CN104189960A - Preparation method for composite hydrogel - Google Patents
Preparation method for composite hydrogel Download PDFInfo
- Publication number
- CN104189960A CN104189960A CN201410467738.9A CN201410467738A CN104189960A CN 104189960 A CN104189960 A CN 104189960A CN 201410467738 A CN201410467738 A CN 201410467738A CN 104189960 A CN104189960 A CN 104189960A
- Authority
- CN
- China
- Prior art keywords
- preparation
- solution
- chitosan
- initiator
- hydroxyapatite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a preparation method for composite hydrogel and belongs to the technical field of polymers. The preparation method comprises the following steps: firstly, preparing hydroxyapatite (HA) and chitosan (CS) into solution; secondly, doping the solution in a polyacrylamide (PAM) network structure. According to the preparation method, the preparation process is simple and convenient to operate and the cost is reduced; besides, the obtained material overcomes the defects that a CS stent is easily bent and is poor in mechanical property, and retains good mechanical properties of tensile strength and compression resistance endowed by the HA; in the preparation process, the HA and the CS which have good biocompatibility are doped in the PAM network structure, and good mechanical properties are endowed for a hydrogel material. Therefore, the composite material can be used as a replacement material of cartilage and has potential application value in the tissue engineering.
Description
Technical field
The preparation method that the present invention relates to a kind of composite aquogel, belongs to polymeric material field.
Background technology
Polyacrylamide (PAM) hydrogel, because having good bio-compatibility, has caused the broad interest of biologic applications circle, biologic applications circle use it for the fields such as the timbering material, cartilaginous tissue substitution material, pharmaceutical carrier of organizational project (
j. P. Gong, Advanced MateriaLs, 2003,15,1155-1158).The hydrogel support especially with some strength has been applied to the research and development of the products such as bone, cartilage and muscle.The intensity of hydrogel and the degree of cross linking and the service condition etc. thereof of gel have certain relation.But general hydrogel is because the long-chain extensively distributing forms random crosslinking points by traditional covalent cross-linking, lack effective energy dissipation mechanism, therefore it presents fragility, low ductility, low mechanical strength, practical application is very limited, therefore need further to improve the mechanical performance of gel rubber material.In the last few years, how to improve the mechanical property of hydrogel and develop the hydrogel with specific function become the research emphasis of scientific circles and business circles (
h. P. Cong, P. Wang, S. H. Yu. SmaLL, 2014,10,448-453).
Hydroxyapatite (HA)/chitosan (CS) composite has important function in bone tissue engineer field, and chitosan (CS) has very many advantages in cartilage tissue engineered field, is regarded as the ideal chose of bone alternate material.The easy bending of CS support and engineering properties, therefore can not load support implants not as natural bone.Compound can the improvement of ceramic material and CS support improved its engineering properties, but CS itself does not but have osteoinductive, so CS support self can not be simulated all character of natural bone.Calcium phosphate ceramic is commonly used to simulate the inorganic constituents of mineralising natural bone, and there is osteoinductive, therefore HA/CS composite the composition of simulation mineralising natural bone and in nature tool have great advantage, more existing research report HA/CS composites are applied to bone tissue engineer.Chitosan just can be used as adjuvant and joins in hydroxyapatite bone cement in the situation that not carrying out any chemical modification, strengthens its syringeability, and HA and CS compound use can be given full play to both advantages, overcomes shortcoming each other.
Summary of the invention
The present invention aims to provide a kind of preparation method of hydroxyapatite/chitosan/polyacrylamide cartilage substitution material with good mechanical property.This technology of preparing has retained hydroxyapatite (HA) and both advantages of chitosan (CS), and has strengthened the mechanical property of polyacrylamide polymers homogenous material, has widened the application category of composite, is expected to be applied in organizational project.This preparation method process is simple, and the mechanics mechanical performance of synthetic hybridized hydrogel material has obtained significant raising.
The preparation method of a kind of composite aquogel provided by the invention, is by hydroxyapatite (HA) and chitosan (CS) wiring solution-forming, is then doped in polyacrylamide (PAM) network structure, specifically comprises the following steps:
(1) preparation hydroxyapatite (HA) aqueous solution: hydroxyapatite (HA) powder is dissolved in to intermediate water, and concussion stirs it is fully dissolved, obtain milky HA solution;
(2) preparation chitosan (CS) aqueous solution: chitosan (CS) powder is dissolved in to intermediate water, and then adds acetic acid, finally concussion is stirred it is dissolved fully fast, obtains the CS solution of milk yellow;
(3) prepare cross-linking agent aqueous solution (MBA): get cross-linking agent N, N'-methylene-bisacrylamide (MBA) is dissolved in the water, ultrasonic concussion 2min makes Solution Dispersion even, obtains cross-linking agent aqueous solution;
(4) prepare initiator solution (KPS): get initiator potassium persulfate (KPS) and be dissolved in the water, ultrasonic concussion 2min makes Solution Dispersion even, obtains initiator solution;
(5) preparation of HA/CS/PAM composite aquogel: add monomer acrylamide in test tube, the cross-linking agent solution that (3) are obtained adds in test tube, respectively get the solution that above-mentioned (1), (2) obtain and drip in test tube, and add intermediate water that monomer acrylamide is fully dissolved; Then by test tube sealing, add subsequently initiator and accelerator, initiated polymerization, reaction is carried out, after 8-16h, preparing HA/CS/PAM composite aquogel at 25 DEG C.
In above-mentioned preparation method, described hydroxyapatite powder crystal grain is 0.04 ~ 12 μ m, and gained solution concentration is 0.01-0.03g/mL; In described preparation chitosan (CS) aqueous solution process, drip upper 0.2-0.5mL acetic acid and accelerate the dissolving of chitosan, the concentration of chitosan solution is 0.005-0.01g/mL.
Described cross-linking agent is N, N'-methylene-bisacrylamide (MBA), and concentration is 0.001-0.005g/mL; Described initiator is potassium peroxydisulfate (KPS), and concentration is 0.005-0.01g/mL.
Described accelerator is N, N, and N', N'-tetramethylethylenediamine (TEMED), its density is 0.775g/mL, the mass ratio of the addition of described accelerator and monomer acrylamide is: 7.75:1000.
The mass ratio of described monomer acrylamide, initiator, cross-linking agent is (250 ~ 1500): 2.5:1; The mass ratio of described hydroxyapatite, chitosan, monomer acrylamide is (0.1-0.5): (0.05-0.2): (2-4).
The inventive method is first by hydroxyapatite (HA) and chitosan (CS) wiring solution-forming, then be doped in polyacrylamide (PAM) network structure, make a kind of good mechanical property that has, can be used as hydroxyapatite (HA)/chitosan (CS)/polyacrylamide (PAM) composite aquogel of cartilage substitution material.The present invention brings
beneficial effect:
(1) polyacrylamide is the cartilage substitution material that a kind of bio-compatibility is good, hydroxyapatite (HA) and chitosan (CS) material are mixed in polyacrylamide (PAM) hydrogel by hydrogen bond action, at hydroxyapatite (HA), chitosan (CS), polyacrylamide (PAM) is separately on the basis of advantage, the mechanical property of this trielement composite material is enhanced, and (while adding hydroxyapatite (HA) and chitosan (CS) mixed solution in polyacrylamide originally, compression stiffness significantly increases, for example: in the time compressing identical 5mm, be increased to 12 newton by 5 original newton.), for its multifunction application provides a technology platform, make it be expected to be applied to field of tissue engineering technology as cartilage substitution material;
(2) chitosan is a kind of softener material, and the present invention has strictly controlled the consumption of chitosan, and resulting materials has overcome the easy bending of chitosan (CS) support and the not good characteristic of engineering properties;
(3) retained good tension, the measuring body mechanical property of hydroxyapatite (HA);
(4) the method preparation process is easy and simple to handle, cost-saving.
Brief description of the drawings
Fig. 1 is the load-displacement curves figure of hydroxyapatite/chitosan/polyacrylamide compound water congealing glue material compression of different proportionings.
Fig. 2 is the load-displacement curves figure of the compound water congealing glue material compression under different chitosan proportionings.
Detailed description of the invention
Further illustrate the present invention below by embodiment, but be not limited to following examples.
embodiment 1:the preparation method of hydroxyapatite/chitosan/polyacrylamide composite aquogel
(1) preparation hydroxyapatite (HA) aqueous solution: 0.1g hydroxyapatite (HA) powder of 12 μ m is dissolved in to 5mL intermediate water, and concussion stirs it is fully dissolved, obtaining concentration is the milky HA solution of 0.02g/mL;
(2) preparation chitosan (CS) aqueous solution: 0.05g chitosan (CS) powder is dissolved in to 5mL intermediate water, and then adds 0.2mL acetic acid, finally concussion is stirred it is dissolved fully fast, and obtaining concentration is the CS solution of 0.01g/mL milk yellow;
(3) prepare cross-linking agent (MBA) aqueous solution: by 0.02g cross-linking agent N, N'-methylene-bisacrylamide (MBA) is dissolved in 5mL intermediate water, ultrasonic concussion 2min makes Solution Dispersion even, obtains the cross-linking agent aqueous solution that concentration is 0.004g/mL;
(4) prepare initiator (KPS) aqueous solution: get 0.05g initiator potassium persulfate (KPS) and be dissolved in 5mL intermediate water, ultrasonic concussion 2min makes Solution Dispersion even, obtains the initiator solution that concentration is 0.01g/mL;
(5) preparation of HA/CS/PAM inorganic-organic hybrid hydrogel: add monomer acrylamide 2g in test tube, then taking 0.5mL cross-linking agent solution drips in test tube, respectively getting the solution that 1mL above-mentioned (1), (2) obtain drips in test tube again, and add the concussion of 3mL intermediate water to shake up, monomer is fully dissolved; Then by test tube sealing, add subsequently 0.5mL initiator and 0.02mL accelerator, initiated polymerization carries out, after 12h, can preparing HA/CS/PAM composite aquogel at 25 DEG C.
Described accelerator is N, N, and N', N'-tetramethylethylenediamine, its density is 0.775g/mL.
Then, it is 13mm that compound water congealing glue material is cut into diameter, and the high cylinder specimen for 15mm carries out compression performance test.The results are shown in Figure 1.The test instrunment using in the present invention is Ai Debao pointer-type pull and push dynamometer NK-20, and method of testing is: the every compression of test specimen 5mm records the numerical value of pressure, finally utilizes SigmaPlot to draw out curve.
the comparative example 1 of embodiment 1:the preparation method of hydroxyapatite/polyacrylamide composite aquogel
Prepare hydroxyapatite (HA) aqueous solution, cross-linking agent (MBA) aqueous solution, initiator (KPS) aqueous solution by the method for embodiment 1;
In test tube, add monomer acrylamide 2g, take respectively 0.5mL cross-linking agent solution and drip in test tube, respectively get 1mL hydroxyapatite (HA) aqueous solution and drip in test tube, and add the concussion of 4mL intermediate water to shake up, monomer is fully dissolved; Then by test tube sealing, add subsequently 0.5mL initiator and 0.02mL accelerator, initiated polymerization carries out after 12h at 25 DEG C, can prepare HA/ PAM composite aquogel.Then, it is 13mm that compound water congealing glue material is cut into diameter, and the high cylinder specimen for 15mm carries out compression performance test.The results are shown in Figure 1.
the comparative example 2 of embodiment 1:the preparation method of polyacrylamide
Prepare cross-linking agent (MBA) aqueous solution, initiator (KPS) aqueous solution by the method for embodiment 1;
In test tube, add monomer acrylamide 2g, take 0.5mL cross-linking agent solution and drip in test tube, and add the concussion of 5mL intermediate water to shake up, monomer is fully dissolved; Then by test tube sealing, add subsequently 0.5mL initiator and 0.02mL accelerator, initiated polymerization carries out, after 12h, can preparing PAM polymer at 25 DEG C.Then, it is 13mm that compound water congealing glue material is cut into diameter, and the high cylinder specimen for 15mm carries out compression performance test.The results are shown in Figure 1.
The test result analysis of embodiment 1 and comparative example thereof:
Fig. 1 is the load-displacement curves figure of hydroxyapatite/chitosan/polyacrylamide compound water congealing glue material compression of different proportionings.W(HA in embodiment 1): w(CS): w(PAM)=0.02:0.01:2; W(HA in comparative example 1): w(PAM)=0.02:2; W(PAM in comparative example 2)=2; As can be seen from the figure, polyacrylamide adds that the compression stiffness of composite after hydroxyapatite and chitosan strengthens than independent polyacrylamide, and only contain the composite compression stiffness maximum of hydroxyapatite and polyacrylamide, visible chitosan is a kind of softener material.
embodiment 2:the preparation method of hydroxyapatite/chitosan/polyacrylamide composite aquogel
(1) preparation hydroxyapatite (HA) aqueous solution: 0.2g hydroxyapatite (HA) powder of 12 μ m is dissolved in to 10mL intermediate water, and concussion stirs it is fully dissolved, obtaining concentration is the milky HA solution of 0.02g/mL;
(2) preparation chitosan (CS) aqueous solution: 0.1g chitosan (CS) powder is dissolved in to 10mL intermediate water, and then adds 0.2mL acetic acid, finally concussion is stirred it is dissolved fully fast, and obtaining concentration is the CS solution of 0.01g/mL milk yellow;
(3) prepare cross-linking agent aqueous solution (MBA): by 0.04g cross-linking agent N, N'-methylene-bisacrylamide (MBA) is dissolved in 10mL intermediate water, ultrasonic concussion 2min makes Solution Dispersion even, obtains the cross-linking agent aqueous solution that concentration is 0.004g/mL;
(4) prepare initiator solution (KPS): get 0.1g initiator potassium persulfate (KPS) and be dissolved in 10mL intermediate water, ultrasonic concussion 2min makes Solution Dispersion even, obtains the initiator solution that concentration is 0.01g/mL;
(5) preparation of HA/CS/PAM inorganic-organic hybrid hydrogel: add monomer acrylamide 2g in test tube, taking 0.5mL cross-linking agent solution drips in test tube, respectively getting the solution that 1mL above-mentioned (1), (2) obtain drips in test tube again, and add the concussion of 3mL intermediate water to shake up, monomer is fully dissolved; Then by test tube sealing, add subsequently 0.5mL initiator and 0.02mL accelerator, initiated polymerization carries out, after 12h, can preparing HA/CS/PAM composite aquogel at 25 DEG C.
Described accelerator is N, N, and N', N'-tetramethylethylenediamine, its density is 0.775g/mL.
Then, it is 13mm that compound water congealing glue material is cut into diameter, and the high cylinder specimen for 15mm carries out compression performance test.The results are shown in Figure 2.The test instrunment using in the present invention is Ai Debao pointer-type pull and push dynamometer NK-20, and method of testing is: the every compression of test specimen 5mm records the numerical value of pressure, finally utilizes SigmaPlot to draw out curve.
the comparative example 1 of embodiment 2:the preparation method of hydroxyapatite/chitosan/polyacrylamide composite aquogel
This preparation method is identical with embodiment 2, and difference is: the consumption of chitosan (CS) is 2mL; The consumption of intermediate water is 2mL.
The compression performance test result of the present embodiment is shown in Fig. 2.
the comparative example 2 of embodiment 2:the preparation method of hydroxyapatite/chitosan/polyacrylamide composite aquogel
This preparation method is identical with embodiment 2, and difference is: the consumption of chitosan (CS) is 3mL; The consumption of intermediate water is 1mL.
The compression performance test result of the present embodiment is shown in Fig. 2.
the comparative example 3 of embodiment 2:the preparation method of hydroxyapatite/chitosan/polyacrylamide composite aquogel
This preparation method is identical with embodiment 2, and difference is: the consumption of chitosan (CS) is 4mL; The consumption of intermediate water is 0mL.
The compression performance test result of the present embodiment is shown in Fig. 2.
The test result analysis of embodiment 2 and comparative example thereof is as follows:
Fig. 2 is the load-displacement curves figure of the compound water congealing glue material compression under different chitosan proportionings.As can be seen from the figure, along with the increase (from 0.01g to 0.04g) of chitosan, the compressional stiffness of composite reduces gradually, the increase of visible chitosan content can reduce the mechanical property of this trielement composite material on the contrary, therefore chitosan can be used as a kind of composition of the mechanical property of adjusting hydroxyapatite/chitosan/Polyacrylamide Composite, in organizational project application, can regulate like this content of chitosan to make the cartilage substitution material of different-stiffness, for the position of different mechanical properties requirement.
Claims (6)
1. a preparation method for composite aquogel, is characterized in that: by hydroxyapatite and chitosan wiring solution-forming, be then doped in polyacrylamide network structure, specifically comprise the following steps:
(1) preparation hydroxyapatite aqueous solution: hydroxyapatite powder is dissolved in to intermediate water, and concussion stirs it is fully dissolved, obtain milky HA solution;
(2) preparation chitosan aqueous solution: chitosan powder is dissolved in to intermediate water, and then adds acetic acid, finally concussion is stirred it is dissolved fully fast, obtains the CS solution of milk yellow;
(3) prepare cross-linking agent aqueous solution: get cross-linking agent N, N'-methylene-bisacrylamide is dissolved in the water, ultrasonic concussion 2min makes Solution Dispersion even, obtains cross-linking agent aqueous solution;
(4) prepare initiator solution: get initiator potassium persulfate and be dissolved in the water, ultrasonic concussion 2min makes Solution Dispersion even, obtains initiator solution;
(5) preparation of HA/CS/PAM composite aquogel: add monomer acrylamide in test tube, the cross-linking agent solution that (3) are obtained adds in test tube, respectively get the solution that above-mentioned (1), (2) obtain and drip in test tube, and add intermediate water that monomer acrylamide is fully dissolved; Then by test tube sealing, add subsequently initiator and accelerator, initiated polymerization, reaction is carried out, after 8-16h, preparing HA/CS/PAM composite aquogel at 25 DEG C.
2. the preparation method of composite aquogel according to claim 1, is characterized in that: described hydroxyapatite powder grain size is 0.04 ~ 12 μ m, and gained solution concentration is 0.01-0.03g/mL.
3. the preparation method of composite aquogel according to claim 1, is characterized in that: in described preparation chitosan aqueous solution process, splash into 0.2-0.5 mL acetic acid and accelerate the dissolving of chitosan, the concentration of chitosan solution is 0.005-0.01g/mL.
4. the preparation method of composite aquogel according to claim 1, is characterized in that: described cross-linking agent is N, N'-methylene-bisacrylamide, and concentration is 0.001-0.005g/mL; Described initiator is potassium peroxydisulfate, and the initiator concentration of preparation is 0.005-0.01g/mL.
5. the preparation method of composite aquogel according to claim 1, is characterized in that: described accelerator is N, N, and N', N'-tetramethylethylenediamine, the mass ratio of the addition of described accelerator and monomer acrylamide is: 7.75:1000.
6. the preparation method of composite aquogel according to claim 1, is characterized in that: the mass ratio of described monomer acrylamide, initiator, cross-linking agent is (250 ~ 1500): 2.5:1; The mass ratio of described hydroxyapatite, chitosan, monomer acrylamide is (0.1-0.5): (0.05-0.2): (2-4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410467738.9A CN104189960B (en) | 2014-09-15 | 2014-09-15 | A kind of preparation method of composite aquogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410467738.9A CN104189960B (en) | 2014-09-15 | 2014-09-15 | A kind of preparation method of composite aquogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104189960A true CN104189960A (en) | 2014-12-10 |
| CN104189960B CN104189960B (en) | 2015-08-12 |
Family
ID=52075418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410467738.9A Active CN104189960B (en) | 2014-09-15 | 2014-09-15 | A kind of preparation method of composite aquogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104189960B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105232467A (en) * | 2015-10-26 | 2016-01-13 | 郑杉水 | Polyacrylamide gel peptization instant solid composite and preparing method thereof |
| CN107737370A (en) * | 2017-11-20 | 2018-02-27 | 西南交通大学 | It is a kind of to be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel |
| CN111171342A (en) * | 2020-01-19 | 2020-05-19 | 湖南工业大学 | High-toughness self-repairing fluorescent double-network hydrogel and preparation method thereof |
| CN111803697A (en) * | 2020-07-16 | 2020-10-23 | 太原理工大学 | Preparation method of drug-loaded sodium alginate/gelatin composite hydrogel type band-aid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060195179A1 (en) * | 2005-02-18 | 2006-08-31 | Wei Sun | Method for creating an internal transport system within tissue scaffolds using computer-aided tissue engineering |
| CN101130107A (en) * | 2007-08-22 | 2008-02-27 | 武汉大学 | Chitosan polyvinyl alcohol gel rubber containing nano granule of hydroxyapatite, producing method and uses of the same |
| CN102145196A (en) * | 2011-04-02 | 2011-08-10 | 中国人民解放军军事医学科学院基础医学研究所 | Bone tissue engineering scaffold material having anti-infection ability and preparation method of bone tissue engineering scaffold material |
| WO2012048283A1 (en) * | 2010-10-08 | 2012-04-12 | Board Of Regents, The University Of Texas System | One-step processing of hydrogels for mechanically robust and chemically desired features |
| CN102827446A (en) * | 2012-09-14 | 2012-12-19 | 武汉大学 | Temperature response type injectable hydrogel and preparation method and usage thereof |
-
2014
- 2014-09-15 CN CN201410467738.9A patent/CN104189960B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060195179A1 (en) * | 2005-02-18 | 2006-08-31 | Wei Sun | Method for creating an internal transport system within tissue scaffolds using computer-aided tissue engineering |
| CN101130107A (en) * | 2007-08-22 | 2008-02-27 | 武汉大学 | Chitosan polyvinyl alcohol gel rubber containing nano granule of hydroxyapatite, producing method and uses of the same |
| WO2012048283A1 (en) * | 2010-10-08 | 2012-04-12 | Board Of Regents, The University Of Texas System | One-step processing of hydrogels for mechanically robust and chemically desired features |
| CN102145196A (en) * | 2011-04-02 | 2011-08-10 | 中国人民解放军军事医学科学院基础医学研究所 | Bone tissue engineering scaffold material having anti-infection ability and preparation method of bone tissue engineering scaffold material |
| CN102827446A (en) * | 2012-09-14 | 2012-12-19 | 武汉大学 | Temperature response type injectable hydrogel and preparation method and usage thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105232467A (en) * | 2015-10-26 | 2016-01-13 | 郑杉水 | Polyacrylamide gel peptization instant solid composite and preparing method thereof |
| CN105232467B (en) * | 2015-10-26 | 2018-06-26 | 佛山市顺德区易优生物医药有限公司 | Polyacrylamide gel dispersion instant solid composite and preparation method thereof |
| CN107737370A (en) * | 2017-11-20 | 2018-02-27 | 西南交通大学 | It is a kind of to be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel |
| CN111171342A (en) * | 2020-01-19 | 2020-05-19 | 湖南工业大学 | High-toughness self-repairing fluorescent double-network hydrogel and preparation method thereof |
| CN111171342B (en) * | 2020-01-19 | 2022-07-05 | 湖南工业大学 | High-toughness self-repairing fluorescent double-network hydrogel and preparation method thereof |
| CN111803697A (en) * | 2020-07-16 | 2020-10-23 | 太原理工大学 | Preparation method of drug-loaded sodium alginate/gelatin composite hydrogel type band-aid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104189960B (en) | 2015-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104258461B (en) | A kind of preparation method of chitosan/oxidized Graphene/hydroxyapatite/Polyacrylamide Composite | |
| CN104231167A (en) | Preparation method of hydroxyapatite/graphene oxide/polyacrylamide composite hydrogel | |
| CN104189960B (en) | A kind of preparation method of composite aquogel | |
| CN107737370A (en) | It is a kind of to be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel | |
| CN107200799B (en) | Metallic ion coordination natural polymer/polyacrylic acid selfreparing gel process for preparing | |
| CN104177541B (en) | There is the preparation method of carbon point/polyacrylamide cartilage substitution material of fluorescent tracing performance | |
| US11365293B2 (en) | Xylan-based dual network nanocomposite hydrogel, preparation method thereof and use therefor | |
| CN105461945B (en) | A kind of covalent double-network hydrogel of ion and preparation method thereof | |
| CN105175755B (en) | High stretching dual network physical cross-linking hydrogel of a kind of high intensity and preparation method thereof | |
| CN103691000B (en) | The preparation method of micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support | |
| BR112012027407A2 (en) | polyacrylic acid (salt), water-absorbing resin based on polyacrylic acid (salt) and process for producing the same | |
| CN103387646B (en) | A kind of preparation method of the hydroxyapatite hydrogel for osteanagenesis | |
| Nakaoka et al. | Study on the potential of RGD-and PHSRN-modified alginates as artificial extracellular matrices for engineering bone | |
| CN104262881A (en) | Method for preparing high-strength double-network nano silicon dioxide composite hydrogel | |
| CN109134885A (en) | A kind of sodium alginate-chitosan poly ion complexes hydrogel and preparation method thereof | |
| Pescosolido et al. | Injectable and in situ gelling hydrogels for modified protein release | |
| AU2012328386B2 (en) | Highly swellable polymers | |
| CN101161689A (en) | Method for preparing rapid-responding and high mechanical performance hydrogel | |
| CN104341556A (en) | Preparation method of high-strength double-network nano hectorite composite aquagel | |
| CN106620845B (en) | Injectable bone material and method for preparing same | |
| CN106366248A (en) | Starch-based absorbent resin and preparation method therefor | |
| Wright et al. | Bioactive, Ion‐Releasing PMMA Bone Cement Filled with Functional Graphenic Materials | |
| CN101775148B (en) | Preparation method of microgel composite hydrogel | |
| Fan et al. | Highly stretchable, swelling-resistant, self-healed, and biocompatible dual-reinforced double polymer network hydrogels | |
| Akca et al. | Hydrophobically modified nanocomposite hydrogels with self‐healing ability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201116 Address after: Room 323, 301 Hanzhongmen street, Gulou District, Nanjing, Jiangsu Province, 210009 Patentee after: Wutong (Nanjing) Technology Co., Ltd Address before: 030024 Yingze, Shanxi Province, Berlin District, West Street, No. 79, No. Patentee before: Taiyuan University of Technology |