CN104710583B - A kind of preparation method of high intensity hydrogel - Google Patents
A kind of preparation method of high intensity hydrogel Download PDFInfo
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- CN104710583B CN104710583B CN201510080672.2A CN201510080672A CN104710583B CN 104710583 B CN104710583 B CN 104710583B CN 201510080672 A CN201510080672 A CN 201510080672A CN 104710583 B CN104710583 B CN 104710583B
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Abstract
The invention discloses a kind of preparation method of high intensity hydrogel, it is to be well mixed chitosan, methacrylic acid etc. with water first, after addition montmorillonite dispersions stir thereto, form mixed solution, initiator will be added after the mixed solution deoxygenation again, high intensity hydrogel is prepared in isothermal reaction afterwards for a period of time.The present invention prepares high intensity hydrogel by one-step method polymerization, without using the organic chemistry crosslinking agent of small molecule in preparation process, obtained hydrogel has superpower tensile property, its elongation at break is up to more than 3000%, with good biocompatibility, in bio-medical field, as the controlled release etc. of biology sensor, man-made organ, tissue renovation material, medicine has wide practical use.
Description
Technical field
The invention belongs to hydrogel preparation field, and in particular to a kind of preparation method of high intensity hydrogel.
Background technology
Macromolecule hydrogel is that the three-dimensional space network structure formed is swollen in after water by cross-linked polymer, usual netted knot
The water of filling 50~90% inside structure.As a kind of wet soft material, hydrogel in many aspects with some organs of human body and
Organize it is quite similar, therefore in bio-medical field (such as tissue renovation material, artificial muscle, biology sensor and pharmaceutical carrier
Etc.) show good application prospect.But relatively low mechanical property is often presented in traditional synthesis hydrogel, matter is crisp easily
It is broken, it is impossible to meet hydrogel in many field practical application requests.In order to improve the mechanical strength of hydrogel, in recent ten years,
Gel scholar develops some hydrogels for having new network structure and improving mechanical property, is opened up than more typical representative as having
Flutter the hydrogel of structure (or slip ring), organic-inorganic hybrid nanocomposite hydrogel, double-network hydrogel, four arm gels and organic
Macromolecular microspheres plural gel etc..
But the high intensity hydrogel reported often has many deficiencies, such as there is the water-setting of topological structure (or slip ring)
The preparation of glue and four arm hydrogels needs to use the gel precursors with special construction, and the requirement to gel precursors is high, is applicable model
Enclose narrow.Organic-inorganic hybrid nanocomposite hydrogel is due to mainly by being physical crosslinking the network structure formed, causing hydrogel steady
It is qualitative poor.Although the preparation of organic macromolecule microballoon composite aquogel is not required to separately add organic crosslinking agent, but need to prepare first
Contain the polymer microballoon of a large amount of free radicals (or decomposable asymmetric choice net forms the group of free radical) as initiator and big crosslinking agent in surface
To trigger monomer to polymerize, process is complex.Although the double-network hydrogel being made up of the asymmetric two kinds of cross-linked networks of intensity
Suitable for various of monomer, crosslinking agent and cross-linking method, but preparation process is complicated, generally requires the continuous radical polymerization of multistep
Journey, not only take and need to use the organic chemistry crosslinking agent of small molecule.Therefore, simple and easy high intensity hydrogel system is developed
Preparation Method is still a challenging job, has most important theories and actual meaning for the practical application for promoting hydrogel
Justice.
The content of the invention
It is an object of the invention to provide a kind of preparation method of high intensity hydrogel, and it is reacted by one-step polymerization prepares
Form, preparation technology is simple to operation, also, the hydrogel being prepared has superpower tensile property.
Its technical solution includes：
A kind of preparation method of high intensity hydrogel, comprises the following steps successively：
A, chitosan, methacrylic acid or methacrylic acid are mixed with mixture, the water of comonomer, fully stirred
To mix to obtain homogeneous transparent solution, solid content is 15~30% in the solution, wherein, the quality of chitosan point in solid mixture
Number is 4~10%, and surplus is methacrylic acid or the mixture of methacrylic acid and comonomer, and the quality of methacrylic acid is divided
Number accounts for the 3~100% of methacrylic acid and comonomer gross mass；
B, nitrogen is filled with into resulting solution with abundant deoxygenation, then addition initiator is abundant into the solution after removing oxygen
Mixing, the addition of initiator are the 0.5~2.5% of methacrylic acid and comonomer gross mass, are then placed on 25 ± 1
DEG C constant temperature water bath in, isothermal reaction 12-36 hours, produce high intensity hydrogel.
Using methacrylic acid and chitosan reaction generation chitosan methacrylate salt, gather shell originally not soluble in water
Sugar is dissolved in water and forms homogeneous solution, while chitosan methacrylate salt is as the multifunctional macromolecules cross-linking for preparing hydrogel
Agent.
As the preferred scheme of the present invention, in above-mentioned steps a, in step a, chitosan, methacrylic acid or methyl
After the mixture of acrylic acid and comonomer, water are sufficiently mixed, the montmorillonite dispersions that mass fraction is 0.5% are added thereto
It is well mixed, wherein, the mass fraction sum of montmorillonite and chitosan account for methacrylic acid and comonomer gross mass 4~
10%, the mass ratio of chitosan and montmorillonite is 7~25：1.
Montmorillonite is added as Physical crosslinking agent, prepares hydrogel with chitosan methacrylate salt composite crosslinking, favorably
In the mechanical property for improving hydrogel.
As another preferred scheme of the present invention, in step a, above-mentioned comonomer be acrylic acid, 2- acrylamidos-
2- methyl propane sulfonic acids, acrylamide, NIPA, N- vinyl caprolactams, N,N-DMAA, propylene
It is any in sour hydroxyl ethyl ester, hydroxyethyl methacrylate, polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate
It is a kind of.
By introducing different structure and property comonomer, a step section comonomer dosage of going forward side by side, to adjust hydrogel
Mechanical property, swelling behavior and stimuli responsive performance, so as to obtain a variety of difference in functionality hydrogels.
Further, above-mentioned initiator is any one in potassium peroxydisulfate, ammonium persulfate or sodium peroxydisulfate.
The preparation method of above-mentioned montmorillonite dispersions is：Montmorillonite is added to the water, mechanical agitation 30 minutes, ultrasonic disperse
Obtain within 2 hours.
The solid content of above-mentioned solution is 18~25%.
The addition of above-mentioned initiator is the 0.8~1.5% of methacrylic acid and comonomer gross mass.
Advantageous effects caused by the present invention：
The present invention proposes a kind of preparation method of high intensity hydrogel, and it is first by chitosan, methacrylic acid or first
Base acrylic acid is mixed with mixture, the water of comonomer, is formed mixed solution, then will be added after the mixed solution deoxygenation
High intensity hydrogel is prepared in initiator, isothermal reaction afterwards for a period of time；Preferably, it gathers one as the present invention in shell
Sugar, methacrylic acid or methacrylic acid and comonomer, water mixed liquor in add montmorillonite dispersions；Its choosing in raw material
Aspect is selected, by adding montmorillonite dispersions, as Physical crosslinking agent, is advantageous to the raising of gel mechanical property；
The present invention prepares high intensity hydrogel by one-step polymerization reaction, without using the organic of small molecule in preparation process
Chemical cross-linking agent；Obtained hydrogel has superpower tensile property (elongation at break is up to more than 3000%), good
Biocompatibility and pH-, temperature-responsive (partly have) performance, in bio-medical field (such as biology sensor, man-made organ, group
Knit controlled release of repair materials, medicine etc.) have wide practical use.
Prepared by the present invention is single network aqueous gel, without using small molecule organic crosslinking agent in its preparation, relative to existing
The preparation method of technology hydrogel as disclosed in CN103739861A, what it was prepared is double-network hydrogel, agar used, bright
Glue etc. forms the monomers such as the first heavy network therein, acrylamide and forms the second heavy network；Often weighing network is required for crosslinking agent to hand over
Connection, the polyvalent metal ion such as wherein added are mainly the crosslinking agent of the first weight network；The crosslinking agent of second weight network is N, N '-
The organic molecule crosslinking agent of the difunctionalitys such as methylene-bisacrylamide；Preparation technology of the present invention is simple, also, be prepared
Its tensile strength of hydrogel is 2.0MPa~3.7MPa, and stretch modulus is 180KPa~370KPa, and tension fracture elongation rate is
1500%~3800%, modulus of compressibility is 95KPa~305KPa, and compression strain is all higher than 98%.
Embodiment
The present invention proposes a kind of preparation method of high intensity hydrogel, in order that advantages of the present invention, technical scheme are more
Add clear, clear and definite, do further clear, complete explanation to the present invention with reference to specific embodiment.
The invention provides a kind of preparation method of high intensity hydrogel, and in the selection of raw material, selection has illiteracy de- for it
(acrylic acid, 2- acrylamide-2-methylpro panesulfonic acids, acrylamide, N- are different for soil, chitosan, methacrylic acid, comonomer
Propylacrylamide, N- vinyl caprolactams, N,N-DMAA, hydroxy-ethyl acrylate, hydroxyethyl methacrylate,
Polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate), initiator (potassium peroxydisulfate, ammonium persulfate or persulfuric acid
Sodium), above-mentioned raw materials can be commercially available by commercial channel.
A kind of preparation method of high intensity hydrogel, it specifically includes following steps：
Step 1, chitosan, methacrylic acid be well mixed with water three, or by chitosan, methacrylic acid with
The mixture and water of comonomer are mixed, and are sufficiently stirred to obtain homogeneous transparent solution；In the solution solid content be 15~
30%, wherein, the mass fraction of chitosan is 4~10% in solid mixture, and surplus is methacrylic acid either methyl-prop
The mixture of olefin(e) acid and comonomer, the mass fraction of methacrylic acid account for methacrylic acid and comonomer gross mass 3~
100%；
Step 2, nitrogen is filled with abundant deoxygenation into gained mixed solution, then add into the mixed solution after removing oxygen
Enter initiator to be sufficiently mixed, the addition of initiator is the 0.5~2.5% of methacrylic acid and comonomer gross mass, then
It is placed in 25 ± 1 DEG C of constant temperature water bath, isothermal reaction 12-36 hours, produces high intensity hydrogel.
It is following that the present invention will be further described in conjunction with specific embodiments：
Embodiment 1：
Chitosan, methacrylic acid are mixed with water three, are sufficiently stirred to obtain mixed solution；Contain admittedly in the mixed solution
Measure as 15%, wherein, the mass fraction of chitosan is 10% in solid mixture.
Into above-mentioned mixed solution, inflated with nitrogen after abundant deoxygenation, then adds over cure into mixed solution to remove oxygen
Sour aqueous solutions of potassium, the addition of potassium peroxydisulfate are the 1.5% of methacrylic acid gross mass, then transfer the solution into reaction mould
In reacted 12 hours under 25 DEG C of constant temperatures, produce hydrogel.
The hydrogel that the present embodiment is prepared, tensile strength 0.4MPa, stretch modulus 50KPa, tension failure are stretched
Long rate is 1300%, and modulus of compressibility about 25KPa, compression strain are more than 98%.
Embodiment 2：
Difference from Example 1 is：Solid content is 30% in mixed solution, chitosan wherein in solid mixture
Mass fraction is 4%.
The hydrogel that the present embodiment is prepared, tensile strength 1.6MPa, stretch modulus 180KPa, tension failure are stretched
Long rate is 1900%, and modulus of compressibility about 110KPa, compression strain are more than 98%.
Embodiment 3：
Difference from Example 1 is：Solid content is 18% in mixed solution, the quality of chitosan in solid mixture
Fraction is 5.5%.
The hydrogel that the present embodiment is prepared, tensile strength 1.8MPa, stretch modulus 195KPa, tension failure are stretched
Long rate is 3000%, and modulus of compressibility about 95KPa, compression strain are more than 98%.
Embodiment 4：
Difference from Example 1 is：Solid content is 18% in mixed solution, the quality of chitosan in solid mixture
Fraction is 7%.
The hydrogel that the present embodiment is prepared, tensile strength 2.6MPa, stretch modulus 250KPa, tension failure are stretched
Long rate is 3000%, and modulus of compressibility about 195KPa, compression strain are more than 98%.
Embodiment 5：
Difference from Example 1 is：Solid content is 18% in mixed solution, the quality of chitosan in solid mixture
Fraction is 10%.
The hydrogel that the present embodiment is prepared, tensile strength 2.2MPa, stretch modulus 235KPa, tension failure are stretched
Long rate is 3200%, and modulus of compressibility about 215KPa, compression strain are more than 98%.
Embodiment 6：
Chitosan, methacrylic acid, acrylamide are mixed with water, are sufficiently stirred to obtain mixed solution；The mixed solution
Middle solid content is 18%, wherein, the mass fraction of chitosan is 7% in solid mixture, and the mass fraction of methacrylic acid accounts for
Methacrylic acid and the 50% of acrylamide gross mass；
Into above-mentioned mixed solution, inflated with nitrogen after abundant deoxygenation, then adds over cure into mixed solution to remove oxygen
Sour aqueous solutions of potassium, the addition of potassium peroxydisulfate for methacrylic acid and acrylamide quality and 1.5%, then solution is shifted
Reacted 12 hours under 25 DEG C of constant temperatures into reaction mould, produce hydrogel.
The hydrogel that the present embodiment is prepared, tensile strength 2.0MPa, stretch modulus 220KPa, tension failure are stretched
Long rate is 3400%, and modulus of compressibility about 300KPa, compression strain are more than 98%.
Embodiment 7：
Chitosan, methacrylic acid, acrylic acid are mixed with water, are sufficiently stirred to obtain mixed solution；In the mixed solution
Solid content is 18%, wherein, the mass fraction of chitosan is 7% in solid mixture, and the mass fraction of methacrylic acid accounts for first
Base acrylic acid and the 50% of acrylic acid gross mass
Into above-mentioned mixed solution, inflated with nitrogen after abundant deoxygenation, then adds over cure into mixed solution to remove oxygen
Sour aqueous solutions of potassium, the addition of potassium peroxydisulfate for methacrylic acid and acrylic acid quality and 1.5%, then transfer the solution into
Reacted 12 hours under 25 DEG C of constant temperatures in reaction mould, produce hydrogel.
The hydrogel that the present embodiment is prepared, tensile strength 1.5MPa, stretch modulus 180KPa, tension failure are stretched
Long rate is 2100%, and modulus of compressibility about 205KPa, compression strain are more than 98%.
Embodiment 8：
A certain amount of montmorillonite is added to the water be sufficiently stirred 30 minutes, ultrasonic disperse is after 2 hours, montmorillonite quality is made
Fraction is 0.5% montmorillonite dispersions；
Chitosan, methacrylic acid are mixed with water three, is sufficiently stirred to obtain mixed solution, adds montmorillonite thereto
Dispersion liquid；Solid content is 18% in the mixed solution, wherein, chitosan and the mass fraction of montmorillonite are in solid mixture
5%, the mass ratio of chitosan and montmorillonite is 15.
Into above-mentioned mixed solution, inflated with nitrogen after abundant deoxygenation, then adds over cure into mixed solution to remove oxygen
Sour aqueous solutions of potassium, the addition of potassium peroxydisulfate are the 1.5% of methacrylic acid gross mass, then transfer the solution into reaction mould
In reacted 12 hours under 25 DEG C of constant temperatures, produce hydrogel.
The hydrogel that the present embodiment is prepared, tensile strength 2.7MPa, stretch modulus 300KPa, tension failure are stretched
Long rate is 3600%, and modulus of compressibility about 260KPa, compression strain are more than 98%.
Embodiment 9：
A certain amount of montmorillonite is added to the water be sufficiently stirred 30 minutes, ultrasonic disperse is after 2 hours, montmorillonite quality is made
Fraction is 0.5% montmorillonite dispersions；
Chitosan, methacrylic acid are mixed with water three, is sufficiently stirred to obtain mixed solution, adds montmorillonite thereto
Dispersion liquid；Solid content is 18% in the mixed solution, wherein, chitosan and the mass fraction of montmorillonite are in solid mixture
8%, the mass ratio of chitosan and montmorillonite is 15.
Into above-mentioned mixed solution, inflated with nitrogen after abundant deoxygenation, then adds over cure into mixed solution to remove oxygen
Sour aqueous solutions of potassium, the addition of potassium peroxydisulfate are the 1.5% of methacrylic acid gross mass, then transfer the solution into reaction mould
In reacted 12 hours under 25 DEG C of constant temperatures, produce hydrogel.
The hydrogel that the present embodiment is prepared, tensile strength 3.7MPa, stretch modulus 370KPa, tension failure are stretched
Long rate is 3800%, and modulus of compressibility about 305KPa, compression strain are more than 98%.
Comparative example 1：
By 0.15g N, N '-methylene-bisacrylamide, 2.1g methacrylic acids, 11.75g water are separately added into conical flask
In, stirring and dissolving, into solution, inflated with nitrogen is to remove oxygen, and after abundant deoxygenation, then addition potassium peroxydisulfate is water-soluble into solution
Liquid, persulfate aqueous solution are made from 0.0338g potassium peroxydisulfates are dissolved in 1mL water, then to transfer the solution into reaction mould
In reacted 24 hours under 25 ± 1 DEG C of constant temperatures, produce hydrogel.
The hydrogel that this comparative example is prepared, tensile strength 0.07MPa, stretch modulus 3KPa, tension failure are stretched
Long rate is 25%, compressive strength 65KPa, compression strain 75%.
Remaining comonomer not enumerated such as ethene such as polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate
Base monomer, the combination that those skilled in the art obtain under the enlightenment of the present invention, all should be within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of high intensity hydrogel, it is characterised in that comprise the following steps：
A, chitosan, methacrylic acid or methacrylic acid are mixed with mixture, the water of comonomer, are sufficiently stirred
To homogeneous transparent solution, solid content is 15~30% in the solution, wherein, the mass fraction of chitosan is in solid mixture
4~10%, surplus is methacrylic acid or the mixture of methacrylic acid and comonomer, and the mass fraction of methacrylic acid accounts for
The 3~100% of methacrylic acid and comonomer gross mass；
B, nitrogen is filled with into resulting solution with abundant deoxygenation, then adds initiator into the solution after removing oxygen and fully mixes
Close, the addition of initiator is the 0.5~2.5% of methacrylic acid and comonomer gross mass, is then placed on 25 ± 1 DEG C
Constant temperature water bath in, isothermal reaction 12-36 hours, produce high intensity hydrogel；
In step a, the comonomer is acrylic acid, 2- acrylamide-2-methylpro panesulfonic acids, acrylamide, N- isopropyls
Acrylamide, N- vinyl caprolactams, N,N-DMAA, hydroxy-ethyl acrylate, hydroxyethyl methacrylate, poly- second
Any one in diol mono-acrylate or polyethylene glycol monomethacrylate；
In step b, the initiator is any one in potassium peroxydisulfate, ammonium persulfate or sodium peroxydisulfate.
2. the preparation method of high intensity hydrogel according to claim 1, it is characterised in that：In step a, chitosan, first
After mixture, the water of base acrylic or methacrylic acid and comonomer are sufficiently mixed, it is 0.5% to add mass fraction thereto
Montmorillonite dispersions be well mixed, wherein, the mass fraction sum of montmorillonite and chitosan accounts for methacrylic acid and copolymerization is single
The mass ratio of the 4~10% of body gross mass, chitosan and montmorillonite is 7~25：1.
3. the preparation method of high intensity hydrogel according to claim 2, it is characterised in that：The preparation of montmorillonite dispersions
Method is：Montmorillonite is added to the water, mechanical agitation 30 minutes, ultrasonic disperse obtains for 2 hours.
4. the preparation method of high intensity hydrogel according to claim 2, it is characterised in that：The solid content of the solution is
18~25%.
5. the preparation method of high intensity hydrogel according to claim 2, it is characterised in that：In step b, initiator adds
Enter 0.8~1.5% that amount is methacrylic acid and comonomer gross mass.
6. the preparation method of high intensity hydrogel according to claim 2, it is characterised in that：Montmorillonite and the matter of chitosan
Amount fraction sum accounts for the 6~8% of methacrylic acid and comonomer gross mass, the mass ratio of chitosan and montmorillonite for 10~
15：1.
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| CN107537446A (en) * | 2017-10-10 | 2018-01-05 | 长沙爱扬医药科技有限公司 | Organic montmorillonite carried titanium dioxide material and preparation method thereof |
| CN113150320B (en) * | 2021-03-31 | 2022-06-24 | 中国地质大学（武汉） | Preparation method and application of irradiation-initiated chitosan-based double-network high-strength hydrogel |
| CN113461971B (en) * | 2021-06-28 | 2023-12-26 | 广州大学 | Conductive hydrogel and preparation method and application thereof |
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| CN103709328A (en) * | 2013-10-28 | 2014-04-09 | 北京林业大学 | Preparation method of hemicelluloses-based organic-inorganic compound hydrogel |
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