CN109942840A - A kind of polyvinyl alcohol composite hydrogel and preparation method thereof - Google Patents
A kind of polyvinyl alcohol composite hydrogel and preparation method thereof Download PDFInfo
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- CN109942840A CN109942840A CN201910275109.9A CN201910275109A CN109942840A CN 109942840 A CN109942840 A CN 109942840A CN 201910275109 A CN201910275109 A CN 201910275109A CN 109942840 A CN109942840 A CN 109942840A
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Abstract
The invention belongs to technical field of polymer materials, more particularly to a kind of polyvinyl alcohol composite hydrogel and preparation method thereof, halloysite nanotubes are by silane coupler modified, then in ultrasonic disperse water, modified halloysite nanotubes dispersion liquid is slowly dropped in the polyvinyl alcohol water solution of 10-20%, stirring to obtain homogeneous mixture solotion；Mixed solution is poured into mold, glass plate is covered, -20 DEG C of low temperature refrigerator is put into and freezes 12 hours, taking-up is thawed 8 hours at 20 DEG C；So freezing, defrosting three times, both obtain polyvinyl alcohol composite hydrogel.The present invention, which is provided, has the advantages that high mechanical properties, good heat stability good biocompatibility, water conservation imbibition ability is strong using the polyvinyl alcohol composite hydrogel of freeze-thaw method preparation；Toxic solvent is not used in preparation process, preparation method is simple, and raw material is easy to get, environmental-friendly.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of polyvinyl alcohol composite hydrogel and its preparation side
Method.
Background technique
Polyvinyl alcohol hydrogel is wide due to the advantages that toxicity is low, good mechanical performance, water absorption are high and good biocompatibility
It is general to be applied to the every field such as agricultural, medicine, daily-use chemical industry, environmental protection.But its elasticity of polyvinyl alcohol hydrogel is insufficient, flexibility compared with
Difference, hydrophily existing defects and cannot be used alone, usually by various nanofillers, natural polymer etc. to improve polyethylene
The mechanical property of alcohol hydrogel.Jiang Yao Pei etc., polymer material science and engineering, 2018,34 (07), using freeze-thaw side
Method is prepared for polyvinyl alcohol/sodium alginate/graphene oxide composite hydrogel, and research finds to increase with graphene oxide content,
Mechanical property, thermal stability of hydrogel etc. are improved and show excellent biocompatibility.Wang Zhiguo etc., Nanjing industry
College journal (natural science edition), 2017,39 (06) are chemically crosslinked by cellulose nano-fibrous use with polyvinyl alcohol
Method is prepared for cellulose nano-fibrous/polyvinyl alcohol composite hydrogel, the results showed that cellulose nano-fibrous addition can improve
The mechanical property of polyvinyl alcohol hydrogel.Arm spread is super, and modern salt chemical engineering, 2017,44 (03) are prepared for using freeze-thaw method
Polyvinyl alcohol/polyacrylic acid composite hydrogel, research find the water absorbent rate height of composite hydrogel, high mechanical strength.Polyethylene
Alcohol composite hydrogel preparation method is divided into physical crosslinking and chemical crosslink technique by crosslinking method, and wherein chemical crosslink technique preparation is poly-
Polyvinyl alcohol hydrogel cross-linking reaction is insufficient, and mechanical strength is low；Physical crosslinking method applies more, the polyvinyl alcohol hydrogel of preparation
Mechanical strength is high, but complex process technique is not easy to control.
For example, the Chinese invention patent 201710074280.4 of Peng Huafeng first mixes cellulose solution, poly-vinyl alcohol solution
It is even, it is added in assembly mold, pregelatinized obtains the gel of pregelatinized, then displaces solvent, and recrystallization crosslinking is made
Excellent in mechanical performance, in water or humid stability is high, translucency is high polyvinyl alcohol composite hydrogel.
The patent need to impregnate repeatedly during preparing composite hydrogel under the conditions of 5 DEG C displaces solvent, and time-consuming, consumption
Water and easily cause solvent that cannot be precipitated completely.
In addition, the Chinese invention patent 201210329897.3 of leaf woods uses polar elastomers material, through coupling agent treatment
Inorganic nano-particle with polyvinyl alcohol is compound is prepared for a kind of polyethylene by the boric acid aqueous solution crosslinking curing containing curing agent
Alcohol hydrogel.The hydrogel is by playing the toughening effect of elastomeric material and the enhancement effect of inorganic nano-particle, to mention
High density polyethylene alcohol hydrogel mechanical strength and toughness, prolong the service life, and meet requirement of the actual use to mechanical property.
Patent inorganic nano-particle dispersibility in polyvinyl alcohol during preparing polyvinyl alcohol hydrogel is not easily-controllable
System, easily causes gel strength unstable, secondly has biggish cytotoxicity using crosslinking agent boric acid, is not suitable for bio-medical
Material.
Summary of the invention
The object of the present invention is to provide a kind of Novel polyvinyl alcohol composite hydrogel and preparation method thereof, feature first is that
Halloysite nanotubes are introduced in hydrogel network structure, are formed by the hydrogen bond action of its surface hydroxyl abundant and polyvinyl alcohol
Physical cross-linked network makes up the mechanical strength defect of polyvinyl alcohol hydrogel.Feature using circulating frozen-freezing process second is that prepared
Polyethylene composite hydrogel simple process, raw material is easy to get.Feature is third is that polyvinyl alcohol composite hydrogel made from the method has
It is nontoxic, the advantages that preferable swellability, biocompatibility, thermal stability and mechanical property, suitable for doing wound dressing use.
Specific technical solution are as follows:
A kind of polyvinyl alcohol composite hydrogel is made according to parts by weight of following raw material: 50-100 parts of polyvinyl alcohol；Change
25-80 parts of halloysite nanotubes of property；There are also suitable water.
The polyvinyl alcohol is that the polyvinyl alcohol that the degree of polymerization is 700-6000, alcoholysis degree is 70-99% is one or more
Any mixing.
The modification halloysite nanotubes, it is even by silane coupler modified, described silane for halloysite nanotubes
Connection agent is vinyltriethoxysilane, vinyltrimethoxysilane, any in vinyl three (beta-methoxy ethyoxyl) silane
It is a kind of.
The preparation method of the polyvinyl alcohol composite hydrogel, comprising the following steps:
(1) prepared by raw material
Halloysite nanotubes surface treatment: by 5-30 part halloysite nanotubes and 1-30 parts of silane coupling agents be dispersed in water and
Acetone volume ratio is in the solution of 1:8, and 70 DEG C of condensations are stirred at reflux reaction 1-2 hours, and natural cooling filters, and filter cake is placed in 50
It is dry in DEG C baking oven, obtain modified halloysite nanotubes；
The preparation of polyvinyl alcohol water solution: 50-100 parts of polyethylene alcohol and waters are put into three-necked flask, 85-95 is warming up to
DEG C, 2-3 hours polyethylene dissolving alcohol is stirred, the polyvinyl alcohol water solution for both obtaining that concentration is 10-20% is cooled to room temperature；
(2) preparation of polyvinyl alcohol composite hydrogel
By 25-80 parts of modified halloysite nanotubes ultrasonic disperses in 500 parts of water, the ultrasonic disperse time 15 minutes, ultrasound
Wave frequency rate 20KHz, power 300W；Modified halloysite nanotubes dispersion liquid is slowly dropped in polyvinyl alcohol water solution, is stirred
3-4 hours, obtain homogeneous mixture solotion；Mixed solution is poured into mold, glass plate is covered, be put into -20 DEG C of low temperature refrigerator it is cold
Freeze 12 hours, taking-up is thawed 8 hours at 20 DEG C；So freezing, defrosting three times, both obtain polyvinyl alcohol composite hydrogel.
A kind of polyvinyl alcohol composite hydrogel provided by the invention and preparation method thereof, has following technical effect that
(1) polyvinyl alcohol Compound Water compound by polyvinyl alcohol and halloysite nanotubes, being prepared using freeze-thaw method
Gel has the advantages that high mechanical properties, good heat stability good biocompatibility, water conservation imbibition ability is strong；
(2) aldehyde is not used compared with traditional polyvinyl alcohol hydrogel in polyvinyl alcohol composite hydrogel prepared by the present invention
The toxic chemical cross-linking agent such as class, boric acid class, epoxychloropropane, and toxic solvent, preparation method are not used in preparation process
Simply, raw material is easy to get, environmental-friendly.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment is served only for
Invention is further explained, should not be understood as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made to the present invention according to the content of aforementioned present invention.
Embodiment 1
(1) prepared by raw material
Halloysite nanotubes surface treatment: 15g halloysite nanotubes, 5g vinyl triethoxyl are added in 1L there-necked flask
Silane, 500ml water/acetone (volume ratio 1:8) mixed solution, 70 DEG C of condensations, which are stirred at reflux, reacts 1 hour, natural cooling,
It filters, filter cake is placed in drying in 50 DEG C of baking ovens, has both obtained the modified halloysite nanotubes of grey.
The preparation of polyvinyl alcohol water solution: 1788 polyvinyl alcohol 20g and distilled water 300g are put into three-necked flask, are warming up to
90 DEG C, 2 hours polyethylene dissolving alcohol is stirred, is cooled to room temperature and both obtains polyvinyl alcohol water solution.
(2) preparation of polyvinyl alcohol composite hydrogel
By the modified halloysite nanotubes ultrasonic disperse of 10g in 500g water, 15 minutes ultrasonic disperse time (ultrasonic frequency
20KHz, power 300W).It is water-soluble that the polyvinyl alcohol that concentration is 15% is slowly added dropwise in the modified halloysite nanotubes dispersion liquid of 100g
It in liquid, stirs 3 hours, obtains homogeneous mixture solotion.Mixed solution is poured into mold, glass plate is covered, is put into low temperature refrigerator-
20 DEG C freeze 12 hours, and taking-up is thawed 8 hours at 20 DEG C.So freezing, defrosting three times, both obtain polyvinyl alcohol compound water congealing
Glue.
Embodiment 2
(1) prepared by raw material
Halloysite nanotubes surface treatment: 10g halloysite nanotubes, 8g vinyl trimethoxy are added in 1L there-necked flask
Silane, 500ml water/acetone (volume ratio 1:8) mixed solution, 70 DEG C of condensations are stirred at reflux reaction 1.5 hours, naturally cold
But, it filters, filter cake is placed in drying in 50 DEG C of baking ovens, has both obtained the modified halloysite nanotubes of grey.
The preparation of polyvinyl alcohol water solution: 1799 polyvinyl alcohol 25g and distilled water 350g are put into three-necked flask, are warming up to
95 DEG C, 3 hours polyethylene dissolving alcohol is stirred, is cooled to room temperature and both obtains polyvinyl alcohol water solution.
(2) preparation of polyvinyl alcohol composite hydrogel
By the modified halloysite nanotubes ultrasonic disperse of 12g in 500g water, 15 minutes ultrasonic disperse time (ultrasonic frequency
20KHz, power 300W).The polyvinyl alcohol water solution that concentration is 10% is slowly added dropwise in the modified halloysite nanotubes dispersion liquid of 80g
In, it stirs 3.5 hours, obtains homogeneous mixture solotion.Mixed solution is poured into mold, glass plate is covered, is put into low temperature refrigerator-
20 DEG C freeze 12 hours, and taking-up is thawed 8 hours at 20 DEG C.So freezing, defrosting three times, both obtain polyvinyl alcohol compound water congealing
Glue.
Embodiment 3
(1) prepared by raw material
Halloysite nanotubes surface treatment: 15g the halloysite nanotubes, (β-first of 9g vinyl three are added in 1L there-necked flask
Oxygen ethyoxyl) silane, 500ml water/acetone (volume ratio 1:8) mixed solution, 70 DEG C of condensations, which are stirred at reflux, reacts 2 hours,
Natural cooling filters, and filter cake is placed in drying in 50 DEG C of baking ovens, has both obtained the modified halloysite nanotubes of grey.
The preparation of polyvinyl alcohol water solution: 2499 polyvinyl alcohol 15g and distilled water 300g are put into three-necked flask, are warming up to
95 DEG C, 3 hours polyethylene dissolving alcohol is stirred, is cooled to room temperature and both obtains polyvinyl alcohol water solution.
(2) preparation of polyvinyl alcohol composite hydrogel
By the modified halloysite nanotubes ultrasonic disperse of 8g in 500g water, 15 minutes ultrasonic disperse time (ultrasonic frequency
20KHz, power 300W).It is water-soluble that the polyvinyl alcohol that concentration is 20% is slowly added dropwise in the modified halloysite nanotubes dispersion liquid of 120g
It in liquid, stirs 4 hours, obtains homogeneous mixture solotion.Mixed solution is poured into mold, glass plate is covered, is put into low temperature refrigerator-
20 DEG C freeze 12 hours, and taking-up is thawed 8 hours at 20 DEG C.So freezing, defrosting three times, both obtain polyvinyl alcohol compound water congealing
Glue.
Claims (4)
1. a kind of polyvinyl alcohol composite hydrogel, which is characterized in that be made according to parts by weight of following raw material: polyvinyl alcohol
50-100 parts；It is halloysite nanotubes 25-80 parts modified；There are also suitable water.
2. a kind of polyvinyl alcohol composite hydrogel according to claim 1, which is characterized in that the polyvinyl alcohol is poly-
The one or more any mixing of polyvinyl alcohol that right is 700-6000, alcoholysis degree is 70-99%.
3. a kind of polyvinyl alcohol composite hydrogel according to claim 1, which is characterized in that the modification galapectite is received
Mitron, passing through silane coupler modified, described silane coupling agent for halloysite nanotubes is vinyltriethoxysilane, second
Any one in alkenyl trimethoxy silane, vinyl three (beta-methoxy ethyoxyl) silane.
4. according to claim 1 to a kind of 3 described in any item preparation methods of polyvinyl alcohol composite hydrogel, feature exists
In, comprising the following steps:
(1) prepared by raw material
Halloysite nanotubes surface treatment: 5-30 parts of halloysite nanotubes and 1-30 parts of silane coupling agents are dispersed in water and acetone
Volume ratio is in the solution of 1:8, and 70 DEG C of condensations are stirred at reflux reaction 1-2 hours, and natural cooling filters, and filter cake is placed in 50 DEG C of bakings
It is dry in case, obtain modified halloysite nanotubes；
The preparation of polyvinyl alcohol water solution: by polyvinyl alcohol and mixing, it is warming up to 85-95 DEG C, stirs 2-3 hours polyethylene dissolvings
Alcohol is cooled to room temperature the polyvinyl alcohol water solution for both obtaining that concentration is 10-20%；
(2) preparation of polyvinyl alcohol composite hydrogel
Halloysite nanotubes ultrasonic disperse will be modified in 500 parts of water, the ultrasonic disperse time 15 minutes, ultrasonic frequency 20KHz,
Power 300W；Modified halloysite nanotubes dispersion liquid is slowly dropped in polyvinyl alcohol water solution, is stirred 3-4 hours, is obtained
Homogeneous mixture solotion；Mixed solution is poured into mold, glass plate is covered, -20 DEG C of low temperature refrigerator is put into and freezes 12 hours, take out
It thaws 8 hours at 20 DEG C；So freezing, defrosting three times, both obtain polyvinyl alcohol composite hydrogel.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909418A (en) * | 2020-08-17 | 2020-11-10 | 吉林大学 | Modified polyimide aerogel and preparation method and application thereof |
| CN113004578A (en) * | 2021-04-02 | 2021-06-22 | 江苏恒尚节能科技股份有限公司 | Waterproof heat-insulation curtain wall and preparation method thereof |
| CN113750285A (en) * | 2021-08-30 | 2021-12-07 | 方大炭素新材料科技股份有限公司 | Composite aerogel dressing and preparation method thereof |
| CN114395145A (en) * | 2022-03-10 | 2022-04-26 | 西安理工大学 | Preparation method of tannin modified GO/polyvinyl alcohol nano composite hydrogel |
| CN115487757A (en) * | 2022-10-12 | 2022-12-20 | 烟台中科先进材料与绿色化工产业技术研究院 | Halloysite/polyvinyl alcohol aerogel composite material and preparation method and application thereof |
| CN115850733A (en) * | 2022-12-06 | 2023-03-28 | 成都市第三人民医院 | Injectable nano clay hydrogel and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909418A (en) * | 2020-08-17 | 2020-11-10 | 吉林大学 | Modified polyimide aerogel and preparation method and application thereof |
| CN113004578A (en) * | 2021-04-02 | 2021-06-22 | 江苏恒尚节能科技股份有限公司 | Waterproof heat-insulation curtain wall and preparation method thereof |
| CN113004578B (en) * | 2021-04-02 | 2022-03-22 | 江苏恒尚节能科技股份有限公司 | Waterproof heat-insulation curtain wall and preparation method thereof |
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| CN114395145A (en) * | 2022-03-10 | 2022-04-26 | 西安理工大学 | Preparation method of tannin modified GO/polyvinyl alcohol nano composite hydrogel |
| CN115487757A (en) * | 2022-10-12 | 2022-12-20 | 烟台中科先进材料与绿色化工产业技术研究院 | Halloysite/polyvinyl alcohol aerogel composite material and preparation method and application thereof |
| CN115850733A (en) * | 2022-12-06 | 2023-03-28 | 成都市第三人民医院 | Injectable nano clay hydrogel and preparation method and application thereof |
| CN115850733B (en) * | 2022-12-06 | 2023-10-20 | 成都市第三人民医院 | Nanoclay hydrogel for injection and preparation method and application thereof |
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