A polymer composite hydrogel and a preparation method thereof

Abstract

The application discloses a kind of polymer composite hydrogel and preparation method thereof, the polymer composite hydrogel is made of including as follows raw material: chitosan, polyaspartic acid-b-polyethylene glycol, the mass ratio of chitosan and polyaspartic acid-b-polyethylene glycol is 1:10~20;The polymer composite hydrogel of the application uses chitosan and polyaspartic acid-b-polyethylene glycol of different molecular weight of high and low, the amino group is contained in the side chain and main chain of low molecular weight polyaspartic acid-b-polyethylene glycol, can occur crosslinking with high molecular weight chitosan, and then obtain the polymer composite hydrogel with crosslinking structure, and the molecular structure of polyaspartic acid-b-polyethylene glycol contains polyethylene glycol segment with good flexibility, so that the polymer composite hydrogel prepared has good tensile strength, elongation at break and slow-release effect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high molecular composite hydrogel, and particularly relates to a high molecular composite hydrogel and a preparation method thereof. BACKGROUND

[0002] As a kind of high molecular material with three-dimensional network structure, hydrogel has wide application prospect in biomedical, tissue engineering, drug delivery, flexible electronics, intelligent response material and other fields due to its good water absorption, biocompatibility and controllability.

[0003] However, the traditional hydrogel has loose crosslinking, low solid content and lacks multi-level structure, resulting in poor tensile strength, flexibility and slow release effect, which limits the deep application of its products. SUMMARY

[0004] In view of the above deficiencies in the prior art, the present application provides a high molecular composite hydrogel, which is prepared from high and low molecular weight chitosan and polyaspartic acid-b-polyethylene glycol. The low molecular weight polyaspartic acid-b-polyethylene glycol side chain and main chain both contain amino groups, which can crosslink with high molecular weight chitosan, thereby obtaining a high molecular composite hydrogel with crosslinking structure. Moreover, the molecular structure of polyaspartic acid-b-polyethylene glycol contains polyethylene glycol segments with good flexibility, so that the prepared high molecular composite hydrogel has good tensile strength, elongation at break and slow release effect.

[0005] The present application aims to provide a high molecular composite hydrogel prepared from the following raw materials: chitosan and polyaspartic acid-b-polyethylene glycol, wherein the mass ratio of chitosan to polyaspartic acid-b-polyethylene glycol is 1:10-20.

[0006] In some embodiments of the present application, the relative molecular weight of the chitosan is 100-150 kDa.

[0007] In some embodiments of the present application, the molecular weight of the polyaspartic acid segment of the polyaspartic acid-b-polyethylene glycol is 6000, and the molecular weight of the polyethylene glycol segment is 5000.

[0008] In some embodiments of the present application, the polyaspartic acid-b-polyethylene glycol has the following structure:

[0009] ;

[0010] In some embodiments of the present application, the polyaspartic acid segment of the polyaspartic acid-b-polyethylene glycol has a molecular weight of 6000, and the polyethylene glycol segment has a molecular weight of 5000.

[0011] Another object of the present application is to provide a preparation method of the polymer composite hydrogel, comprising the following steps:

[0012] The chitosan and polyaspartic acid-b-polyethylene glycol are dissolved in a fatty acid solution respectively, stirred and dissolved, a dialdehyde compound is added, cross-linked, and the polymer composite hydrogel is obtained.

[0013] In some embodiments of the present application, the fatty acid is selected from at least one of formic acid, acetic acid, propionic acid and butyric acid.

[0014] In some embodiments of the present application, the dialdehyde compound is selected from at least one of glutaraldehyde, glyoxal, malondialdehyde and succinaldehyde.

[0015] In some embodiments of the present application, the mass ratio of the chitosan, the dialdehyde compound and the fatty acid is 1:0.5-2:0.1-0.3.

[0016] In some embodiments of the present application, the cross-linking temperature is room temperature.

[0017] In some embodiments of the present application, the cross-linking time is 20min-24h.

[0018] In some embodiments of the present application, the mass concentration of the fatty acid solution is 0.2-0.6mg / ml.

[0019] Compared with the prior art, the present application has the following beneficial effects:

[0020] The polymer composite hydrogel of the present application adopts chitosan and polyaspartic acid-b-polyethylene glycol with different molecular weights, the low molecular weight polyaspartic acid-b-polyethylene glycol side chain and main chain both contain amino groups, which can be cross-linked with high molecular weight chitosan, and then a polymer composite hydrogel with cross-linked structure is obtained, and the molecular structure of the polyaspartic acid-b-polyethylene glycol contains polyethylene glycol segments with good flexibility, so that the prepared polymer composite hydrogel has good tensile strength, elongation at break and slow release effect. DETAILED DESCRIPTION

[0021] In order to enable the personnel in the technical field to better understand the technical solutions in the present application, the technical solutions of the present application will be described clearly and completely in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by the personnel in the field without creative labor should belong to the scope of protection of the present application.

[0022] All raw materials of the present application are conventional commercial products;

[0023] The polyaspartic acid-b-polyethylene glycol used in the examples and comparative examples was purchased from Xi'an Ruishi Biological Technology Co., Ltd., with the trade name Poly-L-aspartic acid-b-PEG, and the structure was The molecular weight of the polyaspartic acid segment of the polyaspartic acid-b-polyethylene glycol was 6000, and the molecular weight of the polyethylene glycol segment was 5000.

[0024] Example 1

[0025] The present example provides a kind of high molecular composite hydrogel, and its preparation method includes the following steps:

[0026] Chitosan with relative molecular weight of 100kDa 0.1g and polyaspartic acid-b-polyethylene glycol 1g are dissolved in propionic acid 0.01g and water 50ml respectively, stirring dissolving, drop glutaraldehyde 0.05g under stirring at room temperature, stirring 20-30min, place in room temperature and age 24h, obtain the high molecular composite hydrogel.

[0027] Example 2

[0028] The present example provides a kind of high molecular composite hydrogel, and its preparation method includes the following steps:

[0029] Chitosan with relative molecular weight of 100kDa 0.1g and polyaspartic acid-b-polyethylene glycol 2g are dissolved in propionic acid 0.03g and water 50ml respectively, stirring dissolving, drop glutaraldehyde 0.2g under stirring at room temperature, stirring 20-30min, place in room temperature and age 24h, obtain the high molecular composite hydrogel.

[0030] Example 3

[0031] The present example provides a kind of high molecular composite hydrogel, and its preparation method includes the following steps:

[0032] Chitosan with relative molecular weight of 150kDa 0.1g and polyaspartic acid-b-polyethylene glycol 1.5g are dissolved in propionic acid 0.02g and water 50ml respectively, stirring dissolving, drop glutaraldehyde 0.1g under stirring at room temperature, stirring 20-30min, place in room temperature and age 24h, obtain the high molecular composite hydrogel.

[0033] Comparative Example 1

[0034] The present example provides a kind of high molecular composite hydrogel, and its preparation method includes the following steps:

[0035] Chitosan with relative molecular weight of 150kDa 1.6g is dissolved in propionic acid 0.02g and water 50ml, stirring dissolving, drop glutaraldehyde 0.1g under stirring at room temperature, stirring 20-30min, place in room temperature and age 24h, obtain the high molecular composite hydrogel.

[0036] Comparative Example 2

[0037] The present comparative example provides a polymer composite hydrogel, and the preparation method thereof comprises the following steps:

[0038] Polyaspartic acid-b-polyethylene glycol 1.6 g with a relative molecular weight of 50 kDa was dissolved in propionic acid 0.02 g and water 50 ml respectively, stirred and dissolved, and glutaraldehyde 0.1 g was added dropwise under stirring at room temperature, stirred for 20-30 min, and placed in room temperature for aging for 24 h to obtain the polymer composite hydrogel.

[0039] Comparative Example 3

[0040] The present comparative example provides a polymer composite hydrogel, and the preparation method thereof comprises the following steps:

[0041] Chitosan 0.1 g with a relative molecular weight of 150 kDa and polyaspartic acid with a molecular weight of 1000 and polyethylene glycol with a molecular weight of 5000 1.5 g were dissolved in propionic acid 0.02 g and water 50 ml respectively, stirred and dissolved, and glutaraldehyde 0.1 g was added dropwise under stirring at room temperature, stirred for 20-30 min, and placed in room temperature for aging for 24 h to obtain the polymer composite hydrogel.

[0042] Comparative Example 4

[0043] The present comparative example provides a polymer composite hydrogel, and the preparation method thereof comprises the following steps:

[0044] Chitosan 0.1 g with a relative molecular weight of 50 kDa and polyaspartic acid-b-polyethylene glycol 1.5 g were dissolved in propionic acid 0.02 g and water 50 ml respectively, stirred and dissolved, and glutaraldehyde 0.1 g was added dropwise under stirring at room temperature, stirred for 20-30 min, and placed in room temperature for aging for 24 h to obtain the polymer composite hydrogel.

[0045] Comparative Example 5

[0046] The present comparative example provides a polymer composite hydrogel, and the preparation method thereof comprises the following steps:

[0047] Chitosan 0.1 g with a relative molecular weight of 200 kDa and polyaspartic acid-b-polyethylene glycol 1.5 g were dissolved in propionic acid 0.02 g and water 50 ml respectively, stirred and dissolved, and glutaraldehyde 0.1 g was added dropwise under stirring at room temperature, stirred for 20-30 min, and placed in room temperature for aging for 24 h to obtain the polymer composite hydrogel.

[0048] Performance test:

[0049] Elongation at break, tensile strength: the polymer composite hydrogel was cut into a cuboid sample with the size of 40x10x2mm (lengthxwidthxheight), and the MTS Exceed E43 series electronic universal testing machine was used to determine the elongation at break (i.e. the ratio of the elongation at break to the original length) and the tensile strength (the maximum load divided by the original cross-sectional area) of the polymer composite hydrogel by recording and analyzing the load-strain curve in the tensile process; wherein the tensile speed was 100mm / min, and the preload was 0.01N.

[0050] Table 1. Tensile strength and elongation at break of the polymer composite hydrogel

[0051] Sample Tensile strength (MPa) Elongation at break (%) Example 1 4.2 2752 Example 2 4.6 2716 Example 3 3.9 3067 Comparative Example 1 2.1 2013 Comparative Example 2 2.8 2425 Comparative Example 3 3.1 2709 Comparative Example 4 3.3 2724 Comparative Example 5 3.2 2741

[0052] As can be seen from Table 1, the polymer composite hydrogel of the present application has good tensile strength and elongation at break.

[0053] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit it. Although the present application has been described in detail with reference to the above examples, those skilled in the art should understand that the specific embodiments of the present application can still be modified or replaced by equivalents after reading the present application. However, these modifications or changes do not deviate from the scope of the present application.

Claims

1. A macromolecular composite hydrogel, characterized by, The high-molecular composite hydrogel is prepared from the following raw materials: chitosan, poly-aspartic acid-b-polyethylene glycol, and the mass ratio of chitosan to poly-aspartic acid-b-polyethylene glycol is 1:10-20; The relative molecular weight of the chitosan is 100-150 kDa; The poly-aspartic acid-b-polyethylene glycol has the following structure: ; wherein the polyaspartic acid segment of the polyaspartic acid-b-polyethylene glycol has a molecular weight of 6000 and the polyethylene glycol segment has a molecular weight of 5000; The preparation method of the high-molecular composite hydrogel comprises the following steps: The chitosan and the poly-aspartic acid-b-polyethylene glycol are respectively dissolved in a fatty acid solution, stirred and dissolved, a dialdehyde compound is added, cross-linked, and the high-molecular composite hydrogel is obtained.

2. The polymeric composite hydrogel of claim 1, wherein The fatty acid is at least one selected from formic acid, acetic acid, propionic acid and butyric acid.

3. The polymer composite hydrogel of claim 1, wherein The dialdehyde compound is at least one selected from glutaraldehyde, glyoxal, malondialdehyde and succindialdehyde.

4. The polymer composite hydrogel of claim 1, wherein The mass ratio of the chitosan, the dialdehyde compound and the fatty acid is 1:0.5-2:0.1-0.

3.

5. The polymeric composite hydrogel of claim 1, wherein The mass concentration of the fatty acid solution is 0.2-0.6 mg / ml.

6. The polymer composite hydrogel of claim 1, wherein The cross-linking temperature is room temperature, and the cross-linking time is 20 min-24 h.

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