CN107880460A - A kind of cellulose nano-fibrous enhancing composite membrane of UV resistance and preparation method thereof - Google Patents
A kind of cellulose nano-fibrous enhancing composite membrane of UV resistance and preparation method thereof Download PDFInfo
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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
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Abstract
The invention discloses cellulose nano-fibrous enhancing composite membrane of a kind of UV resistance and preparation method thereof.The composite membrane matrix is polyvinyl alcohol, and enhancing is mutually the cellulose nano-fibrous of modification.Prepare the conjugate solution of terminal isocyanate groups first, conjugate solution and be dispersed in dimethyl sulfoxide cellulose nano-fibrous occur esterification at room temperature.After removing unnecessary coupling agent, it is modified it is cellulose nano-fibrous mixed by certain mass ratio with polyvinyl alcohol water solution, oven drying obtains the composite membrane of homogeneous transparent.Raw material in the application comes from biomass, there is that biodegradable and bio-compatibility is good.Instant invention overcomes the shortcomings that small molecule ultraviolet absorber stability difference, nano-particle is dispersed in the base in composite membrane, good mechanical performance simultaneously provides ultraviolet band significant protective action, while the addition of nano-particle regulates and controls the effect of UV absorption in controllable film.There is potential application value in industries such as packaging for foodstuff, traffic, buildings.
Description
Technical field
It is compound more particularly to a kind of cellulose nano-fibrous enhancing of UV resistance the present invention relates to UV resistance technical field of membrane
Film and preparation method thereof.
Background technology
The exhaustion of earth resource, the destruction of the deterioration of ecological environment, particularly ozone layer, make the ultraviolet spoke of earth surface
Penetrate increase.Excessive ultraviolet radioactive can bring numerous negative effects, such as some skins damage to human health and living facilities
Wound, or even induce cutaneum carcinoma, the decolouring of dyestuff and pigment, the photo-aging and food spoilage of some high polymer materials, nutrition
Ingredients from lossing etc..Therefore development new material to ultraviolet light protect extremely urgent.
In order to solve the problems, such as that ultraviolet light is brought, people select the addition of some ultraviolet absorbers in matrix material or selected
The lucifuge material such as paper, aluminium foil is selected commodity are kept in dark place.But the use of opaque material sacrifices the attractive in appearance of commodity
Property.Currently used ultra-violet absorber can be divided into by molecular structure：Salicylate structure, acrylate structural, class benzo three
Azoles structure or the structure of benzophenone etc..For these ultraviolet absorbers because molecule is smaller, heat endurance is poor, limits use.
Also some metallics such as ZnO, TiO2Deng.This kind of inorganic UV absorbent stability and security are stronger, but compare
Skin surface easily is deposited on, therefore is commonly used for sun-screening agent.In addition in the case of UV exposure, metallic has photocatalysis work
With can make Degradation of Polymer Materials, destroy the basic structure of material.
It is cellulose nano-fibrous that there is degradable, good biocompatibility, also with high-specific surface area, high mechanics
The advantages that intensity, it can be used as the supporting material of a variety of high polymer materials.To cellulose nano-fibrous research, trigger exploration new
The upsurge of type nano composite material；It is used as particle filled composite to be scattered in polyvinyl alcohol from cellulose nano-fibrous, can obtain each
Item superior performance, and the novel nanocomposite materials with degradability.The hydroxyl on cellulose nano-fibrous surface has polarity, with
Water-soluble poval compatibility is good.In order to assign cellulose nano-fibrous uv resistance energy, it is necessary to cellulose Nanowire
Dimension carries out surface modification.Study at present it is more there is cellulose nano-fibrous surface modifying method to have, esterification, acetylation, silicon
Alkanisation, grafting macromolecule etc..But some current surface modifying method steps are comparatively laborious, partial reaction condition is more severe
Carve.Therefore simplify chemical surface modification experimental procedure, optimize modified condition, while the requirement for taking into account Green Chemistry seems particularly heavy
Will.
The content of the invention
Goal of the invention：For the deficiencies in the prior art, it is an object of the invention to provide a kind of UV resistance cellulose
Nanofiber strengthens composite membrane, and low in raw material price, operation is simple, and material degradable green simultaneously has efficient uv resistance
Energy.The bright another object of this law is to provide a kind of preparation method of the cellulose nano-fibrous enhancing composite membrane of above-mentioned UV resistance.
Technical scheme：In order to realize foregoing invention purpose, the technical solution adopted by the present invention is：
A kind of cellulose nano-fibrous enhancing composite membrane of UV resistance, is prepared by following steps：
1）The cellulose nano-fibrous aqueous solution removes moisture with the multiple centrifuge washing of ethanol acetone, is dispersed in dimethyl sulfoxide again
In；
2）Toluene di-isocyanate(TDI) is added in dimethyl sulfoxide to react with ESCALOL 567, obtains isocyanic acid
The conjugate solution of ester terminal；
3）Blend step 1）、2）Obtained product, reacts at room temperature；Add acetone into reacted mixture, high-speed stirred,
It is then centrifuged for；Unnecessary coupling agent is washed away with acetone, obtained lower sediment, is dispersed in water again, obtains modified cellulose
The nanofiber aqueous solution；
4）Polyvinyl alcohol high-speed stirred is dissolved in deionized water solution, obtains polyvinyl alcohol water solution；By step 3）Obtain
The modified cellulose nanofiber aqueous solution mixed with polyvinyl alcohol water solution, mixed liquor closed ultrasonic in frozen water disperses；
5）By step 4）Obtained mixed liquor, it is poured in super flat culture dish, oven drying, it is cellulose nano-fibrous obtains UV resistance
Strengthen composite membrane.
Step 1）In, the mass percentage concentration of described cellulose nano-fibrous dimethyl sulfoxide solution is 0.25-1.0%.
Step 2）In, the mol ratio of described ESCALOL 567 and toluene di-isocyanate(TDI) is not less than
2:1, reaction time 1h-3h.
Step 3）In, 0.1h-0.5h is reacted at room temperature.
Step 3）In, the described modified cellulose nanofiber aqueous solution, mass percentage concentration 0.25-1.0%.
Step 1 and step 3）In, described centrifugation be with centrifugal rotational speed be 12500rpm/min desk centrifuges at a high speed
Centrifugation.
Step 4）In, described polyvinyl alcohol is 1788 types, alcoholysis degree 87%-89%.
Step 4）In, described polyvinyl alcohol water solution concentration is 2.5%.
A kind of method for preparing the cellulose nano-fibrous enhancing composite membrane of described UV resistance, comprises the following steps：
1）It is dispersed in cellulose nano-fibrous in dimethyl sulfoxide；
2）Toluene di-isocyanate(TDI) is added in dimethyl sulfoxide to react with ESCALOL 567, obtains isocyanic acid
The conjugate solution of ester terminal；
3）Blend step 1）, 2）Obtained product, reacts 0.1h-0.5h at room temperature；Reacted mixture adds acetone, at a high speed
Stirring, is then centrifuged for；Unnecessary coupling agent is washed away with acetone；Obtained lower sediment is dispersed in water again, is obtained
The 0.25%-1.0% modified cellulose nanofiber aqueous solution；
4）By step 3）The obtained modified cellulose nanofiber aqueous solution mixes with 2.5% polyvinyl alcohol water solution, mixed liquor in
Closed ultrasonic disperses 0.5h in frozen water；
5）By step 4）Obtained mixed liquor, it is poured in super flat culture dish, oven drying, it is cellulose nano-fibrous obtains UV resistance
Composite membrane.
Step 4）In, described modified cellulose nanofiber, the mass ratio of polyvinyl alcohol is 1 ~ 10:100.
Beneficial effect：Compared with prior art, remarkable advantage of the invention has：
1）The present invention has the characteristics that degradable, good biocompatibility, UV resistance, excellent in mechanical performance, reaction condition are gentle.
2）The cellulose nano-fibrous method of modifying being related to is simple, and controllability is strong.From electron scanning micrograph
As can be seen that modified is cellulose nano-fibrous dispersed in polyvinyl alcohol, size is Nano grade.
3）Method prepared by compound UV resistance material is compared compared with current material preparation method, and efficiency high, cost are low, are easy to work
Industry.
4）Used as new packaging material, alternative now widely used plastics, solve the ring that petrochemical industry is brought
Border is polluted and safety problem.Can also extend the ultraviolet sensitivity materials'use life-span, increase aesthetic feeling, have great economic benefit with
Social benefit.
5）Confirmed through UV absorbance detection, UV absorption stability is strong, and efficient ultraviolet suction can be also realized in low dosage
Receive, there is good practicality.
Brief description of the drawings
Fig. 1 is cellulose nano-fibrous and modified cellulose nanofiber Fourier transform infrared spectroscopy figure；
Fig. 2 is modified cellulose nanofiber-composite membrane of polyvinyl alcohol photo figure；
Fig. 3 is the electron scanning micrograph of modified cellulose nanofiber-composite membrane of polyvinyl alcohol；
Fig. 4 is the UV absorption spectrogram of modified cellulose nanofiber-composite membrane of polyvinyl alcohol.
Embodiment
With reference to embodiment, the present invention will be described in detail.
Embodiment 1
A kind of cellulose nano-fibrous enhancing composite membrane of UV resistance, is prepared by following steps：
1）By the cellulose nano-fibrous aqueous solution of 10g（Mass fraction is 0.5%, cellulose nano-fibrous a diameter of 5-10nm）First
Centrifuged with desk centrifuge under 12500rpm/min, repeatedly wash removing water with ethanol acetone, then use high speed dispersor
15000rpm ice-water baths are distributed in dimethyl sulfoxide (DMSO)；Obtain modified cellulose nanofiber-dimethyl sulfoxide solution.
2）It is 10 that mol ratio is added in 4mL dimethyl sulfoxides：1 ESCALOL 567 and toluene two are different
Cyanate, 1h is reacted at room temperature, obtain the conjugate solution of terminal isocyanate groups；The cellulose nano-fibrous room temperature in dimethyl sulfoxide
High-speed stirred 2h；The conjugate solution of obtained terminal isocyanate groups is added into cellulose nano-fibrous-dimethyl sulfoxide solution, room temperature
Lower reaction 0.1h；
3）Above-mentioned reacted mixture is added into acetone, first high-speed stirred, then 12500rpm centrifugations；Will be unnecessary with acetone
Coupling agent washes away；Obtained lower sediment is disperseed with high speed dispersor 15000rpm in ice-water bath, is dispersed in water, is obtained again
To modified cellulose nanofiber-aqueous solution；
4）Take the modified cellulose nanofiber aqueous solution obtained above to be diluted with water to 15mL, add 0.375g polyvinyl alcohol
1788 types（Alcoholysis degree is 87%-89%）, mixed at high speed stirring.Modified cellulose nanofiber, the mass ratio of polyvinyl alcohol is 1:
100.Mixed liquor closed ultrasonic in frozen water disperses（Supersonic frequency：100KHz）0.5h, it is stand-by.
5）By 4）In mixed liquor pour into super flat culture dish, 60 DEG C of oven drying 24h, produce UV resistance cellulose nanometer
Composite fiber membrane.
Embodiment 2
A kind of cellulose nano-fibrous enhancing composite membrane of UV resistance, is prepared by following steps：
1）By the cellulose nano-fibrous aqueous solution of 10g（Mass fraction is 0.5%, cellulose nano-fibrous a diameter of 5-10nm）First
Centrifuged with desk centrifuge under 12500rpm/min, repeatedly wash removing water with ethanol acetone, then use high speed dispersor
15000rpm ice-water baths are distributed in dimethyl sulfoxide (DMSO)；Obtain modified cellulose nanofiber-dimethyl sulfoxide solution.
2）It is 10 that mol ratio is added in 4mL dimethyl sulfoxides：1 ESCALOL 567 and toluene two are different
Cyanate, 2h is reacted at room temperature, obtain the conjugate solution of terminal isocyanate groups；The cellulose nano-fibrous room temperature in dimethyl sulfoxide
High-speed stirred 2h；The conjugate solution of obtained terminal isocyanate groups is added into cellulose nano-fibrous-dimethyl sulfoxide solution, room temperature
Lower reaction 0.1h；
3）Above-mentioned reacted mixture is added into acetone, first high-speed stirred, then 12500rpm centrifugations；Will be unnecessary with acetone
Coupling agent washes away；Obtained lower sediment is disperseed with high speed dispersor 15000rpm in ice-water bath, is dispersed in water, is obtained again
To modified cellulose nanofiber-aqueous solution；
4）Take the modified cellulose nanofiber aqueous solution obtained above to be diluted with water to 15mL, add 0.375g polyvinyl alcohol
1788 types（Alcoholysis degree is 87%-89%）, mixed at high speed stirring.Modified cellulose nanofiber, the mass ratio of polyvinyl alcohol is 1:
100.Mixed liquor closed ultrasonic in frozen water disperses（Supersonic frequency：100KHz）0.5h, it is stand-by.
5）By 4）In mixed liquor pour into super flat culture dish, 60 DEG C of oven drying 24h, produce UV resistance cellulose nanometer
Composite fiber membrane.
Embodiment 3
A kind of cellulose nano-fibrous enhancing composite membrane of UV resistance, is prepared by following steps：
1）By the cellulose nano-fibrous aqueous solution of 10g（Mass fraction is 0.5%, cellulose nano-fibrous a diameter of 5-10nm）First
Centrifuged with desk centrifuge under 12500rpm/min, repeatedly wash removing water with ethanol acetone, then use high speed dispersor
15000rpm ice-water baths are distributed in dimethyl sulfoxide (DMSO)；Obtain modified cellulose nanofiber-dimethyl sulfoxide solution.
2）It is 10 that mol ratio is added in 4mL dimethyl sulfoxides：1 ESCALOL 567 and toluene two are different
Cyanate, 3h is reacted at room temperature, obtain the conjugate solution of terminal isocyanate groups；The cellulose nano-fibrous room temperature in dimethyl sulfoxide
High-speed stirred 2h；The conjugate solution of obtained terminal isocyanate groups is added into cellulose nano-fibrous-dimethyl sulfoxide solution, room temperature
Lower reaction 0.1h；
3）Above-mentioned reacted mixture is added into acetone, first high-speed stirred, then 12500rpm centrifugations；Will be unnecessary with acetone
Coupling agent washes away；Obtained lower sediment is disperseed with high speed dispersor 15000rpm in ice-water bath, is dispersed in water, is obtained again
To modified cellulose nanofiber-aqueous solution；
4）Take the modified cellulose nanofiber aqueous solution obtained above to be diluted with water to 15mL, add 0.375g polyvinyl alcohol
1788 types（Alcoholysis degree is 87%-89%）, mixed at high speed stirring.Modified cellulose nanofiber, the mass ratio of polyvinyl alcohol is 1:
100.Mixed liquor closed ultrasonic in frozen water disperses（Supersonic frequency：100KHz）0.5h, it is stand-by.
5）By 4）In mixed liquor pour into super flat culture dish, 60 DEG C of oven drying 24h, produce UV resistance cellulose nanometer
Composite fiber membrane.
Embodiment 4
A kind of cellulose nano-fibrous enhancing composite membrane of UV resistance, is prepared by following steps：
1）By the cellulose nano-fibrous aqueous solution of 10g（Mass fraction is 0.5%, cellulose nano-fibrous a diameter of 5-10nm）First
Centrifuged with desk centrifuge under 12500rpm/min, repeatedly wash removing water with ethanol acetone, then use high speed dispersor
15000rpm ice-water baths are distributed in dimethyl sulfoxide (DMSO)；Obtain modified cellulose nanofiber-dimethyl sulfoxide solution.
2）It is 10 that mol ratio is added in 4mL dimethyl sulfoxides：1 ESCALOL 567 and toluene two are different
Cyanate, 2h is reacted at room temperature, obtain the conjugate solution of terminal isocyanate groups；The cellulose nano-fibrous room temperature in dimethyl sulfoxide
High-speed stirred 2h；The conjugate solution of obtained terminal isocyanate groups is added into cellulose nano-fibrous-dimethyl sulfoxide solution, room temperature
Lower reaction 0.3h；
3）Above-mentioned reacted mixture is added into acetone, first high-speed stirred, then 12500rpm centrifugations；Will be unnecessary with acetone
Coupling agent washes away；Obtained lower sediment is disperseed with high speed dispersor 15000rpm in ice-water bath, is dispersed in water, is obtained again
To modified cellulose nanofiber-aqueous solution；
4）Take the modified cellulose nanofiber aqueous solution obtained above to be diluted with water to 15mL, add 0.375g polyvinyl alcohol
1788 types（Alcoholysis degree is 87%-89%）, mixed at high speed stirring.Modified cellulose nanofiber, the mass ratio of polyvinyl alcohol is 1:
100.Mixed liquor closed ultrasonic in frozen water disperses（Supersonic frequency：100KHz）0.5h, it is stand-by.
5）By 4）In mixed liquor pour into super flat culture dish, 60 DEG C of oven drying 24h, produce UV resistance cellulose nanometer
Composite fiber membrane.
Embodiment 5
A kind of cellulose nano-fibrous enhancing composite membrane of UV resistance, is prepared by following steps：
1）By the cellulose nano-fibrous aqueous solution of 10g（Mass fraction is 0.5%, cellulose nano-fibrous a diameter of 5-10nm）First
Centrifuged with desk centrifuge under 12500rpm/min, repeatedly wash removing water with ethanol acetone, then use high speed dispersor
15000rpm ice-water baths are distributed in dimethyl sulfoxide (DMSO)；Obtain modified nanometer cellulose-dimethyl sulfoxide solution.
2）It is 10 that mol ratio is added in 4mL dimethyl sulfoxides：1 ESCALOL 567 and toluene two are different
Cyanate, 2h is reacted at room temperature, obtain the conjugate solution of terminal isocyanate groups；Nano-cellulose room temperature high speed in dimethyl sulfoxide
Stir 2h；The conjugate solution of obtained terminal isocyanate groups is added into nano-cellulose-dimethyl sulfoxide solution, reacted at room temperature
0.5h；
3）Above-mentioned reacted mixture is added into acetone, first high-speed stirred, then 12500rpm centrifugations；Will be unnecessary with acetone
Coupling agent washes away；Obtained lower sediment is disperseed with high speed dispersor 15000rpm in ice-water bath, is dispersed in water, is obtained again
To modified nanometer cellulose-aqueous solution；
4）Take the modified cellulose nanofiber aqueous solution obtained above to be diluted with water to 15mL, add 0.375g polyvinyl alcohol
1788 types（Alcoholysis degree is 87%-89%）, mixed at high speed stirring.Modified cellulose nanofiber, the mass ratio of polyvinyl alcohol is 1:
100.Mixed liquor closed ultrasonic in frozen water disperses（Supersonic frequency：100KHz）0.5h, it is stand-by.
5）By 4）In mixed liquor pour into super flat culture dish, 60 DEG C of oven drying 24h, produce UV resistance cellulose nanometer
Composite fiber membrane.
Embodiment 6
A kind of cellulose nano-fibrous enhancing composite membrane of UV resistance, is prepared by following steps：
1）By the cellulose nano-fibrous aqueous solution of 10g（Mass fraction is 0.5%, cellulose nano-fibrous a diameter of 5-10nm）First
Centrifuged with desk centrifuge under 12500rpm/min, repeatedly wash removing water with ethanol acetone, then use high speed dispersor
15000rpm ice-water baths are distributed in dimethyl sulfoxide (DMSO)；Obtain modified cellulose nanofiber-dimethyl sulfoxide solution.
2）It is 10 that mol ratio is added in 4mL dimethyl sulfoxides：1 ESCALOL 567 and toluene two are different
Cyanate, 2h is reacted at room temperature, obtain the conjugate solution of terminal isocyanate groups；The cellulose nano-fibrous room temperature in dimethyl sulfoxide
High-speed stirred 2h；The conjugate solution of obtained terminal isocyanate groups is added into cellulose nano-fibrous-dimethyl sulfoxide solution, room temperature
Lower reaction 0.5h；
3）Above-mentioned reacted mixture is added into acetone, first high-speed stirred, then 12500rpm centrifugations；Will be unnecessary with acetone
Coupling agent washes away；Obtained lower sediment is disperseed with high speed dispersor 15000rpm in ice-water bath, is dispersed in water, is obtained again
To modified cellulose nanofiber-aqueous solution；
4）Take the modified cellulose nanofiber aqueous solution obtained above to be diluted with water to 15mL, add 0.375g polyvinyl alcohol
1788 types（Alcoholysis degree is 87%-89%）, mixed at high speed stirring.Modified cellulose nanofiber, the mass ratio of polyvinyl alcohol is 5:
100.Mixed liquor closed ultrasonic in frozen water disperses（Supersonic frequency：100KHz）0.5h, it is stand-by.
5）By 4）In mixed liquor pour into super flat culture dish, 60 DEG C of oven drying 24h, produce UV resistance cellulose nanometer
Composite fiber membrane.
Embodiment 7
A kind of cellulose nano-fibrous enhancing composite membrane of UV resistance, is prepared by following steps：
1）By the cellulose nano-fibrous aqueous solution of 10g（Mass fraction is 0.5%, cellulose nano-fibrous a diameter of 5-10nm）First
Centrifuged with desk centrifuge under 12500rpm/min, repeatedly wash removing water with ethanol acetone, then use high speed dispersor
15000rpm ice-water baths are distributed in dimethyl sulfoxide (DMSO)；Obtain modified cellulose nanofiber-dimethyl sulfoxide solution.
2）It is 10 that mol ratio is added in 4mL dimethyl sulfoxides：1 ESCALOL 567 and toluene two are different
Cyanate, 2h is reacted at room temperature, obtain the conjugate solution of terminal isocyanate groups；The cellulose nano-fibrous room temperature in dimethyl sulfoxide
High-speed stirred 2h；The conjugate solution of obtained terminal isocyanate groups is added into cellulose nano-fibrous-dimethyl sulfoxide solution, room temperature
Lower reaction 0.5h；
3）Above-mentioned reacted mixture is added into acetone, first high-speed stirred, then 12500rpm centrifugations；Will be unnecessary with acetone
Coupling agent washes away；Obtained lower sediment is disperseed with high speed dispersor 15000rpm in ice-water bath, is dispersed in water, is obtained again
To modified cellulose nanofiber-aqueous solution；
4）Take the modified cellulose nanofiber aqueous solution obtained above to be diluted with water to 15mL, add 0.375g polyvinyl alcohol
1788 types（Alcoholysis degree is 87%-89%）, mixed at high speed stirring.Modified cellulose nanofiber, the mass ratio of polyvinyl alcohol is 10
:100.Mixed liquor closed ultrasonic in frozen water disperses（Supersonic frequency：100KHz）0.5h, it is stand-by.
5）By 4）In mixed liquor pour into super flat culture dish, 60 DEG C of oven drying 24h, produce UV resistance cellulose nanometer
Composite fiber membrane.
Polyvinyl alcohol film is labeled as PVA, embodiment 5, embodiment 6, the obtained different modified celluloses in embodiment 7
The composite membrane of polyvinyl alcohol of nanofiber ratio is respectively labeled as：DT-CNF/PVA 1%, DT-CNF/PVA 5%, DT-CNF/PVA
10%。
As shown in figure 1, the cellulose nano-fibrous chemical constitution infrared analysis that conjugate solution is modified, with unmodified
Cellulose nano-fibrous infrared figure be contrast, two figures have the presence of hydroxyl（In 3450 cm-1That locates is unimodal）, also exist
C-H stretching vibration（In 2895cm-1That locates is unimodal）, the C-O-C connecting keys of cellulose（In 1165 cm-1The bands of a spectrum at place）, C-O
Stretching motion（In 1118 cm-1That locates is unimodal）, the C-O-C characteristic groups of ethers（In 1061 cm-1That locates is unimodal）, and β-
Glucose is in 897 cm-1The key band at place.
After chemical modification being carried out with benzophenone, 1730 cm-1There are a new bands of a spectrum in place, because new occur
C=O.It is by the characteristic group of the ester of-COOH of cellulose-OH and conjugate solution reaction generations.In 1597 cm-1Place
There are the bands of a spectrum relevant with the phenyl ring from benzophenone and isocyanates, it was demonstrated that cellulose modified success.
2265 cm-1The group relevant with isocyanates is not observed in place, it was demonstrated that modified cellulose by ethanol after washing
All it is cleaned.
Composite membrane is in highly transparent in Fig. 2, has good pliability.
As can be seen that smooth homogeneous state is presented in matrix material polyvinyl alcohol in Fig. 3, modified cellulose nanofiber exists
It is uniformly distributed in composite membrane.
From Fig. 4, it is apparent that as the raising of modified cellulose nanofiber ratio, the UV absorption of composite membrane are strong
Spend increasing.Composite membrane has three obvious absworption peaks in ultraviolet light wave band, has benefited from modified cellulose nanometer in composite membrane
The addition of fiber, while also demonstrate cellulose modified success.Can be by adjusting the addition of modified cellulose, simply
Change the uv resistance energy of composite membrane.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
The equivalent structure or equivalent flow conversion that bright specification and accompanying drawing content are made, or directly or indirectly it is used in other related skills
Art field, is included within the scope of the present invention.
Claims (10)
1. a kind of cellulose nano-fibrous enhancing composite membrane of UV resistance, it is characterised in that be prepared by following steps：
1）The cellulose nano-fibrous aqueous solution removes moisture with the multiple centrifuge washing of ethanol acetone, is dispersed in dimethyl sulfoxide again
In；
2）Toluene di-isocyanate(TDI) is added in dimethyl sulfoxide to react with ESCALOL 567, obtains isocyanic acid
The conjugate solution of ester terminal；
3）Blend step 1）、2）Obtained product, reacts at room temperature；Add acetone into reacted mixture, high-speed stirred,
It is then centrifuged for；Unnecessary coupling agent is washed away with acetone, obtained lower sediment, is dispersed in water again, obtains modified cellulose
The nanofiber aqueous solution；
4）By the dissolving of polyvinyl alcohol high-speed stirred in deionized water, polyvinyl alcohol water solution is obtained；By step 3）What is obtained changes
The cellulose nano-fibrous aqueous solution of property mixes with polyvinyl alcohol water solution, and mixed liquor closed ultrasonic in frozen water disperses；
5）By step 4）Obtained mixed liquor, it is poured in super flat culture dish, oven drying, it is cellulose nano-fibrous obtains UV resistance
Strengthen composite membrane.
2. the cellulose nano-fibrous enhancing composite membrane of UV resistance according to claim 1, it is characterised in that step 1）In,
The mass percentage concentration of described cellulose nano-fibrous dimethyl sulfoxide solution is 0.25-1.0%.
3. the cellulose nano-fibrous enhancing composite membrane of UV resistance according to claim 1, it is characterised in that step 2）In,
Described ESCALOL 567 and the mol ratio of toluene di-isocyanate(TDI) are not less than 2:1, reaction time 1h-
3h。
4. the cellulose nano-fibrous enhancing composite membrane of UV resistance according to claim 1, it is characterised in that step 3）In,
0.1h-0.5h is reacted at room temperature.
5. the cellulose nano-fibrous enhancing composite membrane of UV resistance according to claim 1, it is characterised in that step 3）In,
The described modified cellulose nanofiber aqueous solution, mass percentage concentration 0.25-1.0%.
6. the cellulose nano-fibrous enhancing composite membrane of UV resistance according to claim 1, it is characterised in that step 1 and
Step 3）In, it with centrifugal rotational speed is 12500rpm/min desk centrifuge high speed centrifugations that described centrifugation, which is,.
7. the cellulose nano-fibrous enhancing composite membrane of UV resistance according to claim 1, it is characterised in that step 4）In,
Described polyvinyl alcohol is 1788 types, alcoholysis degree 87%-89%.
8. the cellulose nano-fibrous enhancing composite membrane of UV resistance according to claim 1, it is characterised in that step 4）In,
Described polyvinyl alcohol water solution concentration is 2.5%.
A kind of 9. method of the cellulose nano-fibrous enhancing composite membrane of UV resistance prepared described in claim 1, it is characterised in that
Comprise the following steps：
1）It is dispersed in cellulose nano-fibrous in dimethyl sulfoxide；
2）Toluene di-isocyanate(TDI) is added in dimethyl sulfoxide to react with ESCALOL 567, obtains isocyanic acid
The conjugate solution of ester terminal；
3）Blend step 1）, 2）Obtained product, reacts 0.1h-0.5h at room temperature；Reacted mixture adds acetone, at a high speed
Stirring, is then centrifuged for；Unnecessary coupling agent is washed away with acetone；Obtained lower sediment is dispersed in water again, is modified
The cellulose nano-fibrous aqueous solution；
4）By step 3）The obtained modified cellulose nanofiber aqueous solution mixes with 2.5% polyvinyl alcohol water solution, mixed liquor in
Closed ultrasonic disperses 0.5h in frozen water；
5）By step 4）Obtained mixed liquor, it is poured in super flat culture dish（Thickness control is at 30-50 μm）, oven drying, obtain
The cellulose nano-fibrous enhancing composite membrane of UV resistance.
10. the method according to claim 9 for preparing the cellulose nano-fibrous enhancing composite membrane of UV resistance, its feature exist
In step 4）In, described modified cellulose nanofiber, the mass ratio of polyvinyl alcohol is 1 ~ 10:100.
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