CN108395549A - A kind of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel and preparation method thereof - Google Patents
A kind of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
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Abstract
The invention belongs to functionalization field of new materials, specifically disclose a kind of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, are prepared by polyvinyl alcohol and tea polyphenols.The invention also discloses the preparation methods of the hydrogel, include the following steps:(1)Polyvinyl alcohol is added to the water and prepares suspension, stirring is warming up to 95 DEG C of polyvinyl alcohol water solutions derived above;(2)Tea polyphenols are added into polyvinyl alcohol water solution, are stirred at 90 DEG C or more, obtain the mixed liquor of tea polyphenols and polyvinyl alcohol;(3)Mixed liquor is transferred in mold and is molded at room temperature, subzero freezing is placed in, is subsequently placed in and thaws at room temperature, which is a Frozen-thawed cycled;(4)Repeat Frozen-thawed cycled.Hydrogel ultimate tensile strength prepared by the present invention and maximum fracture rate elongation are to be not added with 2.7 times and 2.5 times of tea polyphenols polyvinyl alcohol hydrogel, and show good antibiotic property respectively.
Description
Technical field
The invention belongs to functionalization field of new materials, and in particular to a kind of polyethylene having high-intensity and high-tenacity antimicrobial form
Alcohol hydrogel and preparation method thereof.
Background technology
Macromolecule hydrogel is that have three-dimensional net structure by the one kind of polymer segment through being physically or chemically cross-linked to form,
It can save a large amount of aqueous solvents, and the novel soft wet composite material with certain mechanical strength.Compared with traditional rigid material,
Macromolecule hydrogel has certain deformation nature, and shape memory function can be responded and had to extraneous stimulation,
Therefore there is very extensive application in terms of industry, agricultural, organizational project and bio-medical material.Due to such hydrogel
Containing a large amount of water, cause its mechanical property poor, therefore develops the macromolecule hydrogel with higher-strength and toughness still
It is so the hot spot direction studied now.
Polyvinyl alcohol abbreviation PVA, molecular formula are [C2H4O]n, it is a kind of quite extensive water soluble polymer polymerization of purposes
Object has good biocompatibility and nontoxicity.Polyvinyl alcohol has many excellent characteristics, such as good film forming and machine
Tool performance etc..Polyvinyl alcohol is widely used in terms of membrane material at present.By by polyvinyl alcohol water solution by repeatedly freezing-solving
Freeze cyclic process(Frozen-thawed cycled)Polyvinyl alcohol hydrogel is made, the physical crosslinking point of gel comes from polyvinyl alcohol intersegmental part
Divide hydroxyl because of a large amount of crystallite areas of hydrogen bond action and chilled inductive formation, ultimately forms the three-dimensional network of physical crosslinking, obtain
To with certain mechanical strength hydrogel material, and the mechanical strength of hydrogel is by polyvinyl alcohol and concentration and freezing-thawing cycles
Influence.Under normal conditions, the mechanical strength of hydrogel can be obviously increased by improving concentration and increasing freezing-thawing cycles, but with
The increase of crosslinking points, toughness can be then decreased obviously.
Tea polyphenols(Tea Polyphenol, TP)It is a kind of polyphenol hydroxyl class organic compound extracted from tealeaves
Object, main component are catechin compounds.Tea polyphenols are a kind of natural high-efficiency antioxidant agent, ultraviolet absorber and have wide
Spectrum, the performance of antibacterial disinfection, at present it has been reported that polyphenol compound is added to polyurethane(J. Appl. Polym.
Sci.,2003, 90: 2756-2763)Phenolic resin(J. Appl. Polym. Sci., 2001, 8l: 1567-1571)
The middle function of assigning its antibacterial and deodouring, and tea polyphenols are added in poly-vinyl alcohol solution and prepare high intensity, high tenacity and antibacterial
The hydrogel material of function does not have been reported that so far.
Invention content
Having high intensity, the polyvinyl alcohol based of higher toughness and good antibiotic property the purpose of the present invention is to provide a kind of
Hydrogel, it is another purpose of invention to provide its corresponding preparation method then.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, is prepared by polyvinyl alcohol and tea polyphenols.
Further, in hydrogel, the mass ratio of polyvinyl alcohol and tea polyphenols is(5~15):(0.2~5).
The preparation method of above-mentioned high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, includes the following steps:
(1)Polyvinyl alcohol is added to the water and prepares suspension, stirring is warming up to 95 DEG C of polyvinyl alcohol water solutions derived above;
(2)Tea polyphenols are added into polyvinyl alcohol water solution, are stirred at 90 DEG C or more, obtain the mixing of tea polyphenols and polyvinyl alcohol
Liquid;
(3)Mixed liquor is transferred in mold and is molded at room temperature, subzero freezing is placed in, is subsequently placed in and thaws at room temperature,
The freeze-thaw cyclic process is a Frozen-thawed cycled;
(4)Repeat Frozen-thawed cycled.
Further, step(1)In, the mass fraction of polyvinyl alcohol is 10~20% in polyvinyl alcohol water solution.
Further, step(2)In, water is added while tea polyphenols are added into polyvinyl alcohol water solution, due to poly- second
Enol heating stirring is relatively time-consuming, first in step(1)It is middle to prepare the polyvinyl alcohol water solution of high concentration, then add needed for water is diluted to
Concentration, it is possible to reduce the reaction time improves efficiency, saves energy consumption.
Further, step(2)In, the mass fraction of polyvinyl alcohol is 5~15% in mixed liquor, the quality point of tea polyphenols
Number is 0.2~5%.
Further, step(2)In, whipping temp is 90~95 DEG C, and mixing time is 10~30min.
Further, step(3)In, cryogenic temperature is -18 DEG C, cooling time 12h, thawing time 6h.
Further, step(4)In, repeat Frozen-thawed cycled at least 3 times.
Since tea polyphenols are a kind of polyphenol compounds naturally extracted, have excellent antibiotic property, inoxidizability etc. excellent
Benign matter.The application has good anti-microbial property using tea polyphenols and composite hydrogel prepared by polyvinyl alcohol.
Meanwhile after mixing tea polyphenols with polyvinyl alcohol water solution, the phenolic hydroxyl group and polyvinyl alcohol on tea polyphenols surface are utilized
Hydroxyl on main chain forms hydrogen bond action, and then forms first physical cross-linked network;The progress freeze thawing of obtained hydrogel is followed
Ring, hydroxyl in polyvinyl alcohol segments constitutes physics crosslinking points because hydrogen bond action forms crystallite area, to form second object
Manage cross-linked network;With the increase of freezing-thawing cycles, the physical crosslinking point being made of crystallite area also accordingly increases, gained water-setting
The mechanical performance of glue is also obviously improved, this double physical cross-linked networks impart the higher tensile strength of hydrogel, toughness and
Tear resistance.
Compared to the PVA hydrogels for being not added with TP, as TP contents increase, ultimate tensile strength is substantially with extension at break
The increase of rate and increase, show to increase with the content of TP, the physical crosslinking point that TP and PVA segments are formed gradually increases, segment
Intermolecular forces enhancing, impart the higher toughness of gel.Under the premise of elasticity modulus is held essentially constant, with elongation
Increase, tensile strength is also significantly increased.The ultimate tensile strength and maximum for the hydrogel that especially prepared by the present invention are disconnected
It splits rate elongation or even can enhance as original 2.7 times and 2.5 times.
In conclusion hydrogel provided by the invention be it is a kind of with good antibiotic property, high intensity, high tenacity it is novel
Hydrogel composite material.The preparation method of hydrogel provided by the invention is controllable with preparation condition, preparation method is simple
Etc. advantages.
Description of the drawings
Fig. 1 is that the hydrogel tensile strength prepared by 1-4 of the embodiment of the present invention and comparative example changes with elongation at break
Curve graph;
The ultimate tensile strength figure of hydrogel when Fig. 2 is different tea polyphenols additive amounts in the embodiment of the present invention;
The fracture rate elongation figure of hydrogel when Fig. 3 is different tea polyphenols additive amounts in the embodiment of the present invention;
Fig. 4 is the counterweight figure that the hydrogel dumbbell shape sample prepared by the embodiment of the present invention 3 lifts that weight is 2 kg;
Fig. 5 is hydrogel sample prepared by 1-3 of the embodiment of the present invention and comparative example to Escherichia coli and staphylococcus aureus
The antibacterial experiment figure of sample.
Specific implementation mode
The following describes the present invention in detail with reference to examples.
Embodiment 1
A kind of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, is prepared, polyvinyl alcohol by polyvinyl alcohol and tea polyphenols
Mass ratio with tea polyphenols is 15:5.
The preparation method of above-mentioned high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, step are:
(1)By 20.0 g polyvinyl alcohol(PVA)It is scattered in 80.0 g deionized waters, is heated to 95 DEG C and stirs 2h, prepare high
Viscosity, homogeneous mass fraction are 20% polyvinyl alcohol water solution;
(2)6.7 g tea polyphenols are added into above-mentioned polyvinyl alcohol water solution(TP)With 26.3 g deionized waters, and stirred at 90 DEG C
After mixing 30min, stands 10min and bubble is discharged, prepare tea polyphenols/polyvinyl alcohol liquid, the quality of polyvinyl alcohol in mixed liquor
Score is 15%, and the mass fraction of tea polyphenols is 5%;
(3)Above-mentioned mixed liquor is transferred in parallel glass board mold, after standing 2h moldings at room temperature, transfer is placed in -18 DEG C
After freezing 12h in environment, taking-up is placed in the 6h that thaws at room temperature, repeats Frozen-thawed cycled three times, prepares the water-setting of PVA-15%-TP-5%
Glue.
Embodiment 2
A kind of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, is prepared, polyvinyl alcohol by polyvinyl alcohol and tea polyphenols
Mass ratio with tea polyphenols is 15:3.
The preparation method of above-mentioned high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, step are:
(1)With reference to embodiment 1, the polyvinyl alcohol water solution 100.0g that mass fraction is 20% is prepared;
(2)4.0g tea polyphenols and 29.0g deionized waters are added into above-mentioned aqueous solution, and is stood after stirring 30min at 90 DEG C
Bubble is discharged in 10min, prepares tea polyphenols/polyvinyl alcohol liquid, and the mass fraction of polyvinyl alcohol is 15% in mixed liquor, and tea is more
The mass fraction of phenol is 3%;
(3)Above-mentioned mixed liquor is transferred in parallel glass board mold, after standing 2h at room temperature, transfer is placed in -18 DEG C of environment
After middle freezing 12h, taking-up is placed in the 6h that thaws at room temperature;It repeats Frozen-thawed cycled three times, prepares the hydrogel of PVA-15%-TP-3%.
Embodiment 3
A kind of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, is prepared, polyvinyl alcohol by polyvinyl alcohol and tea polyphenols
Mass ratio with tea polyphenols is 15:1.
The preparation method of above-mentioned high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, step are:
(1)With reference to embodiment 1, the polyvinyl alcohol water solution 100.0g that mass fraction is 20% is prepared;
(2)1.3g tea polyphenols and 32.0g deionized waters are added into above-mentioned aqueous solution, and 30min is stirred at 90 DEG C, it is then quiet
10min discharge bubbles are set, prepare tea polyphenols/polyvinyl alcohol liquid, the mass fraction of polyvinyl alcohol is 15% in mixed liquor, tea
The mass fraction of polyphenol is 1%;
(3)Above-mentioned mixed liquor is transferred in parallel glass board mold, after standing 2h at room temperature, transfer is placed in -18 DEG C of environment
After middle freezing 12h, taking-up is placed in the 6h that thaws at room temperature;It repeats Frozen-thawed cycled three times, prepares the hydrogel of PVA-15%-TP-1%.
Embodiment 4
A kind of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, is prepared, polyvinyl alcohol by polyvinyl alcohol and tea polyphenols
Mass ratio with tea polyphenols is 15:0.2.
The preparation method of above-mentioned high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, step are:
(1)With reference to embodiment 1, the polyvinyl alcohol water solution 100.0g that mass fraction is 20% is prepared;
(2)0.27g tea polyphenols and 33.0g deionized waters are added into above-mentioned aqueous solution, and 30min is stirred at 90 DEG C, then
It standing 10min and bubble is discharged, prepare tea polyphenols/polyvinyl alcohol liquid, the mass fraction of polyvinyl alcohol is 15% in mixed liquor,
The mass fraction of tea polyphenols is 0.2%;
(3)Above-mentioned mixed liquor is transferred in parallel glass board mold, after standing 2h at room temperature, transfer is placed in -18 DEG C of environment
After middle freezing 12h, taking-up is placed in the 6h that thaws at room temperature;It repeats Frozen-thawed cycled three times, prepares the water-setting of PVA-15%-TP-0.2%
Glue.
Comparative example
A kind of preparation method of polyvinyl alcohol hydrogel, step are:
(1)15.0 g PVA are scattered in 85.0 g aqueous solutions, be heated to 95 DEG C and stir 1h, it is 15% to prepare mass fraction
Homogeneous PVA solution;
(b)10 minutes discharge bubbles are stood at 90 DEG C;
(c)Obtained mixture is transferred in parallel glass board mold and stands 2h, until room temperature forming, then carries out 3 jellies
Melt cycle, obtains the hydrogel of PVA-15%.
Embodiment 5
A kind of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, is prepared, polyvinyl alcohol by polyvinyl alcohol and tea polyphenols
Mass ratio with tea polyphenols is 8:1.
The preparation method of above-mentioned high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, step are:
(1)By 6.0 g polyvinyl alcohol(PVA)It is scattered in 54.0g deionized waters, prepares the polyvinyl alcohol water of mass fraction 10%
Solution 60.0g;
(2)0.75g tea polyphenols are added into above-mentioned aqueous solution(TP)With 14.3g deionized waters, and 30min is stirred at 90 DEG C,
10min discharge bubbles are then allowed to stand, prepare tea polyphenols/polyvinyl alcohol liquid, the mass fraction of polyvinyl alcohol is in mixed liquor
8%, the mass fraction of tea polyphenols is 1%;
(3)Above-mentioned mixed liquor is transferred in parallel glass board mold, after standing 2h at room temperature, transfer is placed in -18 DEG C of environment
After middle freezing 12h, taking-up is placed in the 6h that thaws at room temperature;It repeats Frozen-thawed cycled four times, prepares the hydrogel of PVA-8%-TP-1%.
Embodiment 6
A kind of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, is prepared, polyvinyl alcohol by polyvinyl alcohol and tea polyphenols
Mass ratio with tea polyphenols is 5:0.5.
The preparation method of above-mentioned high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, step are:
(1)With reference to embodiment 5, the polyvinyl alcohol water solution 60.0g of mass fraction 10% is prepared;
(2)0.6g tea polyphenols and 59.4g deionized waters are added into above-mentioned aqueous solution, and 30min is stirred at 90 DEG C, it is then quiet
10min discharge bubbles are set, prepare tea polyphenols/polyvinyl alcohol liquid, the mass fraction of polyvinyl alcohol is 8% in mixed liquor, and tea is more
The mass fraction of phenol is 1%;
(3)Above-mentioned mixed liquor is transferred in parallel glass board mold, after standing 2h at room temperature, transfer is placed in -18 DEG C of environment
After middle freezing 12h, taking-up is placed in the 6h that thaws at room temperature;It repeats Frozen-thawed cycled four times, prepares the hydrogel of PVA-5%-TP-0.5%.
Performance test is tested
(1)Mechanics Performance Testing
By the hydrogel sample standard dog bone cut-off knife prepared by above-described embodiment 1~4 and comparative example(65×4 mm)It cuts
At the testing bar that thickness is 1.4 mm, sample is installed to tensilon(Shimadzu AGX-100N)Fixture on, marked between fixture
Away from for 20 mm or so, rate of extension is set as 50 mm/min, carries out tensile test, and all samples are measured more than three times, asked
Average value, concrete outcome are shown in Fig. 1~3.
As shown in Figures 1 to 3, when tea polyphenols mass fraction is 0(Comparative example)When, polyvinyl alcohol hydrogel ultimate tensile strength
For 1.35 MPa, fracture rate elongation is about 270%;When tea polyphenols mass fraction is 0.2%, Frozen-thawed cycled is three times(Embodiment 4)When,
Hydrogel ultimate tensile strength is 1.58 MPa, and fracture rate elongation is 333%;When tea polyphenols mass fraction be 1%, Frozen-thawed cycled three
It is secondary(Embodiment 3)When, hydrogel ultimate tensile strength is 2.35MPa, and fracture rate elongation is 360%;When tea polyphenols mass fraction is
3%, Frozen-thawed cycled is three times(Embodiment 2)When, the ultimate tensile strength of hydrogel is 2.84MPa, and fracture rate elongation is 550%;When
Tea polyphenols mass fraction is 5%(Embodiment 1)When, the ultimate tensile strength of hydrogel is 3.60MPa, and fracture rate elongation is 680%.
When tea polyphenols mass fraction be less than or equal to 5% when, as polyphenol content increases, hydrogel ultimate tensile strength with
The increase of elongation at break and increase;This is because with the increase of polyphenol content, tea polyphenols are formed with polyvinyl alcohol segments
Physical crosslinking point gradually increase, the intermolecular forces of segment also enhance therewith, impart the higher toughness of hydrogel;In springform
Under the premise of amount is held essentially constant, with the increase of elongation at break, tensile strength is also significantly increased, but draws high intensity
Not there is a peak-peak, this is related with the additive amount of tea polyphenols;When polyvinyl alcohol mass fraction in the embodiment of the present invention
When being 15%, tea polyphenols highest mass fractions are 5%, and tea polyphenols account for the 30% of polyvinyl alcohol quality, when further only addition improves tea
When the content of polyphenol, it may occur that phenomenon of phase separation, polyvinyl alcohol can be precipitated from solution.
In addition, thawing number equally has the performance of composite hydrogel the apparent hydrogel for influencing, being prepared with example 3
(PVA-15-TP-1)For, after measured, after a freeze thawing, ultimate tensile strength is 0.45 Mpa, is broken rate elongation
It is 300%;After thawing twice, ultimate tensile strength can reach 1.1Ma, and fracture rate elongation is 310%;And passes through and freeze three times
After melting, hydrogel ultimate tensile strength is 2.35MPa, and fracture rate elongation is 360%.
After mixing tea polyphenols with polyvinyl alcohol water solution, on the phenolic hydroxyl group and polyvinyl alcohol backbones on tea polyphenols surface
Hydroxyl formed hydrogen bond action, formed first physical cross-linked network;Obtained hydrogel is subjected to Frozen-thawed cycled, polyvinyl alcohol
Hydroxyl on segment constitutes physics crosslinking points because of hydrogen bond action formation crystallite area, to form second physical cross-linked network;
With the increase of freezing-thawing cycles, the physical crosslinking point being made of crystallite area also accordingly increases, the mechanicalness of gained hydrogel
It can also be obviously improved, this double physical cross-linked networks impart the higher tensile strength of hydrogel and more preferable tear resistance.
Fig. 4 is that polyvinyl alcohol mass fraction is 15%, and tea polyphenols mass fraction is 1%(Embodiment 3)When hydrogel sample
Item(Thickness:1.40 mm;Width:4.00 mm)Lift the counterweight that quality is 2 kg.
(2)Anti-microbial property test
The preparation of inoculum in antibacterial experiment:10 g of peptone, 5 g of yeast powder, 10 g of sodium chloride is taken to be dissolved in 0.9 L
Water in, until completely dissolved, utilize 1N sodium hydroxide adjust PH to 7.0.
Antibacterial test:Hydrogel sample is cut by a diameter of 16 mm using cut-off knife, the disc-shaped that thickness is 3 mm tries
Sample.Gently be fitted in the culture dish of the nutrition lyogel of coated Escherichia coli and staphylococcus aureus, after will culture
Ware is placed on 12h in 37 DEG C of insulating box, observes inhibition zone size.
Fig. 5 is polyvinyl alcohol mass fraction when being 15%, hydrogel when tea polyphenols mass fraction is 0,1%, 3% and 5%
Anti-microbial property test;As shown in Figure 5, whether to Escherichia coli(Fig. 5 a)Or to staphylococcus aureus(Fig. 5 b), addition
Have and occur inhibition zone around the hydrogel sample of tea polyphenols, is demonstrated by stronger antibiotic property, and with tea polyphenols concentration
Increase, the diameter of inhibition zone is also increasing;Without adding the polyvinyl alcohol hydrogel of tea polyphenols without any antibiotic property.
Claims (9)
1. a kind of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, which is characterized in that prepared by polyvinyl alcohol and tea polyphenols
It forms.
2. high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel according to claim 1, which is characterized in that the water-setting
In glue, the mass ratio of polyvinyl alcohol and tea polyphenols is(5~15):(0.2~5).
3. a kind of preparation method of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel, which is characterized in that include the following steps:
(1)Polyvinyl alcohol is added to the water and prepares suspension, stirring is warming up to 95 DEG C of polyvinyl alcohol water solutions derived above;
(2)Tea polyphenols are added into the polyvinyl alcohol water solution, are stirred at 90 DEG C or more, obtain tea polyphenols and polyvinyl alcohol
Mixed liquor;
(3)The mixed liquor is transferred in mold and is molded at room temperature, subzero freezing is placed in, is subsequently placed in and solves at room temperature
Freeze, which is a Frozen-thawed cycled;
(4)Repeat the Frozen-thawed cycled.
4. the preparation method of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel according to claim 3, feature exist
In step(1)In, the mass fraction of polyvinyl alcohol is 10~20% in the polyvinyl alcohol water solution.
5. the preparation method of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel according to claim 3 or 4, feature
It is, step(2)In, add water while tea polyphenols are added into the polyvinyl alcohol water solution.
6. the preparation method of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel according to claim 5, feature exist
In step(2)In, the mass fraction of polyvinyl alcohol is 5~15% in the mixed liquor, the mass fractions of tea polyphenols is 0.2~
5%。
7. the preparation method of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel according to claim 6, feature exist
In step(2)In, whipping temp is 90~95 DEG C, and mixing time is 10~30min.
8. the preparation method of the high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel according to claim 3 or 4 or 6,
It is characterized in that, step(3)In, cryogenic temperature is -18 DEG C, cooling time 12h, thawing time 6h.
9. the preparation method of high-intensity and high-tenacity antimicrobial form polyvinyl alcohol hydrogel according to claim 8, feature exist
In step(4)In, repeat Frozen-thawed cycled at least 3 times.
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