CN104693360A - Method for preparing high-strength hydrogel - Google Patents

Method for preparing high-strength hydrogel Download PDF

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CN104693360A
CN104693360A CN201510079586.XA CN201510079586A CN104693360A CN 104693360 A CN104693360 A CN 104693360A CN 201510079586 A CN201510079586 A CN 201510079586A CN 104693360 A CN104693360 A CN 104693360A
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acrylamide
methylpro panesulfonic
panesulfonic acid
chitosan
preparation
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CN104693360B (en
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马晓梅
夏延致
纪全
张振江
陈同旭
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Qingdao University
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Qingdao University
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Abstract

The invention discloses a method for preparing high-strength hydrogel. The method comprises the steps of firstly uniformly mixing chitosan, 2-acrylamido-2-methyl propanesulfonic acid and the like with water so as to obtain a mixture, adding a montmorillonite dispersion solution into the mixture, uniformly stirring so as to form a mixed solution, deoxidizing the mixed solution, then, adding an initiator, reacting for a period of time at a constant temperature, thereby preparing the high-strength hydrogel. According to the method, the high-strength hydrogel is prepared through one-step method polymerization, micromolecular organic chemical crosslinking agents are not used during preparation, and the prepared hydrogel has a super-strong tensile property, the elongation at break of over 4000% to the highest and good biocompatibility and has a broad application prospect in biomedical fields, such as biosensors, artificial organs, tissue repair materials and the controlled release of drugs.

Description

A kind of preparation method of high intensity hydrogel
Technical field
The invention belongs to hydrogel preparation field, be specifically related to a kind of preparation method of high intensity hydrogel.
Background technology
Macromolecule hydrogel is the three-dimensional space network structure formed after swelling in water by cross-linked polymer, and the water of 50 ~ 90% is filled in usual reticulated structure inside.As a kind of wet soft material, hydrogel is quite similar with some Organ and tissues of human body in many aspects, therefore demonstrates good application prospect at bio-medical field (in tissue renovation material, artificial muscle, biosensor and pharmaceutical carrier etc.).But traditional synthetic water gel often presents lower mechanical property, and matter is crisp frangible, hydrogel practical application request in a lot of fields can not be met.In order to improve the physical strength of hydrogel, in recent ten years, gel scholar develops some hydrogels having new network structure and improve mechanical property, relatively more typical hydrogel, organic-inorganic hybrid nanocomposite hydrogel, double-network hydrogel, four arm gels and the organic macromolecule microballoon plural gel etc. represented as having topological framework (or slip ring).
But often there is many deficiencies in the high intensity hydrogel reported, preparation as the hydrogel and four arm hydrogels with topological framework (or slip ring) needs to use the gel precursor with special construction, narrow application range high to the requirement of gel precursor.Organic-inorganic hybrid nanocomposite hydrogel, due to mainly by the network structure that physical crosslinking is formed, causes hydrogel less stable.Although the preparation of organic macromolecule microballoon composite aquogel does not need separately to add organic crosslinking agent, but need first to prepare the polymer microballoon of surface containing a large amount of free radical (or decomposable asymmetric choice net forms the group of free radical) and carry out trigger monomer polymerization as initiator and large linking agent, process is comparatively complicated.Although the double-network hydrogel be made up of the asymmetric two kinds of cross-linked networks of intensity is applicable to various of monomer, linking agent and cross-linking method, but preparation process is complicated, often need the continuous radical polymerization process of multistep, not only consuming time and need to use micromolecular organic chemistry linking agent.Therefore, develop simple high intensity hydrogel preparation method and remain a challenging job, for the practical application promoting hydrogel, there is most important theories and practical significance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high intensity hydrogel, it is prepared from by one-step polymerization reaction, and preparation technology is simple to operation, and the hydrogel prepared has superpower tensile property.
Its technical solution comprises:
A preparation method for high intensity hydrogel, comprises the following steps successively:
A, by chitosan, the mixture of 2-acrylamide-2-methylpro panesulfonic acid or 2-acrylamide-2-methylpro panesulfonic acid and comonomer, water mixes, abundant stirring obtains homogeneous transparent solution, in described solution, solid content is 10 ~ 30%, wherein, in solid mixture, the massfraction of chitosan is 4 ~ 10%, surplus is the mixture of 2-acrylamide-2-methylpro panesulfonic acid or 2-acrylamide-2-methylpro panesulfonic acid and comonomer, the massfraction of 2-acrylamide-2-methylpro panesulfonic acid accounts for 7 ~ 100% of 2-acrylamide-2-methylpro panesulfonic acid and comonomer total mass,
B, in gained solution, be filled with nitrogen with abundant deoxygenation, in the solution after removing oxygen, add initiator more fully to mix, the add-on of initiator is 0.5 ~ 2.5% of 2-acrylamide-2-methylpro panesulfonic acid and comonomer total mass, then be placed in the constant temperature water bath of 25 ± 1 DEG C, isothermal reaction 12-36 hour, obtains high intensity hydrogel.
Utilize 2-acrylamide-2-methylpro panesulfonic acid and chitosan reaction generating chitosan 2-acrylamide-2-methylpro panesulfonic acid salt, make water-fast chitosan originally be dissolved in water and form homogeneous solution, chitosan 2-acrylamide-2-methylpro panesulfonic acid salt is as the multifunctional macromolecules cross-linking agent preparing hydrogel simultaneously.
As a preferred version of the present invention, in above-mentioned steps a, after the mixture of chitosan, 2-acrylamide-2-methylpro panesulfonic acid or 2-acrylamide-2-methylpro panesulfonic acid and comonomer, water fully mix, add wherein massfraction be 0.5% montmorillonite dispersions mix, wherein, the massfraction sum of polynite and chitosan accounts for 4 ~ 10% of 2-acrylamide-2-methylpro panesulfonic acid and comonomer total mass, and the mass ratio of chitosan and polynite is 7 ~ 25:1.
Add polynite as physical crosslinking agent, prepare hydrogel with chitosan 2-acrylamide-2-methylpro panesulfonic acid salt composite crosslinking, be conducive to the mechanical property improving hydrogel.
As another preferred version of the present invention, in step a, above-mentioned comonomer is any one in methacrylic acid, vinylformic acid, acrylamide, NIPA, N-vinyl caprolactam, N,N-DMAA, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate.
By introducing different structure and character comonomer, a step joint comonomer consumption of going forward side by side, regulates the mechanical property of hydrogel, swelling behavior and stimuli responsive performance, thus obtains multiple difference in functionality hydrogel.
Further, above-mentioned initiator is any one in Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
The preparation method of above-mentioned montmorillonite dispersions is: polynite be added to the water, mechanical stirring 30 minutes, and ultrasonic disperse obtains for 2 hours.
The solid content of above-mentioned solution is 10 ~ 15%.
The add-on of above-mentioned initiator is 0.8 ~ 1.5% of 2-acrylamide-2-methylpro panesulfonic acid and comonomer total mass.
The Advantageous Effects that the present invention brings:
The present invention proposes a kind of preparation method of high intensity hydrogel, first the mixture of chitosan, 2-acrylamide-2-methylpro panesulfonic acid or 2-acrylamide-2-methylpro panesulfonic acid and comonomer, water mix by it, form mixing solutions, then add initiator by after this mixing solutions deoxygenation, isothermal reaction prepares high intensity hydrogel after for some time; As of the present invention one preferably, it adds montmorillonite dispersions in the mixed solution of chitosan, 2-acrylamide-2-methylpro panesulfonic acid or 2-acrylamide-2-methylpro panesulfonic acid and comonomer, water; It is in the selection of raw material, by adding montmorillonite dispersions, as physical crosslinking agent, being conducive to gel mechanical property and improving;
The present invention is reacted by one-step polymerization and prepares high intensity hydrogel, does not use micromolecular organic chemistry linking agent in preparation process; Obtained hydrogel has superpower tensile property (elongation at break is up to more than 4000%), good biocompatibility and pH, temperature response (part has) performance, and in bio-medical field, (in the controlled release etc. of biosensor, artificial organ, tissue renovation material, medicine) has wide practical use.
Prepared by the present invention is single network aqueous gel, small molecules organic crosslinking agent is not used in its preparation, relative to the preparation method of prior art hydrogel disclosed in CN103739861A, what it was prepared is double-network hydrogel, agar used, gelatin etc. form the first heavy network wherein, and the monomers such as acrylamide form the second heavy network; Often heavy network all needs cross-linking agents, as the linking agent of the polyvalent metal ion that wherein adds mainly the first heavy network; The linking agent of the second heavy network is N, N ' the dual functional organic molecule linking agent such as-methylene-bisacrylamide; Preparation technology of the present invention is simple, and its tensile strength of the hydrogel prepared is 2.0MPa ~ 3.3MPa, tensile modulus is 165KPa ~ 320KPa, tension fracture elongation rate is 1600% ~ 4200%, and modulus of compression is 95KPa ~ 310KPa, and compressive strain is all greater than 98%.
Embodiment
The present invention proposes a kind of preparation method of high intensity hydrogel, in order to make advantage of the present invention, technical scheme clearly, clearly, below in conjunction with specific embodiment, explanation clear, complete further being done to the present invention.
The invention provides a kind of preparation method of high intensity hydrogel, it is in the selection of raw material, that selects has polynite, chitosan, 2-acrylamide-2-methylpro panesulfonic acid, comonomer (methacrylic acid, vinylformic acid, acrylamide, NIPA, N-vinyl caprolactam, N, N-DMAA, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate), initiator (Potassium Persulphate, ammonium persulphate or Sodium Persulfate), above-mentioned raw materials is all bought by commercial channel and is obtained.
A preparation method for high intensity hydrogel, it specifically comprises the following steps:
Step 1, chitosan, 2-acrylamide-2-methylpro panesulfonic acid to be mixed with water three, or the mixture of chitosan, 2-acrylamide-2-methylpro panesulfonic acid and comonomer and water are mixed, fully stir and obtain homogeneous transparent solution; In this solution, solid content is 10 ~ 30%, wherein, in solid mixture, the massfraction of chitosan is 4 ~ 10%, surplus is the mixture of 2-acrylamide-2-methylpro panesulfonic acid or 2-acrylamide-2-methylpro panesulfonic acid and comonomer, and the massfraction of 2-acrylamide-2-methylpro panesulfonic acid accounts for 7 ~ 100% of 2-acrylamide-2-methylpro panesulfonic acid and comonomer total mass;
Step 2, in gained mixing solutions, be filled with nitrogen with abundant deoxygenation, in the mixing solutions after removing oxygen, add initiator more fully to mix, the add-on of initiator is 0.5 ~ 2.5% of 2-acrylamide-2-methylpro panesulfonic acid and comonomer total mass, then be placed in the constant temperature water bath of 25 ± 1 DEG C, isothermal reaction 12-36 hour, obtains high intensity hydrogel.
It is following that the present invention will be further described in conjunction with specific embodiments:
Embodiment 1:
Chitosan, 2-acrylamide-2-methylpro panesulfonic acid are mixed with water three, fully stirs and obtain mixing solutions; In this mixing solutions, solid content is 10%, and wherein, in solid mixture, the massfraction of chitosan is 10%.
In above-mentioned mixing solutions, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, persulfate aqueous solution is added again in mixing solutions, the add-on of Potassium Persulphate is 1.5% of 2-acrylamide-2-methylpro panesulfonic acid total mass, then solution is transferred in reaction mould and react 12 hours under 25 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that the present embodiment prepares, tensile strength is 0.25MPa, tensile modulus is 30KPa, tension fracture elongation rate is 1600%, and modulus of compression is about 22KPa, compressive strain is greater than 98%.
Embodiment 2:
Difference from Example 1 is: in mixing solutions, solid content is 30%, and wherein in solid mixture, the massfraction of chitosan is 4%.
The hydrogel that the present embodiment prepares, tensile strength is 1.6MPa, tensile modulus is 180KPa, tension fracture elongation rate is 2400%, and modulus of compression is about 100KPa, compressive strain is greater than 98%.
Embodiment 3:
Difference from Example 1 is: in mixing solutions, solid content is 15%, and in solid mixture, the massfraction of chitosan is 5.5%.
The hydrogel that the present embodiment prepares, tensile strength is 1.8MPa, tensile modulus is 195KPa, tension fracture elongation rate is 3700%, and modulus of compression is about 95KPa, compressive strain is greater than 98%.
Embodiment 4:
Difference from Example 1 is: in mixing solutions, solid content is 15%, and in solid mixture, the massfraction of chitosan is 7%.
The hydrogel that the present embodiment prepares, tensile strength is 2.2MPa, tensile modulus is 225KPa, tension fracture elongation rate is 3300%, and modulus of compression is about 195KPa, compressive strain is greater than 98%.
Embodiment 5:
Difference from Example 1 is: in mixing solutions, solid content is 15%, and in solid mixture, the massfraction of chitosan is 10%.
The hydrogel that the present embodiment prepares, tensile strength is 2.0MPa, tensile modulus is 210KPa, tension fracture elongation rate is 3000%, and modulus of compression is about 205KPa, compressive strain is greater than 98%.
Embodiment 6:
Chitosan, 2-acrylamide-2-methylpro panesulfonic acid, acrylamide are mixed with water, fully stirs and obtain mixing solutions; In this mixing solutions, solid content is 15%, and wherein, in solid mixture, the massfraction of chitosan is that the massfraction of 7%, 2-acrylamide-2-methylpro panesulfonic acid accounts for 50% of 2-acrylamide-2-methylpro panesulfonic acid and acrylamide total mass;
In above-mentioned mixing solutions, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, persulfate aqueous solution is added again in mixing solutions, the add-on of Potassium Persulphate be 2-acrylamide-2-methylpro panesulfonic acid and acrylamide quality and 1.5%, then solution is transferred in reaction mould and react 12 hours under 25 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that the present embodiment prepares, tensile strength is 2.05MPa, tensile modulus is 230KPa, tension fracture elongation rate is 3600%, and modulus of compression is about 310KPa, compressive strain is greater than 98%.
Embodiment 7:
Chitosan, 2-acrylamide-2-methylpro panesulfonic acid, methacrylic acid are mixed with water, fully stirs and obtain mixing solutions; In this mixing solutions, solid content is 15%, and wherein, in solid mixture, the massfraction of chitosan is that the massfraction of 7%, 2-acrylamide-2-methylpro panesulfonic acid accounts for 50% of 2-acrylamide-2-methylpro panesulfonic acid and methacrylic acid total mass;
In above-mentioned mixing solutions, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, persulfate aqueous solution is added again in mixing solutions, the add-on of Potassium Persulphate be 2-acrylamide-2-methylpro panesulfonic acid and methacrylic acid quality and 1.5%, then solution is transferred in reaction mould and react 12 hours under 25 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that the present embodiment prepares, tensile strength is 1.5MPa, tensile modulus is 165KPa, tension fracture elongation rate is 2100%, and modulus of compression is about 195KPa, compressive strain is greater than 98%.
Embodiment 8:
A certain amount of polynite is added to the water abundant stirring 30 minutes, ultrasonic disperse after 2 hours, obtained polynite massfraction is the montmorillonite dispersions of 0.5%;
Chitosan, 2-acrylamide-2-methylpro panesulfonic acid are mixed with water three, fully stirs and obtain mixing solutions, add montmorillonite dispersions wherein; In this mixing solutions, solid content is 15%, and wherein, the massfraction of chitosan and polynite in solid mixture is 5%, and the mass ratio of chitosan and polynite is 15;
In above-mentioned mixing solutions, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, persulfate aqueous solution is added again in mixing solutions, the add-on of Potassium Persulphate is 1.5% of 2-acrylamide-2-methylpro panesulfonic acid total mass, then solution is transferred in reaction mould and react 12 hours under 25 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that the present embodiment prepares, tensile strength is 2.6MPa, tensile modulus is 290KPa, tension fracture elongation rate is 3900%, and modulus of compression is about 200KPa, compressive strain is greater than 98%.
Embodiment 9:
A certain amount of polynite is added to the water abundant stirring 30 minutes, ultrasonic disperse after 2 hours, obtained polynite massfraction is the montmorillonite dispersions of 0.5%;
Chitosan, 2-acrylamide-2-methylpro panesulfonic acid are mixed with water three, fully stirs and obtain mixing solutions, add montmorillonite dispersions wherein; In this mixing solutions, solid content is 15%, and wherein, the massfraction of chitosan and polynite in solid mixture is 8%, and the mass ratio of chitosan and polynite is 15.
In above-mentioned mixing solutions, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, persulfate aqueous solution is added again in mixing solutions, the add-on of Potassium Persulphate is 1.5% of 2-acrylamide-2-methylpro panesulfonic acid total mass, then solution is transferred in reaction mould and react 12 hours under 25 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that the present embodiment prepares, tensile strength is 3.3MPa, tensile modulus is 320KPa, tension fracture elongation rate is 4200%, and modulus of compression is about 270KPa, compressive strain is greater than 98%.
Comparative example 1:
By 0.11g N, N '-methylene-bisacrylamide, 1.39g 2-acrylamide-2-methylpro panesulfonic acid, 12.5g water add in Erlenmeyer flask respectively, stirring and dissolving, in solution, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, then add persulfate aqueous solution in solution, it is obtained that persulfate aqueous solution is that 0.0208g Potassium Persulphate is dissolved in 1mL water, then solution is transferred in reaction mould and react 24 hours under 25 ± 1 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that this comparative example prepares, tensile strength is 0.02MPa, tensile modulus is 0.5KPa, tension fracture elongation rate is about 20%, compressive strength 60KPa, compressive strain 55%.
All the other comonomers do not exemplified are as the vinyl monomer such as polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, and the combination that those skilled in the art obtain under enlightenment of the present invention, all should within protection scope of the present invention.

Claims (8)

1. a preparation method for high intensity hydrogel, is characterized in that, comprises the following steps:
A, by chitosan, the mixture of 2-acrylamide-2-methylpro panesulfonic acid or 2-acrylamide-2-methylpro panesulfonic acid and comonomer, water mixes, abundant stirring obtains homogeneous transparent solution, in described solution, solid content is 10 ~ 30%, wherein, in solid mixture, the massfraction of chitosan is 4 ~ 10%, surplus is the mixture of 2-acrylamide-2-methylpro panesulfonic acid or 2-acrylamide-2-methylpro panesulfonic acid and comonomer, the massfraction of 2-acrylamide-2-methylpro panesulfonic acid accounts for 7 ~ 100% of 2-acrylamide-2-methylpro panesulfonic acid and comonomer total mass,
B, in gained solution, be filled with nitrogen with abundant deoxygenation, in the solution after removing oxygen, add initiator more fully to mix, the add-on of initiator is 0.5 ~ 2.5% of 2-acrylamide-2-methylpro panesulfonic acid and comonomer total mass, then be placed in the constant temperature water bath of 25 ± 1 DEG C, isothermal reaction 12-36 hour, obtains high intensity hydrogel.
2. the preparation method of high intensity hydrogel according to claim 1, it is characterized in that: in step a, after the mixture of chitosan, 2-acrylamide-2-methylpro panesulfonic acid or 2-acrylamide-2-methylpro panesulfonic acid and comonomer, water fully mix, add wherein massfraction be 0.5% montmorillonite dispersions mix, wherein, the massfraction sum of polynite and chitosan accounts for 4 ~ 10% of 2-acrylamide-2-methylpro panesulfonic acid and comonomer total mass, and the mass ratio of chitosan and polynite is 7 ~ 25:1.
3. the preparation method of high intensity hydrogel according to claim 1 and 2, it is characterized in that: in step a, described comonomer is any one in methacrylic acid, vinylformic acid, acrylamide, NIPA, N-vinyl caprolactam, N,N-DMAA, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate.
4. the preparation method of high intensity hydrogel according to claim 3, is characterized in that: in step b, and described initiator is any one in Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
5. the preparation method of high intensity hydrogel according to claim 3, is characterized in that: the preparation method of montmorillonite dispersions is: polynite be added to the water, mechanical stirring 30 minutes, and ultrasonic disperse obtains for 2 hours.
6. the preparation method of high intensity hydrogel according to claim 3, is characterized in that: the solid content of described solution is 10 ~ 15%.
7. the preparation method of high intensity hydrogel according to claim 3, is characterized in that: in step b, and the add-on of initiator is 0.8 ~ 1.5% of 2-acrylamide-2-methylpro panesulfonic acid and comonomer total mass.
8. the preparation method of high intensity hydrogel according to claim 2, it is characterized in that: the massfraction sum of polynite and chitosan accounts for 6 ~ 8% of 2-acrylamide-2-methylpro panesulfonic acid and comonomer total mass, the mass ratio of chitosan and polynite is 10 ~ 15:1.
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CN107629219A (en) * 2017-10-10 2018-01-26 戴琪 A kind of preparation method of high intensity hydrogel
CN109575508A (en) * 2018-11-14 2019-04-05 安徽明光中兴阳光新能源科技有限公司 A kind of phenolic resin compound insulating material and preparation method thereof
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CN113150320A (en) * 2021-03-31 2021-07-23 中国地质大学(武汉) Preparation method and application of irradiation-initiated chitosan-based double-network high-strength hydrogel
CN114196046A (en) * 2021-12-23 2022-03-18 北京理工大学 Process for preparing self-growing hydrogel

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