阅读说明：本技术 一种活性微凝胶增强水凝胶及制备方法 (Active microgel reinforced hydrogel and preparation method thereof ) 是由 李建辉 杨海恩 吕宝强 李向平 康博 卜军 达引朋 黄婷 杨立安 董奇 于 2020-11-14 设计创作，主要内容包括：本发明公开了一种活性微凝胶增强水凝胶及制备方法,第一步、将明胶、2-丙烯酰胺-2-甲基丙磺酸、N,N-亚甲基双丙烯酰胺、过硫酸钾、丙烯酰胺溶解到水中,高温下反应,取出,打碎后烘干,研磨,得到活性微凝胶；第二步、将活性微凝胶与含有丙烯酰胺、过硫酸钾、N,N-亚甲基双丙烯酰胺的溶液混合均匀,静置一段时间后,在一定温度下反应数小时,得到活性微凝胶复合水凝胶；第三步、将活性微凝胶复合水凝胶浸泡在戊二醛溶液中,得到活性微凝胶增强水凝胶。通过在微凝胶中引入明胶制备活性微凝胶,然后利用活性微凝胶制备活性微凝胶增强水凝胶,进一步提升微凝胶增强水凝胶的机械性能使其能够扩展应用领域。(The invention discloses an active microgel reinforced hydrogel and a preparation method thereof, wherein in the first step, gelatin, 2-acrylamide-2-methylpropanesulfonic acid, N-methylene bisacrylamide, potassium persulfate and acrylamide are dissolved in water, and the mixture reacts at a high temperature, is taken out, is smashed, is dried and is ground to obtain active microgel; step two, uniformly mixing the active microgel and a solution containing acrylamide, potassium persulfate and N, N-methylene bisacrylamide, standing for a period of time, and reacting for several hours at a certain temperature to obtain the active microgel composite hydrogel; and thirdly, soaking the active microgel composite hydrogel in a glutaraldehyde solution to obtain the active microgel reinforced hydrogel. The gelatin is introduced into the microgel to prepare the active microgel, and then the active microgel is used for preparing the active microgel reinforced hydrogel, so that the mechanical property of the microgel reinforced hydrogel is further improved, and the application field can be expanded.)

1. A preparation method of an active microgel reinforced hydrogel is characterized by comprising the following steps:

dissolving gelatin, 2-acrylamide-2-methylpropanesulfonic acid, N-methylene bisacrylamide, potassium persulfate and acrylamide in water, reacting at 50-70 ℃, taking out, crushing, drying and grinding to obtain active microgel;

step two, uniformly mixing the active microgel and a solution containing acrylamide, potassium persulfate and N, N-methylene bisacrylamide, standing, and reacting at 50-70 ℃ for 3 hours to obtain the active microgel composite hydrogel;

and thirdly, soaking the active microgel composite hydrogel in a glutaraldehyde solution to obtain the active microgel reinforced hydrogel.

2. The method of claim 1, wherein the active microgel-reinforced hydrogel comprises: gelatin in the first step: 2-acrylamido-2-methylpropanesulfonic acid: n, N-methylenebisacrylamide: potassium persulfate: acrylamide: the mass ratio of water is 15: 20: 0.6: 0.3: 0.3: 100.

3. the method of claim 1, wherein the active microgel-reinforced hydrogel comprises: the drying temperature in the first step is 50-70 ℃.

4. The method of claim 1, wherein the active microgel-reinforced hydrogel comprises: the reaction time in the first step was 3 hours.

5. The method of claim 1, wherein the active microgel-reinforced hydrogel comprises: in the second step, the active microgel: acrylamide: potassium persulfate: n, N-methylenebisacrylamide: the mass ratio of water is 0.12-2.32: 15: 0.05: 0.017: 100.

6. the method of claim 1, wherein the active microgel-reinforced hydrogel comprises: in the second step, the drying temperature is 50-70 ℃.

7. The method of claim 1, wherein the active microgel-reinforced hydrogel comprises: the concentration of the glutaraldehyde solution is 1%.

8. The method of claim 1, wherein the active microgel-reinforced hydrogel comprises: the soaking time was 24 hours.

9. An active microgel reinforced hydrogel prepared by the method for preparing the active microgel reinforced hydrogel according to any one of claims 1 to 8.

Technical Field

The invention belongs to the field of hydrogel, and particularly relates to active microgel reinforced hydrogel and a preparation method thereof.

Background

The hydrogel is a soft and wet material, generally consists of a hydrophilic three-dimensional polymer network and a large amount of water (50-99 percent), has the advantages of good biocompatibility, low friction coefficient and the like, but the application fields of the traditional hydrogel, such as the field of tissue engineering and the field of petroleum, are limited due to weaker mechanical properties. Haque M A, Kurokawa T, Gong J P. Super tough double network hydrogels and the same applications as biomaterials [ J ] Polymer, 2012, 53(9): 1805-.

In recent years, hydrogels having excellent mechanical properties have been developed, such as nanocomposite hydrogels, double-network hydrogels, microgel-reinforced hydrogels, and the like. The double-network hydrogel shows extremely excellent mechanical strength and toughness due to the synergistic effect of different networks, but is usually obtained by a two-step method when the double-network (DN) hydrogel is synthesized, swelling, diffusion and two-step polymerization initiation processes are involved during synthesis, the processes are complex and long in time consumption, the monomer molar ratio is difficult to control, the mechanical properties of each batch of products cannot be kept consistent, and the complex synthesis steps lead to harsh requirements on application fields. The microgel reinforced hydrogel is hydrogel with excellent mechanical properties developed on the basis of the double-network hydrogel, the mechanical strength of the microgel reinforced hydrogel is almost the same as that of the double-network hydrogel, but the microgel exists in a dispersed phase in the hydrogel, so that the toughness of the microgel reinforced hydrogel is lower.

Disclosure of Invention

The invention aims to provide an active microgel reinforced hydrogel and a preparation method thereof, so as to improve the mechanical property of the microgel reinforced hydrogel.

The invention aims to realize the technical means that the preparation method of the active microgel reinforced hydrogel comprises the following steps:

dissolving gelatin, 2-acrylamide-2-methylpropanesulfonic acid, N-methylene bisacrylamide, potassium persulfate and acrylamide in water, reacting at 50-70 ℃, taking out, crushing, drying and grinding to obtain active microgel;

step two, uniformly mixing the active microgel and a solution containing acrylamide, potassium persulfate and N, N-methylene bisacrylamide, standing, and reacting at 50-70 ℃ for 3 hours to obtain the active microgel composite hydrogel;

and thirdly, soaking the active microgel composite hydrogel in a glutaraldehyde solution to obtain the active microgel reinforced hydrogel.

Gelatin in the first step: 2-acrylamido-2-methylpropanesulfonic acid: n, N-methylenebisacrylamide: potassium persulfate: acrylamide: the mass ratio of water is 15: 20: 0.6: 0.3: 0.3: 100.

the drying temperature in the first step is 50-70 ℃.

The reaction time in the first step was 3 hours.

In the second step, the active microgel: acrylamide: potassium persulfate: n, N-methylenebisacrylamide: the mass ratio of water is 0.12-2.32: 15: 0.05: 0.017: 100.

in the second step, the drying temperature is 50-70 ℃.

The concentration of the glutaraldehyde solution is 1%.

The soaking time was 24 hours.

The active microgel reinforced hydrogel is characterized by being prepared by the preparation method of the active microgel reinforced hydrogel.

The invention has the beneficial effects that: the method comprises the following steps of adding gelatin into a first network to prepare active microgel, combining the active microgel serving as the first network with a second network consisting of solutions of acrylamide, potassium persulfate and N, N-methylene bisacrylamide to obtain the active microgel reinforced hydrogel, polymerizing the microgel in the hydrogel, wherein the microgel is not in a dispersed state, and further improving the mechanical properties of the microgel reinforced hydrogel to expand the application field.

Drawings

FIG. 1 is a graph showing the results of mechanical property tests of an active microgel-reinforced hydrogel;

FIG. 2 is a graphic diagram illustrating the results of a toughness test of an active microgel-reinforced hydrogel.

The present invention will be described in further detail with reference to the accompanying drawings and examples.

Detailed Description

[ example 1 ]

A preparation method of active microgel reinforced hydrogel comprises the following steps:

dissolving gelatin, 2-acrylamide-2-methylpropanesulfonic acid, N-methylene bisacrylamide, potassium persulfate and acrylamide in water, reacting at 50-70 ℃, taking out, crushing, drying and grinding to obtain active microgel; grinding the reaction product into powder by means of crushing and grinding, and dissolving the powder in a solution composed of acrylamide, potassium persulfate and N, N-methylene-bisacrylamide in the second step.

Step two, uniformly mixing the active microgel and a solution containing acrylamide, potassium persulfate and N, N-methylene bisacrylamide, standing, and reacting at 50-70 ℃ for 3 hours to obtain the active microgel composite hydrogel;

and thirdly, soaking the active microgel composite hydrogel in a glutaraldehyde solution to obtain the active microgel reinforced hydrogel.

Gelatin in the first step: 2-acrylamido-2-methylpropanesulfonic acid: n, N-methylenebisacrylamide: potassium persulfate: acrylamide: the mass ratio of water is 15: 20: 0.6: 0.3: 0.3: 100.

the drying temperature in the first step is 50-70 ℃.

The reaction time in the first step was 3 hours.

In the second step, the active microgel: acrylamide: potassium persulfate: n, N-methylenebisacrylamide: the mass ratio of water is 0.12-2.32: 15: 0.05: 0.017: 100.

in the second step, the drying temperature is 50-70 ℃.

The concentration of the glutaraldehyde solution is 1%.

The soaking time was 24 hours.

The invention relates to an active microgel reinforced hydrogel which is prepared by adopting the preparation method of the active microgel reinforced hydrogel.

Dissolving 15 parts by weight of gelatin, 20 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 0.6 part by weight of N, N-methylenebisacrylamide, 0.3 part by weight of potassium persulfate, and 0.3 part by weight of acrylamide in 100 parts by weight of water, namely 15: 20: 0.6: 0.3: 0.3: 100, obtaining a mixed solution; and adding the obtained mixed solution into a cylindrical die, reacting for 3 hours at the temperature of 50-70 ℃, discharging, smashing, drying at the temperature of 60 ℃, taking out, and grinding to obtain the active microgel.

Dissolving 0.12-2.32 parts by weight of active microgel, 15 parts by weight of acrylamide, 0.05 part by weight of potassium persulfate and 0.017 part by weight of N, N-methylene bisacrylamide into 100 parts by weight of water to obtain a pre-polymerization solution; and standing for a period of time, adding the prepolymerization solution into a cylindrical die, reacting for 3 hours at the temperature of 50-70 ℃, discharging to obtain the active microgel composite hydrogel, and soaking the obtained active microgel composite hydrogel in a 1% glutaraldehyde solution for 24 hours to obtain the active microgel reinforced hydrogel.

As shown in fig. 1, the compressive stress strain curves of the microgel reinforced hydrogel and the active microgel reinforced hydrogel are shown. As can be seen from fig. 1, the compressive strength of the active microgel reinforced hydrogel is 100.9 MPa, which is 165% higher than that of the microgel reinforced hydrogel, indicating that the compressive strength of the active microgel reinforced hydrogel is significantly improved. As can be seen from FIG. 2, the active microgel enhanced hydrogel has a toughness of 562.34 MJ/m³Compared with the microgel reinforced hydrogel, the toughness is increased by 177%, which shows that the toughness of the active microgel reinforced hydrogel is obviously improved. It can be seen that the active microgel reinforced hydrogel possesses better mechanical properties.

[ example 2 ]

In a first step, 1.5 g of gelatin, 2g of 2-acrylamido-2-methylpropanesulfonic acid, 0.06 g of N, N-methylenebisacrylamide, 0.03 g of potassium persulfate, and 0.03 g of acrylamide were dissolved in 10 g of water on the basis of example 1 to obtain a mixed solution; and adding the mixed solution into a cylindrical die, reacting for 3 hours at the temperature of 60 ℃, discharging, smashing, drying at the temperature of 60 ℃, taking out, and grinding to obtain the active microgel. Gelatin: 2-acrylamido-2-methylpropanesulfonic acid: n, N-methylenebisacrylamide: potassium persulfate: acrylamide: the mass ratio of water is 15: 20: 0.6: 0.3: 0.3: 100.

and secondly, dissolving 0.1 g of active microgel, 1.5 g of acrylamide, 0.005 g of potassium persulfate and 0.0017 g of N, N-methylenebisacrylamide in 10 g of water to obtain a prepolymerization liquid, standing for a period of time, adding the prepolymerization liquid into a cylindrical die, reacting for 3 hours at the temperature of 60 ℃, and discharging to obtain the active microgel composite hydrogel. Active microgel: acrylamide: potassium persulfate: n, N-methylenebisacrylamide: the mass ratio of water is 1 (between 0.12 and 2.32): 15: 0.05: 0.017: 100.

and thirdly, soaking the obtained active microgel composite hydrogel in a 1% glutaraldehyde solution for 24 hours to obtain the active microgel reinforced hydrogel. The compression strength of the active microgel reinforced hydrogel is 100.9 MPa.

[ example 3 ]

In a first step, 1.5 g of gelatin, 2g of 2-acrylamido-2-methylpropanesulfonic acid, 0.06 g of N, N-methylenebisacrylamide, 0.03 g of potassium persulfate, and 0.03 g of acrylamide were dissolved in 10 g of water on the basis of example 1 to obtain a mixed solution; and adding the mixed solution into a cylindrical die, reacting for 3 hours at the temperature of 50 ℃, discharging, smashing, drying at the temperature of 60 ℃, taking out, and grinding to obtain the active microgel. Gelatin: acrylamide-2-methylpropanesulfonic acid: n, N-methylenebisacrylamide: potassium persulfate: acrylamide: the mass ratio of water is 15: 20: 0.6: 0.3: 0.3: 100.

and secondly, dissolving 0.15 g of active microgel, 1.5 g of acrylamide, 0.005 g of potassium persulfate and 0.0017 g of N, N-methylenebisacrylamide in 10 g of water to obtain a prepolymerization liquid, standing for a period of time, adding the prepolymerization liquid into a cylindrical die, reacting for 3 hours at the temperature of 50 ℃, and discharging to obtain the active microgel composite hydrogel. Active microgel: acrylamide: potassium persulfate: n, N-methylenebisacrylamide: the mass ratio of water is 1.5 (between 0.12 and 2.32): 15: 0.05: 0.017: 100.

and thirdly, soaking the obtained active microgel composite hydrogel in a 1% glutaraldehyde solution for 24 hours to obtain the active microgel reinforced hydrogel. The compressive strength of the active microgel reinforced hydrogel is 98.6 MPa.

[ example 4 ]

In a first step, 1.5 g of gelatin, 2g of 2-acrylamido-2-methylpropanesulfonic acid, 0.06 g of N, N-methylenebisacrylamide, 0.03 g of potassium persulfate, and 0.03 g of acrylamide were dissolved in 10 g of water on the basis of example 1 to obtain a mixed solution; and adding the mixed solution into a cylindrical die, reacting for 3 hours at the temperature of 70 ℃, discharging, smashing, drying at the temperature of 60 ℃, taking out, and grinding to obtain the active microgel. Acrylamide-2-methylpropanesulfonic acid: n, N-methylenebisacrylamide: potassium persulfate: acrylamide: the mass ratio of water is 15: 20: 0.6: 0.3: 0.3: 100.

and secondly, dissolving 0.1 g of active microgel, 1.5 g of acrylamide, 0.005 g of potassium persulfate and 0.0017 g of N, N-methylenebisacrylamide in 10 g of water to obtain a prepolymerization liquid, standing for a period of time, adding the prepolymerization liquid into a cylindrical die, reacting for 3 hours at the temperature of 70 ℃, and discharging to obtain the active microgel composite hydrogel. Active microgel: acrylamide: potassium persulfate: n, N-methylenebisacrylamide: the mass ratio of water is 1 (between 0.12 and 2.32): 15: 0.05: 0.017: 100.

and thirdly, soaking the obtained active microgel composite hydrogel in a 1% glutaraldehyde solution for 24 hours to obtain the active microgel reinforced hydrogel. The compressive strength of the active microgel reinforced hydrogel is 100.2 MPa.

[ example 5 ]

In a first step, 1.5 g of gelatin, 2g of 2-acrylamido-2-methylpropanesulfonic acid, 0.06 g of N, N-methylenebisacrylamide, 0.03 g of potassium persulfate, and 0.03 g of acrylamide were dissolved in 10 g of water on the basis of example 1 to obtain a mixed solution; and adding the mixed solution into a cylindrical die, reacting for 3 hours at the temperature of 60 ℃, discharging, smashing, drying at the temperature of 60 ℃, taking out, and grinding to obtain the active microgel.

And secondly, dissolving 0.15 g of active microgel, 1.5 g of acrylamide, 0.005 g of potassium persulfate and 0.0017 g of N, N-methylenebisacrylamide in 10 g of water to obtain a prepolymerization liquid, standing for a period of time, adding the prepolymerization liquid into a cylindrical die, reacting for 3 hours at the temperature of 60 ℃, and discharging to obtain the active microgel composite hydrogel. Active microgel: acrylamide: potassium persulfate: n, N-methylenebisacrylamide: the mass ratio of water is 1.5 (between 0.12 and 2.32): 15: 0.05: 0.017: 100.

and thirdly, soaking the obtained active microgel composite hydrogel in a 1% glutaraldehyde solution for 24 hours to obtain the active microgel reinforced hydrogel. The compressive strength of the active microgel reinforced hydrogel is 102.9 MPa.