prepared by latcheng et al in one step [ Nature, 2012, 489 (7414): 133-136), the hydrogel has good biocompatibility, excellent lubricity and wear resistance, and can meet the requirement of replacing cartilage tissues. Bakarich et al prepared fiber-reinforced PAM/CaAlg hydrogel artificial articular cartilage substitutes using 3D printing techniques [ ACS Applied Materials & Interfaces, 2014, 6 (18): 15998-. However, under physiological environment, the cross-linking ions in the double-network hydrogel are released, so that the mechanical property of the gel is rapidly reduced. The incorporation of silica into PAM/CaAlg hydrogels by willow pearl et al increased the breaking stress and young's modulus of the double-network gel [ chemical engineering Journal, 2014, 240 (6): 331-337 ]. Kim et al obtained PAM/CaAlg hybrid hydrogel that could maintain mechanical properties in physiological solution for a long time by using van der Waals force and hydrogen bond effect between mesoporous molecular sieve and polymer. Wudecheng et al first incorporated short chain Chitosan (CS) into the polyacrylamide network by hydrogen bonding, allowing it to form CS crystallites and an entangled network, resulting in a double-network hydrogel with high mechanical properties [ Advanced Materials, 2016, 28(33), 7178-. But the swelling problem of hydrogels under physiological conditions is not solved. Tiller and the like initiate by enzyme to form uniformly dispersed nano calcium phosphate in the double-network hydrogel, so that the elastic modulus of the hydrogel reaches 440MPa [ Nature, 2017, 543 (7645): 407- & ltSUB & gt 410- & gt, but the toughness is poor, and the application to cartilage replacement is difficult.
The invention provides a preparation method of high-strength hydrogel obtained by secondary swelling and crosslinking. Firstly, dissolving sodium silicate with lower concentration, acrylamide and sodium alginate in water together to initiate acrylamide polymerization, generating calcium silicate nano particles with larger particles in situ in hydrogel through calcium ion crosslinking, then soaking the hybrid hydrogel into a sodium silicate aqueous solution again, enabling the sodium silicate to be diffused into the hydrogel through moderate swelling of the hydrogel, crosslinking the swollen hydrogel with calcium ions again, and generating more calcium silicate nano particles in situ in the hydrogel. Reacting hydrogen ions released by hydrolysis of the gluconic acid-delta-lactone with calcium silicate to generate the calcium silicate with mesoporous silica gel on the surface. The mesoporous silica gel has hydrogen bond effect with calcium alginate and polyacrylamide, thereby improving the strength and stability of the hydrogel in physiological environment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problem that the polyacrylamide/calcium alginate double-network hydrogel is difficult to maintain high strength, high toughness and low swelling in a physiological environment due to calcium ion loss.
The invention solves the problem that the polyacrylamide/calcium alginate double-network hydrogel is difficult to maintain high strength, high toughness and low swelling in a physiological environment due to calcium ion loss.
The invention provides a preparation method of high-strength hydrogel obtained by secondary swelling and crosslinking, which is characterized by comprising the following steps:
a) weighing 0.01-2g of sodium silicate, 5-15g of acrylamide, 0.5-2g of sodium alginate and 0.03-0.30% of chemical cross-linking agent in mass percent of acrylamide, dissolving the sodium silicate, the acrylamide and the chemical cross-linking agent in 50-100ml of deionized water, uniformly stirring and dissolving the mixture, and standing and defoaming the mixture to obtain a membrane casting solution;
b) preparing 0.5-50% soluble calcium salt water solution;
c) adding ammonium persulfate with the mass percent of acrylamide of 0.1-5%, sodium bisulfite with the mass percent of acrylamide of 0.1-5% and tetramethylethylenediamine with the mass percent of acrylamide of 0.01-2% into the casting solution prepared in the step a), stirring and dispersing uniformly, immediately pouring the solution onto a dry and clean glass plate, scraping into a liquid film with uniform thickness by using a film scraping rod, and adding N into the liquid film2Under protection, ultraviolet irradiation is carried out for 1-30min to initiate acrylamide polymerization, and a chemically crosslinked gel film is obtained;
d) soaking the chemically crosslinked gel film obtained in the step c) and the glass plate into the soluble calcium salt aqueous solution obtained in the step b) for 0.1 to 24 hours, the gel film is stripped from the glass plate in the soaking process, soluble calcium salt reacts with sodium alginate to form calcium alginate hydrogel with an ion cross-linked network structure, simultaneously, soluble calcium salt reacts with sodium silicate to generate calcium silicate nano particles in situ in the polyacrylamide/calcium alginate hydrogel, calcium silicate and alginic acid molecular chains are crosslinked through calcium ions to form an organic-inorganic hybrid structure, the hybrid structures improve the stability of an alginate gel network, enhance the entanglement between the alginate network and a polyacrylamide network, share the stress transferred by the deformation of a bearing network, improve the strength of the hybrid hydrogel and reduce the swelling of the hydrogel in a physiological environment;
e) washing the gel film containing the calcium silicate obtained in the step d) by using deionized water to remove surface calcium ions, soaking the gel film into a sodium silicate aqueous solution with the mass percentage concentration of 0.001-5% for 0.1-24h to enable the sodium silicate to be diffused into the swollen hydrogel, and then soaking the swollen hydrogel into a soluble calcium salt aqueous solution again for 0.1-24h to carry out secondary calcium ion crosslinking;
f) preparing a gluconic acid-delta-lactone aqueous solution with the mass percentage concentration of 0.1-10%, soaking the secondary calcium ion crosslinked gel film obtained in the step e) into the gluconic acid-delta-lactone aqueous solution for 0.1-24h, hydrolyzing the gluconic acid-delta-lactone to release hydrogen ions, reacting the hydrogen ions with calcium silicate, and forming a mesoporous silica gel structure on the surface of calcium silicate nano particles to obtain the hybrid hydrogel keeping high strength in a physiological environment; the mesoporous silica gel, calcium alginate and polyacrylamide have hydrogen bond interaction, and the enhancement effect of the nano particles improves the mechanical stability and the swelling resistance of the polyacrylamide/calcium alginate hydrogel in a physiological environment.
The chemical cross-linking agent is any one or a mixture of more than two of ethylene glycol dimethacrylate, divinyl benzene, N' -methylene bisacrylamide and diisocyanate, and the soluble calcium salt aqueous solution is any one or a mixture of more than two of calcium nitrate, calcium chloride, calcium dihydrogen phosphate and calcium sulfate aqueous solution.
The preparation method is simple, and no organic solvent is used, so that the obtained material has good biocompatibility and can be used for artificial skin, articular cartilage substitutes and artificial tendons.
Detailed Description
Specific examples of the present invention will be described below, but the present invention is not limited to the examples.
Example 1.
a) Weighing 0.01g of sodium silicate, 5g of acrylamide, 0.5g of sodium alginate and 0.03% of ethylene glycol dimethacrylate by mass of the acrylamide, dissolving the components in 50ml of deionized water, uniformly stirring and dissolving, and standing for defoaming to obtain a casting solution;
b) preparing 0.5 mass percent of calcium nitrate aqueous solution;
c) adding ammonium persulfate with the mass percent of acrylamide of 0.1%, sodium bisulfite with the mass percent of acrylamide of 0.1% and tetramethylethylenediamine with the mass percent of acrylamide of 0.01% into the casting solution prepared in the step a), stirring and dispersing uniformly, immediately pouring the solution onto a dry and clean glass plate, scraping into a liquid film with uniform thickness by using a film scraping rod, and adding N into the liquid film2Carrying out ultraviolet irradiation for 1min under protection to initiate acrylamide polymerization to obtain a chemically crosslinked gel film;
d) soaking the chemically crosslinked gel film obtained in the step c) and the glass plate into the calcium nitrate aqueous solution obtained in the step b) for 0.1h, the gel film is stripped from the glass plate in the soaking process, calcium nitrate reacts with sodium alginate to form calcium alginate hydrogel with an ionic crosslinking network structure, simultaneously, calcium nitrate reacts with sodium silicate to generate calcium silicate nano particles in situ in the polyacrylamide/calcium alginate hydrogel, calcium silicate and alginic acid molecular chains are crosslinked through calcium ions to form an organic-inorganic hybrid structure, the hybrid structures improve the stability of an alginate gel network, enhance the entanglement between the alginate network and a polyacrylamide network, share the stress transferred by the deformation of a bearing network, improve the strength of the hybrid hydrogel and reduce the swelling of the hydrogel in a physiological environment;
e) cleaning the gel membrane containing the calcium silicate obtained in the step d) by using deionized water to remove surface calcium ions, soaking the gel membrane into a sodium silicate aqueous solution with the mass percentage concentration of 0.001% for 0.1 hour to enable the sodium silicate to be diffused into the swollen hydrogel, and then soaking the swollen hydrogel into a calcium nitrate aqueous solution again for 0.1 hour to carry out secondary calcium ion crosslinking;
f) preparing a gluconic acid-delta-lactone aqueous solution with the mass percentage concentration of 0.1%, soaking the secondary calcium ion crosslinked gel film obtained in the step e) into the gluconic acid-delta-lactone aqueous solution for 0.1h, hydrolyzing the gluconic acid-delta-lactone to release hydrogen ions, reacting the hydrogen ions with calcium silicate, and forming a mesoporous silica gel structure on the surface of calcium silicate nanoparticles to obtain the hybrid hydrogel keeping high strength in a physiological environment; the mesoporous silica gel, calcium alginate and polyacrylamide have hydrogen bond interaction, and the enhancement effect of the nano particles improves the mechanical stability and the swelling resistance of the polyacrylamide/calcium alginate hydrogel in a physiological environment.
Example 2.
a) Weighing 2g of sodium silicate, 15g of acrylamide, 2g of sodium alginate and diisocyanate with the mass percent of the acrylamide being 0.30%, dissolving the sodium silicate, the acrylamide and the diisocyanate in 100ml of deionized water, stirring and dissolving the mixture uniformly, and standing and defoaming the mixture to obtain a membrane casting solution;
b) preparing 50% calcium chloride aqueous solution by mass percent;
c) adding ammonium persulfate with 5 percent of acrylamide by mass, sodium bisulfite with 5 percent of acrylamide by mass and tetramethylethylenediamine with 2 percent of acrylamide by mass into the casting solution prepared in the step a), stirring and dispersing uniformly, pouring the solution onto a dry and clean glass plate immediately, scraping into a liquid film with uniform thickness by using a film scraping rod, and performing N-phase separation on the liquid film2Carrying out ultraviolet irradiation for 30min under protection to initiate acrylamide polymerization to obtain a chemically crosslinked gel film;
d) soaking the chemically crosslinked gel membrane obtained in the step c) and the glass plate into the calcium chloride aqueous solution obtained in the step b) for 24 hours, the gel film is stripped from the glass plate in the soaking process, calcium chloride reacts with sodium alginate to form calcium alginate hydrogel with an ion cross-linked network structure, simultaneously, calcium chloride reacts with sodium silicate to generate calcium silicate nano particles in situ in the polyacrylamide/calcium alginate hydrogel, calcium silicate and alginic acid molecular chains are crosslinked through calcium ions to form an organic-inorganic hybrid structure, the hybrid structures improve the stability of an alginate gel network, enhance the entanglement between the alginate network and a polyacrylamide network, share the stress transferred by the deformation of a bearing network, improve the strength of the hybrid hydrogel and reduce the swelling of the hydrogel in a physiological environment;
e) washing the gel membrane containing the calcium silicate obtained in the step d) by using deionized water to remove surface calcium ions, soaking the gel membrane into a sodium silicate aqueous solution with the mass percentage concentration of 5% for 24 hours to enable the sodium silicate to be diffused into the swollen hydrogel, and then soaking the swollen hydrogel into a calcium chloride aqueous solution again for 24 hours to carry out secondary calcium ion crosslinking;
f) preparing a gluconic acid-delta-lactone aqueous solution with the mass percentage concentration of 10%, soaking the secondary calcium ion crosslinked gel film obtained in the step e) into the gluconic acid-delta-lactone aqueous solution for 24 hours, hydrolyzing the gluconic acid-delta-lactone to release hydrogen ions, and reacting the hydrogen ions with calcium silicate to form a mesoporous silica gel structure on the surface of calcium silicate nano particles to obtain the hybrid hydrogel keeping high strength in a physiological environment; the mesoporous silica gel, calcium alginate and polyacrylamide have hydrogen bond interaction, and the enhancement effect of the nano particles improves the mechanical stability and the swelling resistance of the polyacrylamide/calcium alginate hydrogel in a physiological environment.
Example 3.
a) Weighing 1g of sodium silicate, 1g of acrylamide, 1g of sodium alginate and N, N '-methylene bisacrylamide with the mass percent of the acrylamide being 0.10%, dissolving the sodium silicate, the acrylamide and the N, N' -methylene bisacrylamide in 60ml of deionized water, stirring and dissolving the mixture uniformly, and standing the mixture for defoaming to obtain a membrane casting solution;
b) preparing a calcium dihydrogen phosphate aqueous solution with the mass percentage of 5%;
c) adding ammonium persulfate with the mass percent of acrylamide of 1 percent, sodium bisulfite with the mass percent of acrylamide of 1 percent and tetramethylethylenediamine with the mass percent of acrylamide of 1 percent into the casting solution prepared in the step a), stirring and dispersing uniformly, pouring the solution onto a dry and clean glass plate immediately, scraping into a liquid film with uniform thickness by using a film scraping rod, and performing N-phase separation on the liquid film2Carrying out ultraviolet irradiation for 10min under protection to initiate acrylamide polymerization to obtain a chemically crosslinked gel film;
d) soaking the chemically crosslinked gel membrane obtained in the step c) and the glass plate into the calcium dihydrogen phosphate aqueous solution obtained in the step b) for 1h, the gel film is uncovered from the glass plate in the soaking process, calcium dihydrogen phosphate reacts with sodium alginate to form calcium alginate hydrogel with an ion cross-linked network structure, simultaneously, calcium dihydrogen phosphate reacts with sodium silicate to generate calcium silicate nano particles in situ in the polyacrylamide/calcium alginate hydrogel, calcium silicate and alginic acid molecular chains are crosslinked through calcium ions to form an organic-inorganic hybrid structure, the hybrid structures improve the stability of an alginate gel network, enhance the entanglement between the alginate network and a polyacrylamide network, share the stress transferred by the deformation of a bearing network, improve the strength of the hybrid hydrogel and reduce the swelling of the hydrogel in a physiological environment;
e) cleaning the gel membrane containing calcium silicate obtained in the step d) by using deionized water to remove surface calcium ions, soaking the gel membrane into a sodium silicate aqueous solution with the mass percentage concentration of 1% for 1h to enable the sodium silicate to be diffused into the swollen hydrogel, and then soaking the swollen hydrogel into a calcium dihydrogen phosphate aqueous solution again for 1h to carry out secondary calcium ion crosslinking;
f) preparing a gluconic acid-delta-lactone aqueous solution with the mass percentage concentration of 1%, soaking the secondary calcium ion crosslinked gel film obtained in the step e) into the gluconic acid-delta-lactone aqueous solution for 1h, hydrolyzing the gluconic acid-delta-lactone to release hydrogen ions, and reacting the hydrogen ions with calcium silicate to form a mesoporous silica gel structure on the surface of calcium silicate nano particles to obtain a hybrid hydrogel which keeps high strength in a physiological environment; the mesoporous silica gel, calcium alginate and polyacrylamide have hydrogen bond interaction, and the enhancement effect of the nano particles improves the mechanical stability and the swelling resistance of the polyacrylamide/calcium alginate hydrogel in a physiological environment.
Example 4.
a) Weighing 1.5g of sodium silicate, 10g of acrylamide, 1.5g of sodium alginate and 0.10% of divinylbenzene by mass percent of acrylamide, dissolving the sodium silicate, the acrylamide and the divinylbenzene in 80ml of deionized water, uniformly stirring and dissolving, and standing for defoaming to obtain a casting solution;
b) preparing 1% calcium sulfate aqueous solution by mass percent;
c) adding ammonium persulfate with the mass percent of acrylamide of 1 percent, sodium bisulfite with the mass percent of acrylamide of 1 percent and tetramethylethylenediamine with the mass percent of acrylamide of 1 percent into the casting solution prepared in the step a), stirring and dispersing uniformly, pouring the solution onto a dry and clean glass plate immediately, scraping into a liquid film with uniform thickness by using a film scraping rod, and performing N-phase separation on the liquid film2Carrying out ultraviolet irradiation for 3min under protection to initiate acrylamide polymerization to obtain a chemically crosslinked gel film;
d) soaking the chemically crosslinked gel film obtained in the step c) and the glass plate into the calcium sulfate aqueous solution obtained in the step b) for 2 hours, the gel film is stripped from the glass plate in the soaking process, calcium sulfate reacts with sodium alginate to form calcium alginate hydrogel with an ion cross-linked network structure, simultaneously, calcium sulfate reacts with sodium silicate to generate calcium silicate nano particles in situ in the polyacrylamide/calcium alginate hydrogel, calcium silicate and alginate molecular chains are crosslinked through calcium ions to form an organic-inorganic hybrid structure, the hybrid structures improve the stability of an alginate gel network, enhance the entanglement between the alginate network and a polyacrylamide network, share the stress transferred by the deformation of a bearing network, improve the strength of the hybrid hydrogel and reduce the swelling of the hydrogel in a physiological environment;
e) cleaning the gel membrane containing the calcium silicate obtained in the step d) by using deionized water to remove surface calcium ions, soaking the gel membrane into a sodium silicate aqueous solution with the mass percentage concentration of 2% for 2 hours to enable the sodium silicate to be diffused into the swollen hydrogel, and then soaking the swollen hydrogel into a calcium sulfate aqueous solution again for 2 hours to carry out secondary calcium ion crosslinking;
f) preparing a gluconic acid-delta-lactone aqueous solution with the mass percentage concentration of 2%, soaking the secondary calcium ion crosslinked gel film obtained in the step e) into the gluconic acid-delta-lactone aqueous solution for 2h, hydrolyzing the gluconic acid-delta-lactone to release hydrogen ions, and reacting the hydrogen ions with calcium silicate to form a mesoporous silica gel structure on the surface of calcium silicate nano particles to obtain a hybrid hydrogel which keeps high strength in a physiological environment; the mesoporous silica gel, calcium alginate and polyacrylamide have hydrogen bond interaction, and the enhancement effect of the nano particles improves the mechanical stability and the swelling resistance of the polyacrylamide/calcium alginate hydrogel in a physiological environment.
Claims (3)
1. A preparation method of high-strength hydrogel obtained by secondary swelling and crosslinking is characterized by comprising the following steps:
a) weighing 0.01-2g of sodium silicate, 5-15g of acrylamide, 0.5-2g of sodium alginate and 0.03-0.30% of chemical cross-linking agent in mass percent of acrylamide, dissolving the sodium silicate, the acrylamide and the chemical cross-linking agent in 50-100ml of deionized water, uniformly stirring and dissolving the mixture, and standing and defoaming the mixture to obtain a membrane casting solution;
b) preparing 0.5-50% soluble calcium salt water solution;
c) adding ammonium persulfate with the mass percent of acrylamide of 0.1-5%, sodium bisulfite with the mass percent of acrylamide of 0.1-5% and tetramethylethylenediamine with the mass percent of acrylamide of 0.01-2% into the casting solution prepared in the step a), stirring and dispersing uniformly, immediately pouring the solution onto a dry and clean glass plate, scraping into a liquid film with uniform thickness by using a film scraping rod, and adding N into the liquid film2Under protection, ultraviolet irradiation is carried out for 1-30min to initiate acrylamide polymerization, and a chemically crosslinked gel film is obtained;
d) soaking the chemically crosslinked gel film obtained in the step c) and the glass plate into the soluble calcium salt aqueous solution obtained in the step b) for 0.1 to 24 hours, the gel film is stripped from the glass plate in the soaking process, soluble calcium salt reacts with sodium alginate to form calcium alginate hydrogel with an ion cross-linked network structure, simultaneously, soluble calcium salt reacts with sodium silicate to generate calcium silicate nano particles in situ in the polyacrylamide/calcium alginate hydrogel, calcium silicate and alginic acid molecular chains are crosslinked through calcium ions to form an organic-inorganic hybrid structure, the hybrid structures improve the stability of an alginate gel network, enhance the entanglement between the alginate network and a polyacrylamide network, share the stress transferred by the deformation of a bearing network, improve the strength of the hybrid hydrogel and reduce the swelling of the hydrogel in a physiological environment;
e) washing the gel membrane containing the calcium silicate obtained in the step d) by using deionized water to remove calcium ions on the surface, soaking the gel membrane into a sodium silicate aqueous solution with the mass percentage concentration of 0.001-5% for 0.1-24h to enable the sodium silicate to be diffused into the swollen hydrogel, and then soaking the swollen hydrogel into a soluble calcium salt aqueous solution again for 0.1-24h to carry out secondary calcium ion crosslinking;
f) preparing a gluconic acid-delta-lactone aqueous solution with the mass percentage concentration of 0.1-10%, soaking the secondary calcium ion crosslinked gel film obtained in the step e) into the gluconic acid-delta-lactone aqueous solution for 0.1-24h, hydrolyzing the gluconic acid-delta-lactone to release hydrogen ions, reacting the hydrogen ions with calcium silicate, and forming a mesoporous silica gel structure on the surface of calcium silicate nano particles to obtain the hybrid hydrogel keeping high strength in a physiological environment; the mesoporous silica gel, calcium alginate and polyacrylamide have hydrogen bond interaction, and the enhancement effect of the nano particles improves the mechanical stability and the swelling resistance of the polyacrylamide/calcium alginate hydrogel in a physiological environment.
2. The method according to claim 1, wherein the chemical crosslinking agent is one or more selected from the group consisting of ethylene glycol dimethacrylate, divinylbenzene and N, N' -methylenebisacrylamide.
3. The method for preparing high-strength hydrogel by secondary swelling and crosslinking according to claim 1, wherein the aqueous solution of soluble calcium salt is any one of aqueous solutions of calcium nitrate and calcium chloride.
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