CN109824916A - A kind of composite hydrogel, compound water congealing glue film and its preparation method and application - Google Patents
A kind of composite hydrogel, compound water congealing glue film and its preparation method and application Download PDFInfo
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- CN109824916A CN109824916A CN201910123113.3A CN201910123113A CN109824916A CN 109824916 A CN109824916 A CN 109824916A CN 201910123113 A CN201910123113 A CN 201910123113A CN 109824916 A CN109824916 A CN 109824916A
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Abstract
The present invention relates to polymeric material fields, in particular to a kind of composite hydrogel, compound water congealing glue film and its preparation method and application, composite hydrogel is mainly by complete alcoholysis type polyvinyl alcohol, partial alcoholysis type polyvinyl alcohol, natural macromolecular material, salicylic acid, surfactant, silane coupling agent, nano graphene oxide, ZnOw, nano-titanium dioxide, the raw materials such as water are made, the present invention uses water soluble polymer substrate, with water as solvent, add natural macromolecular material, without harmful chemical or pungent, environmental protection, safety, with salicylic acid, nano-titanium dioxide, ZnOw is as antibacterial agent and UV resistant agent, to Escherichia coli good anti-bacterial effect, the injury of ultraviolet light is effectively reduced, compound water congealing mechanics performance of latex film is preferable, it can be used as antibacterial, antiultraviolet purposes, as touch screen is sterilized, The antibacterial of textile material and antiultraviolet etc..
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of composite hydrogel and preparation method thereof.
Background technique
Macromolecule hydrogel is a kind of can be water-swellable but the polymer with three-dimensional net structure not soluble in water.Its energy
The sensitivity response to environmental stimuli is enough realized by the swelling of volume or contraction.Polyvinyl alcohol (PVA) hydrogel is current
One of hydrogel being most widely used.PVA not only has the water suction of general hydrogel, water conservation, sustained release and to environmental stimuli
The performances such as sensitivity response, due also to its special nature and there are low toxicity, bio-compatible and the advantageous properties such as transparent, in biology
Medicine, the fields such as food industry have a wide range of applications.
Textile material mainly has cotton, fiber crops, silk, hair and all kinds of chemical fibres, easily affected by many factors and aging of degrading.It spins
Knit material has moisture absorption ventilative, antistatic, comfortable and easy to wear, soft, economical with many excellent performances, such as cotton fabric
The advantages that economical, popular among consumers, market prospects are boundless.However, textile is easy under certain mal-conditions
Discoloration and aging phenomenon occurs, leads to the reduction of its service performance.Currently, hydrogel is applied to textile material by some scholars
Protection, but the antibiotic property of hydrogel and anti-ultraviolet scarce capacity.So developing a kind of with antibacterial, uvioresistant function
The hydrogel of energy is of great significance.
Summary of the invention
In order to overcome the shortcomings in the background art, the present invention discloses a kind of with various functions such as antibacterial, uvioresistants
Composite hydrogel and compound water congealing glue film.
For achieving the above object, the present invention adopts the following technical scheme:
Composite hydrogel of the invention, is mainly prepared from the following raw materials in parts by weight:
Preferably, the mass ratio of the complete alcoholysis type polyvinyl alcohol and the partial alcoholysis type polyvinyl alcohol is (1.5-
2): 1.
Preferably, the alcoholysis degree of the partial alcoholysis type polyvinyl alcohol is 75-80%.
Preferably, the natural macromolecular material is sodium alginate, chitin derivativ, hyaluronic acid, carragheen, shell gather
Sugar and one of chitosan derivatives, starch and starch derivatives, guar gum, cellulose derivative, collagen, gelatin or
It is a variety of.
The method that the present invention prepares composite hydrogel, comprising the following steps:
(1) complete alcoholysis type polyvinyl alcohol, partial alcoholysis type polyvinyl alcohol and natural macromolecular material are dissolved in 80 DEG C -95
In DEG C water, high molecular material aqueous solution is obtained；
(2) 20-50% of the high molecular material aqueous solution volume of step (1) is taken, surfactant and silane is added
Coupling agent stirs evenly；
(3) nano-titanium dioxide, nano graphene oxide and ZnOw is added, is uniformly dispersed；
(4) product of step (3) is added in step (1) in the remaining high molecular material aqueous solution, is uniformly mixed；
(5) salicylic acid is added in the product of step (4), is uniformly mixed at 75 DEG C -95 DEG C, obtains composite hydrogel；
Wherein, uniformly mixed mode uses mechanical stirring or/and ultrasonic disperse.
Above-mentioned composite hydrogel is coated in plate interlayer, repeatedly by the preparation process of compound water congealing glue film of the present invention
Freezing and defrosting repeatedly, obtain compound water congealing glue film after dry.
Preferably, concrete technology is to apply film coating machine using bar type, and film molding seals the glass plate after film,
In thaw at RT 4-10h after freezing 15-23h at -20 DEG C to -10 DEG C, freeze-thaw is operated 3-8 times, 40 DEG C -65 DEG C repeatedly
Lower drying, obtains compound water congealing glue film.
The preparation process of compound water congealing glue film in another program of the present invention, by above-mentioned composite hydrogel vacuumizing and defoaming,
Casting film-forming, 110 DEG C several minutes of -120 DEG C of dryings, obtain compound water congealing glue film.
The present invention includes the touch screen inorganic agent of above-mentioned composite hydrogel.
The present invention includes the textile protection materials of above-mentioned composite hydrogel.
Due to the adoption of the technical scheme as described above, the invention has the following beneficial effects:
(1) present invention uses water soluble polymer substrate, with water as solvent, natural macromolecular material is added, without nocuousness
Chemical substance or pungent, environmental protection, safety.
(2) salicylic acid is added, compound water congealing glue film strong antibacterial plays the role of sterilization.
(3) nano-titanium dioxide is added, compound water congealing glue film uviolresistance is strong, can effectively prevent the inside object of its packaging
Product photic deterioration because of ultraviolet light irradiation.
(4) ZnOw has the function of antibacterial, absorbs ultraviolet light, higher to the strains killing rate such as Escherichia coli.
(5) pass through proportion, the content of natural macromolecular material, different materials of the polyvinyl alcohol of the different alcoholysis degrees of control
Proportion, the content of graphene oxide etc., adjust the mechanical strength of compound water congealing glue film, control freeze drying process is controllable
The aperture of compound water congealing glue film.
(6) present invention also can be used as other antibacterials, antiultraviolet purposes, as touch screen sterilization, textile material antibacterial and
Antiultraviolet etc..
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without making creative work, belongs to protection of the present invention
Range.
In this embodiment, composite hydrogel of the invention, is mainly prepared from the following raw materials in parts by weight:
Wherein, with two kinds of complete alcoholysis type polyvinyl alcohol, partial alcoholysis type polyvinyl alcohol composition combinations, they are easy in water
Micropore is formed, by adjusting the different ratio of two kinds of compositions, to control the Air permenbility of polyvinyl alcohol compound film, principle is benefit
With the good water solubility of partial alcoholysis type polyvinyl alcohol, composite membrane is made easily to form micropore in water, so that it is ventilative to increase it
Amount.But partial alcoholysis type polyvinyl alcohol ratio is too big, easily leads to composite membrane perforation；Conversely, if partial alcoholysis type polyvinyl alcohol institute
Accounting example is too small, and composite membrane gas permeability is too low.
Wherein, the mass ratio of complete alcoholysis type polyvinyl alcohol and partial alcoholysis type polyvinyl alcohol is (1.5-2): 1.
Wherein, the alcoholysis degree of partial alcoholysis type polyvinyl alcohol is 75-80%.
Wherein, natural macromolecular material is sodium alginate, chitin derivativ, hyaluronic acid, carragheen, chitosan and shell
One of polysaccharid derivative, starch and starch derivatives, guar gum, cellulose derivative, collagen, gelatin are a variety of.?
In certain embodiments of the present invention, natural macromolecular material is the mixture of sodium alginate and chitosan, weight part ratio 3:2；
In another embodiment, mixture of the natural macromolecular material for starch derivatives and cellulose derivative, weight part ratio 1:
2；In another embodiment, natural macromolecular material is the mixture of chitin derivativ, carragheen and sodium alginate, weight
Part is than being 1:2:7.
Wherein, salicylic acid (SA) has anti-microbial property, and there are polyphenol oxidase in Escherichia coli body, are lauched in its effect
Poplar acid, which can be changed into, more highly toxic quinones substance, and quinones substance can inhibit the phosphorylase of Escherichia coli, transhydrogenase
Activity, and further to the pectin decomposing enzyme of Escherichia coli, cellulolytic enzyme plays strong inhibiting effect, to press down
The growth of Escherichia coli processed.
Wherein, surfactant can change the interface state of solution system, significantly reduce table (boundary) face tension, substance is made to exist
The surface of solution can align.Surfactant is preferably lauryl sodium sulfate, lauryl alcohol polyoxyethylene in the present embodiment
Hydramine, neopelex, dioctyl succinate disulfonate acid, sodium glycocholate, polyoxyethylene alkyl phenyl ether, polyoxy second
Allylic alkylation ether, alkyl phenol polyoxyethylene ether, tween, fatty acid sorbitan, alkylolamides, cocoyl glucoside, lauryl Portugal
One of glucosides, cetearyl glucoside.
Wherein, purity >=98% of nano graphene oxide, the lamellar spacing 0.5-2nm of nano graphene oxide, nanometer
The lamella length of graphene oxide is 100-800nm.Favorable dispersibility of the nano graphene oxide in PVA matrix, the two it
Between by Hydrogenbond, the addition of nano graphene oxide makes compound water congealing glue film have good activeness and quietness effect, simultaneously
Improve the mechanical property of compound water congealing glue film.The present invention has no special limitation to the source of nano-graphene, general commercially available
?.In certain embodiments of the present invention, nano-graphene is selected from the production of Nanjing Xian Feng Nono-material Science & Technology Ltd.
XF179 7440-44-0 graphene.
Wherein, ZnOw (Zinc oxide whisker, write a Chinese character in simplified form ZnOw) is three-dimensional four whiskers bodies, whisker knot
Structure is complete, and almost without any crystal defect, intensity and modulus is very high, can isotropically improve the mechanical property of material,
It can be used as hydrogel enhancing, have the function of antibacterial, absorb ultraviolet light.Its Antibacterial Mechanism: due to the distinctive surface of nanoparticle
Effect is easy to generate affinity with the bacterium contacted, and has sterilizing ability；ZnOW slow release zinc in water-bearing media
Ion, zinc ion gradually separate out, due to the oxidation-reduction quality of zinc ion, when it and bacterial cell membrane combine, with
Organic matter therein reacts, and destroys the structure of memebrane protein, causes it to lose its activity, and reaches sterilization purpose.Meanwhile nanometer
The hole on the surface ZnOW can generate electronics, directly participate in reaction, number of cavities is more will to generate more electronics, sterilization
Ability is increased by.
In the present invention, nano-titanium dioxide (TiO2) it is used as inorganic UV reflective agent, due to nano-TiO2Particle size it is remote
Less than the wavelength of ultraviolet light, its refractive index with higher plays refraction and reflex to ultraviolet luminous energy, to reduce photograph
Penetrate the uitraviolet intensity in direction；When nano-titanium dioxide encounters bacterium, can attack bacterium cell, have it intracellular
Machine object decomposes, and is gone out with this except bacterium, and be allowed to decompose.Nano-titanium dioxide powder is added in PVA hydrogel, PVA water can be made
Gel had not only had the function of hydrogel water conservation, the performance being sustained but also had had antibacterial, antiultraviolet, while inorganic nano-particle adds
Enter organic basis material, additionally it is possible to improve its mechanical property.The present invention has no special limit to the source of nano-titanium dioxide
System, it is general commercially available.In certain embodiments of the present invention, it is limited to be selected from Hangzhou intelligence titanium purification science and technology for nano-titanium dioxide
The VK-T25F rutile type nano titanic oxide of company's production.
In the present invention, the purpose for adding silane coupling agent is to improve the serious agglomeration problem of nanoparticle, makes it in poly- second
It is uniformly dispersed in enol matrix, preferably plays nanoparticle small-size effect, the present embodiment is preferably aminopropyl-triethoxy
Silane (KH550), γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570), vinyltriethoxysilane, ethylene
Base trimethoxy silane, vinyl three (beta-methoxy ethyoxyl) silane, N- (mono- aminoethyl of β)-γ-aminopropyl front three (second) oxygen
One of base silane (KH792).
The method that the present invention prepares composite hydrogel, comprising the following steps:
(1) complete alcoholysis type polyvinyl alcohol, partial alcoholysis type polyvinyl alcohol and natural macromolecular material are dissolved in 80 DEG C -95
In DEG C water, high molecular material aqueous solution is obtained；
(2) it takes the 20-50% of the high molecular material aqueous solution volume of step (1), surfactant and silane coupled is added
Agent stirs evenly；
(3) nano-titanium dioxide, nano graphene oxide and ZnOw is added, is uniformly dispersed；
(4) product of step (3) is added in step (1) in remaining high molecular material aqueous solution, is uniformly mixed；
(5) salicylic acid is added in the product of step (4), is uniformly mixed at 75 DEG C -95 DEG C, obtains composite hydrogel；
Wherein, uniformly mixed mode uses mechanical stirring or/and ultrasonic disperse.
Above-mentioned composite hydrogel is coated in plate interlayer, repeatedly by the preparation process of compound water congealing glue film of the present invention
Freezing and defrosting repeatedly, obtain compound water congealing glue film after dry.
Wherein, concrete technology is to apply film coating machine using bar type, and film molding seals the glass plate after film,
In thaw at RT 4-10h after freezing 15-23h at -20 DEG C to -10 DEG C, freeze-thaw is operated 3-8 times, 40 DEG C -65 DEG C repeatedly
Lower drying, obtains compound water congealing glue film.
The preparation process of compound water congealing glue film in another embodiment of the present invention vacuumizes above-mentioned composite hydrogel de-
Bubble, casting film-forming, 110 DEG C several minutes of -120 DEG C of dryings, obtain compound water congealing glue film.
The present invention includes the touch screen inorganic agent of above-mentioned composite hydrogel.
Application method 1: it under ventilated environment, takes composite hydrogel to be applied to mobile phone and uses surface；After hydrogel is dry
It can form a film, open mobile phone screen (not influencing to use)；It opens mobile phone screen to keep in service, 30min screen surface bacterium
It can be fully erased；Film after screen surface of tearing hydrogel is dry, bacterium and fungi and dust can be fully erased.
Application method 2: touch screen surface is simply cleared up, is advisable with the spot for not seeing big；By compound water congealing
Glue is poured on touch screen surface, is uniformly smeared with hand or other tools；It is placed at room temperature, ventilation waits for that its automatic drying forms a film；
It opens touch screen and utilizes screen itself illumination, sterilize in composite hydrogel；Film, table are torn off after a period of time
Face bacterium and some small spots can be fully erased.
The present invention includes the textile protection materials of above-mentioned composite hydrogel.
Application method 1: under ventilated environment, composite hydrogel is taken to be applied to textile surface；Hydrogel to be composite is dry
After can form layer protecting film in textile surface, reduce damage of the ultraviolet light to textile, textile ageing resistance obtains
To being obviously improved, it can also prevent bacterium from extending the service life of textile to the erosion of textile.
Application method 2: being wrapped up textile using the compound water congealing glue film that the present invention obtains, and is protected textile, is subtracted
The injury of few ultraviolet light, can also prevent bacterium from extending the service life of textile to the erosion of textile.
The formula of specific embodiments of the present invention such as the following table 1, in parts by weight:
Each Example formulations table of table 1
The compound water congealing glue film of embodiment 1-4 preparation carries out mechanical property, anti-ultraviolet property, antibiotic property test, test
Data such as the following table 2.GBT1040-1992 is tested the mechanical property of compound water congealing glue film according to national standards, and gel mould is cut into
Specification is 50mm × 150mm size, and sample is placed in two fixtures of testing machine, adjusts position, elastic moderate, setting
Good testing machine parameter, starts testing machine and is tested, and measures the gel film dynamic performance of different synthetic method synthesis, including draws
Stretch two parameters of intensity and elongation at break.According to the ultraviolet-resistent property of GB/T 18830-2002 standard test compound water congealing glue film
Can, using ultraviolet ray transmissivity as parameter.The anti-microbial property of compound water congealing glue film is according to Japanese JIS Z2801:2010 standard testing
Its antibiotic rate to Escherichia coli.
The physical property table of each embodiment of table 2
By the tensile strength of embodiment 1-4, elongation at break, ultraviolet ray transmissivity, antibiotic rate test result it is found that this hair
Bright middle compound water congealing glue film has preferable mechanical property, anti-ultraviolet property, antibiotic property.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, defined herein
General Principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, originally
Invention is not intended to be limited to the embodiments shown herein, and is to fit to special with principles disclosed herein and novelty
The consistent widest scope of point.
Claims (10)
1. a kind of composite hydrogel, which is characterized in that be mainly prepared from the following raw materials in parts by weight:
20-30 parts of complete alcoholysis type polyvinyl alcohol；
10-20 parts of partial alcoholysis type polyvinyl alcohol；
5-15 parts of natural macromolecular material；
1-2 parts of salicylic acid；
0.4-0.7 parts of surfactant；
0.01-0.03 parts of silane coupling agent；
0.15-0.40 parts of nano graphene oxide；
0.05-0.20 parts of ZnOw；
1-3 parts of nano-titanium dioxide；
150-300 parts of water.
2. composite hydrogel according to claim 1, which is characterized in that the complete alcoholysis type polyvinyl alcohol and the portion
The mass ratio for dividing alcoholysis type polyvinyl alcohol is (1.5-2): 1.
3. composite hydrogel according to claim 1, which is characterized in that the alcoholysis degree of the partial alcoholysis type polyvinyl alcohol
For 75-80%.
4. composite hydrogel according to claim 1, which is characterized in that the natural macromolecular material be sodium alginate,
Chitin derivativ, hyaluronic acid, carragheen, chitosan and chitosan derivatives, starch and starch derivatives, guar gum, fiber
One of plain derivative, collagen, gelatin are a variety of.
5. a kind of method for preparing composite hydrogel described in claim 1, which comprises the following steps:
(1) complete alcoholysis type polyvinyl alcohol, partial alcoholysis type polyvinyl alcohol and natural macromolecular material are dissolved in 80 DEG C -95 DEG C
In water, high molecular material aqueous solution is obtained；
(2) it takes the 20-50% of the high molecular material aqueous solution volume of step (1), surfactant and silane coupled is added
Agent stirs evenly；
(3) nano-titanium dioxide, nano graphene oxide and ZnOw is added, is uniformly dispersed；
(4) product of step (3) is added in step (1) in the remaining high molecular material aqueous solution, is uniformly mixed；
(5) salicylic acid is added in the product of step (4), is uniformly mixed at 75 DEG C -95 DEG C, obtains composite hydrogel；
Wherein, uniformly mixed mode uses mechanical stirring or/and ultrasonic disperse.
6. a kind of preparation process of compound water congealing glue film, which is characterized in that by the described in any item compound water congealings of claim 1-5
Glue is coated in plate interlayer, is freezed and is thawed repeatedly repeatedly, obtains compound water congealing glue film after dry.
7. the preparation process of compound water congealing glue film according to claim 6, which is characterized in that its concrete technology is to use
Bar type apply film coating machine, film molding, by after film glass plate seal, at -20 DEG C to -10 DEG C freezing 15-23 h after in
Thaw at RT 4-10 h, it is dry at freeze-thaw operates 3-8 times, 40 DEG C -65 DEG C repeatedly, obtain compound water congealing glue film.
8. a kind of preparation process of compound water congealing glue film, which is characterized in that by the described in any item compound water congealings of claim 1-5
Glue vacuumizing and defoaming, casting film-forming, 110 DEG C several minutes of -120 DEG C of dryings, obtain compound water congealing glue film.
9. a kind of touch screen inorganic agent comprising composite hydrogel described in claim 1.
10. a kind of textile protection materials comprising composite hydrogel described in claim 1.
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| CN112480436A (en) * | 2020-11-30 | 2021-03-12 | 东南大学成贤学院 | Chitosan-alginate high-strength gel and preparation and application methods thereof |
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