CN102276854B - Preparation method of high strength natural high-molecular hydrogel - Google Patents
Preparation method of high strength natural high-molecular hydrogel Download PDFInfo
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- CN102276854B CN102276854B CN 201110191644 CN201110191644A CN102276854B CN 102276854 B CN102276854 B CN 102276854B CN 201110191644 CN201110191644 CN 201110191644 CN 201110191644 A CN201110191644 A CN 201110191644A CN 102276854 B CN102276854 B CN 102276854B
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- carboxymethyl cellulose
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Abstract
The invention discloses a preparation method of high strength natural high-molecular hydrogel, characterized by that: the carboxymethyl cellulose molecular chain adopted in the invention has a large number of carboxylate ions (-COO-), by being immersed in a high concentration citric acid solution, the carboxylate ions on the carboxymethyl cellulose molecular chain accept a large number of hydrogen ions (H+) in the acid solution to be converted into carboxyl groups (-COOH), hydrogen bonding is generated between carboxyl groups, and a large number of hydrogen bonds taken as cross-link points connect the carboxymethyl cellulose molecular chain to form a tridimensional network, that is, hydrogel. The hydrogel contains a large number of high density hydrogen bonds in the composition, thus having high mechanic strength and stability.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of preparation method of high strength natural high-molecular hydrogel.
Background technology
Macromolecule hydrogel is a kind ofly to have the three-dimensional network space structure and soft, wet materials that water content is very high, and macromolecule hydrogel rapid swelling in water can be dewatered again under certain condition, and can be kept its three-dimensional net structure.A kind ofly to integrate suction, water conservation, slowly-releasing and develop rapidly functional high molecule material.
At present, most mechanical properties natural or hydrogel that synthetic material prepares are all relatively poor, even just chipping under very low pressure.In organizational project, what hope obtained is that a kind of macromolecule hydrogel with biocompatibility and biodegradability replaces the impaired soft tissue of human body, in the ideal case, hydrogel has and the similar performance of this soft tissue, replace soft tissue in human body, to work, hydrogel provides one well to cultivate the space as extracellular matrix to the human body soft tissue cell simultaneously, and hydrogel is also along with slowly degraded in the process of cell proliferation, when cell in hydrogel, cultivate finish after, new soft tissue produces.So with regard to biological degradability, natural polymer hydrogel is fit to the application in the human tissue engineering more.But mechanical property is the bad application and development that has seriously restricted again natural polymer hydrogel all.So synthetic a kind of high-intensity natural polymer hydrogel, and can keep the advantage of natural macromolecular material on biocompatibility, biodegradability, be to solve the key point that natural polymer hydrogel is used bottleneck, but also do not have the preparation method of such natural polymer hydrogel at present.
Summary of the invention
The deficiency that exists in order to overcome above-mentioned prior art, the object of the present invention is to provide a kind of preparation method of high strength natural high-molecular hydrogel, to have overcome mechanical property all relatively poor for the macromolecule hydrogel for preparing of preparation method thus, even under very low pressure with regard to chipping shortcoming, because it contains a large amount of highdensity hydrogen bonds, so mechanical strength and stability are all very high.
In order to achieve the above object, the technical solution adopted in the present invention is:
A kind of preparation method of high strength natural high-molecular hydrogel, step is as follows:
Step 1: at room temperature, be 250000-700000 with molecular weight ranges, substitution value is 0.9 carboxymethyl cellulose powder with pure water according to 20: 80-30: the mass ratio of 70 scopes mixes, after stirring, on mixing roll mixing 10-20 minute, the carboxymethyl cellulose powder after mixing and pure water mixture are pressed into the thick carboxymethyl cellulose hydrogel precursor of 1mm-3mm;
Step 2: at room temperature, the carboxymethyl cellulose hydrogel precursor that suppresses was soaked in the citric acid solution of 7mol/L-9mol/L 72 hours-96 hours, form the carboxymethyl cellulose hydrogel;
Step 3: at room temperature, the carboxymethyl cellulose hydrogel is exchanged to neutrality obtain high strength natural high-molecular hydrogel in pure water.
Exist a large amount of carboxylate radical (COO on the carboxymethyl cellulose molecular chain that the present invention adopts
-), by the immersion of High Content Citric Acid solution, the carboxylate radical on the carboxymethyl cellulose molecular chain is accepted hydrogen ion (H a large amount of in the acid solution
+), change carboxyl into (COOH).Can produce hydrogen bond action between carboxyl and the carboxyl, a large amount of hydrogen bonds couples together the carboxymethyl cellulose molecular chain as cross-linking set and forms tridimensional network, i.e. a hydrogel.Contain a large amount of, highdensity hydrogen bond in this hydrogel structure, so mechanical strength and stability are all very high.
Embodiment
The present invention will be described in more detail below in conjunction with embodiment.
Embodiment 1:
The preparation method of high strength natural high-molecular hydrogel, step is as follows:
Step 1: at room temperature, be 250000 with molecular weight ranges, substitution value is that 0.9 carboxymethyl cellulose powder mixes with the mass ratio of pure water according to 20: 80 scopes, after stirring, on mixing roll mixing 10 minutes, the carboxymethyl cellulose powder after mixing and pure water mixture are pressed into the thick carboxymethyl cellulose hydrogel precursor of 1mm;
Step 2: at room temperature, the carboxymethyl cellulose hydrogel precursor that suppresses was soaked 72 hours in the citric acid solution of 7mol/L, form the carboxymethyl cellulose hydrogel;
Step 3: at room temperature, the carboxymethyl cellulose hydrogel is exchanged to neutrality obtain high strength natural high-molecular hydrogel in pure water.
The strength at break that records the macromolecule hydrogel of this embodiment gained by three parallel tests is respectively: 919.7kPa, 1031.6kPa, 1027.9kPa.The data that measure can confirm from test, and this kind hydrogel mechanical property is good.
Embodiment 2:
The preparation method of high strength natural high-molecular hydrogel, step is as follows:
Step 1: at room temperature, be 300000 with molecular weight ranges, substitution value is that 0.9 carboxymethyl cellulose powder mixes with the mass ratio of pure water according to 25: 75 scopes, after stirring, on mixing roll mixing 15 minutes, the carboxymethyl cellulose powder after mixing and pure water mixture are pressed into the thick carboxymethyl cellulose hydrogel precursor of 2mm;
Step 2: at room temperature, the carboxymethyl cellulose hydrogel precursor that suppresses was soaked 80 hours in the citric acid solution of 8mol/L, form the carboxymethyl cellulose hydrogel;
Step 3: at room temperature, the carboxymethyl cellulose hydrogel is exchanged to neutrality obtain high strength natural high-molecular hydrogel in pure water.
The strength at break that records the macromolecule hydrogel of this embodiment gained by three parallel tests is respectively: 957.9kPa, 893.2kPa, 815.3kPa.The data that measure can confirm from test, and this kind hydrogel mechanical property is good.
Embodiment 3:
The preparation method of high strength natural high-molecular hydrogel, step is as follows:
Step 1: at room temperature, be 700000 with molecular weight ranges, substitution value is that 0.9 carboxymethyl cellulose powder mixes with the mass ratio of pure water according to 30: 70 scopes, after stirring, on mixing roll mixing 20 minutes, the carboxymethyl cellulose powder after mixing and pure water mixture are pressed into the thick carboxymethyl cellulose hydrogel precursor of 3mm;
Step 2: at room temperature, the carboxymethyl cellulose hydrogel precursor that suppresses was soaked 96 hours in the citric acid solution of 9mol/L, form the carboxymethyl cellulose hydrogel;
Step 3: at room temperature, the carboxymethyl cellulose hydrogel is exchanged to neutrality obtain high strength natural high-molecular hydrogel in pure water.
The strength at break that records the macromolecule hydrogel of this embodiment gained by three parallel tests is respectively: 937.6kPa, 900.2kPa, 952kPa.The data that measure can confirm from test, and this kind hydrogel mechanical property is good.
Claims (4)
1. the preparation method of a high strength natural high-molecular hydrogel is characterized in that, step is as follows:
Step 1: at room temperature, be 250000-700000 with molecular weight ranges, substitution value is 0.9 carboxymethyl cellulose powder with pure water according to 20: 80-30: the mass ratio of 70 scopes mixes, after stirring, on mixing roll mixing 10-20 minute, the carboxymethyl cellulose powder after mixing and pure water mixture are pressed into the thick carboxymethyl cellulose hydrogel precursor of 1mm-3mm;
Step 2: at room temperature, the carboxymethyl cellulose hydrogel precursor that suppresses was soaked in the citric acid solution of 7mol/L-9mol/L 72 hours-96 hours, form the carboxymethyl cellulose hydrogel;
Step 3: at room temperature, the carboxymethyl cellulose hydrogel is exchanged to neutrality obtain high strength natural high-molecular hydrogel in pure water.
2. the preparation method of high strength natural high-molecular hydrogel according to claim 1 is characterized in that, step is as follows:
Step 1: at room temperature, be 250000 with molecular weight ranges, substitution value is that 0.9 carboxymethyl cellulose powder mixes with the mass ratio of pure water according to 20: 80 scopes, after stirring, on mixing roll mixing 10 minutes, the carboxymethyl cellulose powder after mixing and pure water mixture are pressed into the thick carboxymethyl cellulose hydrogel precursor of 1mm;
Step 2: at room temperature, the carboxymethyl cellulose hydrogel precursor that suppresses was soaked 72 hours in the citric acid solution of 7mol/L, form the carboxymethyl cellulose hydrogel;
Step 3: at room temperature, the carboxymethyl cellulose hydrogel is exchanged to neutrality obtain high strength natural high-molecular hydrogel in pure water.
3. the preparation method of high strength natural high-molecular hydrogel according to claim 1 is characterized in that, step is as follows:
Step 1: at room temperature, be 300000 with molecular weight ranges, substitution value is that 0.9 carboxymethyl cellulose powder mixes with the mass ratio of pure water according to 25: 75 scopes, after stirring, on mixing roll mixing 15 minutes, the carboxymethyl cellulose powder after mixing and pure water mixture are pressed into the thick carboxymethyl cellulose hydrogel precursor of 2mm;
Step 2: at room temperature, the carboxymethyl cellulose hydrogel precursor that suppresses was soaked 80 hours in the citric acid solution of 8mol/L, form the carboxymethyl cellulose hydrogel;
Step 3: at room temperature, the carboxymethyl cellulose hydrogel is exchanged to neutrality obtain high strength natural high-molecular hydrogel in pure water.
4. the preparation method of high strength natural high-molecular hydrogel according to claim 1 is characterized in that, step is as follows:
Step 1: at room temperature, be 700000 with molecular weight ranges, substitution value is that 0.9 carboxymethyl cellulose powder mixes with the mass ratio of pure water according to 30: 70 scopes, after stirring, on mixing roll mixing 20 minutes, the carboxymethyl cellulose powder after mixing and pure water mixture are pressed into the thick carboxymethyl cellulose hydrogel precursor of 3mm;
Step 2: at room temperature, the carboxymethyl cellulose hydrogel precursor that suppresses was soaked 96 hours in the citric acid solution of 9mol/L, form the carboxymethyl cellulose hydrogel;
Step 3: at room temperature, the carboxymethyl cellulose hydrogel is exchanged to neutrality obtain high strength natural high-molecular hydrogel in pure water.
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| CN103788217B (en) * | 2013-12-26 | 2016-05-11 | 昆明理工大学 | A kind of cellulose gel glue material, Preparation method and use |
| CN105504312B (en) * | 2016-01-12 | 2017-08-15 | 西安交通大学 | The method for quickly preparing carboxymethyl cellulose-based luminous self-healing hydrogel |
| CN107973920A (en) * | 2017-11-15 | 2018-05-01 | 深圳大学 | A kind of cellulose/two-dimensional layer Material cladding hydrogel and preparation method thereof |
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| CN101128488A (en) * | 2004-12-29 | 2008-02-20 | 路易吉·安布罗西奥 | Biodegradable, super absorbent polymer hydrogels and a method for their preparation |
| CN101177488A (en) * | 2007-10-26 | 2008-05-14 | 广东工业大学 | Preparation of rapid swelling aquogel |
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| CN101128488A (en) * | 2004-12-29 | 2008-02-20 | 路易吉·安布罗西奥 | Biodegradable, super absorbent polymer hydrogels and a method for their preparation |
| CN101177488A (en) * | 2007-10-26 | 2008-05-14 | 广东工业大学 | Preparation of rapid swelling aquogel |
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