CN109942849A - A kind of preparation method and applications with stimulating responsive polyvinyl alcohol oxidation-resistant film - Google Patents
A kind of preparation method and applications with stimulating responsive polyvinyl alcohol oxidation-resistant film Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method and applications with stimulating responsive polyvinyl alcohol oxidation-resistant film, belong to medicine food field of packaging material.It is modified using the coumarin derivative with photodimerization using meso-porous nano silica-base material as carrier, mesoporous silicon is made to have the function of stimuli responsive, and stimulating responsive nano material is obtained；Filtration drying carries out ultraviolet light after adsorbing butyl anisole, and mesoporous silicon aperture closure obtains antioxidant and carries stimulating responsive meso-porous nano carrier；The mesoporous silicon that coumarin derivative is modified is mixed with PVAC polyvinylalcohol solution, is formed a film after keeping the temperature a period of time in a vacuum drying oven, there is stimulating responsive polyvinyl alcohol oxidation-resistant film to obtain the final product after dry.The present invention prepare it is resulting with stimulating responsive polyvinyl alcohol oxidation-resistant film can by ultraviolet light irradiation control antioxidant release, thus solve its control release excitation mode.
Description
Technical field
The present invention relates to a kind of preparation method and applications with stimulating responsive polyvinyl alcohol oxidation-resistant film, specifically relate to
And it is a kind of in the packing film for being applied to medicine food field progress antioxygen, belong to medicine food field of packaging material.
Background technique
The research of antioxidant activity packaging suffers from significance, novel antioxygen to industries such as oil prodution industry, food industry
The research and development for changing active packing are the inexorable trends of active packing research.Currently, controlled capability antioxidant activity is packaged in and receives
Rice assembly aspect is discharged on the basis of also resting on nano-carrier, and future direction will solve its excitation mechanism,
Its antioxidant in entirely circulation use process is set to be in controllable state.It is institute's spinosity that antioxidant release is controlled using light
A kind of sharp more feasible mode of responsiveness, and pyranone cumarin is that one kind can carry out photodimerization under ultraviolet light
Cycloaddition reaction is realized the combination between cumarin, meso-porous nano carrier is modified using coumarin derivative, keeps it real in film
Existing photoresponse is a kind of mode in the cards, to push the progress of controlled capability antioxidant activity packaging film.
Summary of the invention
The purpose of the present invention is overcoming above-mentioned shortcoming, provide a kind of with stimulating responsive polyvinyl alcohol oxidation-resistant film
Preparation method and applications.
Technical solution of the present invention, a kind of preparation method with stimulating responsive polyvinyl alcohol oxidation-resistant film, step is such as
Under:
(1) preparation of stimulating responsive nano material: using meso-porous nano silica-base material as carrier, make using with photodimerization
Coumarin derivative is modified, and stimulating responsive nano material is obtained；
(2) antioxidant carries the preparation of stimulating responsive meso-porous nano carrier: crossing and is filtered dry after absorption butyl anisole
Dry carry out ultraviolet light obtains antioxidant and carries stimulating responsive meso-porous nano carrier；
(3) it forms a film: the mesoporous silicon that coumarin derivative is modified being mixed with PVAC polyvinylalcohol solution, in vacuum oven
It forms a film after middle heat preservation, there is stimulating responsive polyvinyl alcohol oxidation-resistant film to obtain the final product after dry.
Further, meso-porous nano silica-base material described in step (1) is specially meso-porous nano silica Si-MCM-
41, by weight the preparation method is as follows:
A, by 6~15 parts of tetradecyl trimethyl ammonium chloride C14The tetramethyl that TMABr and 4~10 part of mass concentration is 25%
Base ammonium hydroxide aqueous solution is dissolved in 900~1200 parts of deionized water, sufficiently dissolves；
B, 2~8 parts of tetraethoxysilane TEOS are added, stir the solution 30 minutes, are then added 60~100 part 0.001
The NaOH solution of~0.005mol/L simultaneously stirs until milk white gel is changed into clear aqueous solution；Solution is adjusted with dilute sulfuric acid
PH to 8~11, solution becomes emulsion from clarifying, and pH remains unchanged two hours of stirring；Gel is transferred to polypropylene vial
In, solidify 1-2d at room temperature, after being heated to 90~120 DEG C, keeps 2-3d curing；
C, step b products therefrom is centrifugated, filtering, 60~100 DEG C of dry 1~3d in air dry oven are placed
It is kept in dark place in sealed bag stand-by.
Further, the coumarin derivative in step (1) with photodimerization is specially 7- [(3- triethoxy first
Silylation) propoxyl group] cumarin；It is prepared in parts by mass, and steps are as follows:
D, 2~7 parts of potassium carbonate or carbonic acid are added in 60~100 parts of acetone solns of 2~5 parts of umbelliferones of Xiang Hanyou
Acquired solution is placed in 60~80 DEG C and flowed back 10~15 hours by calcium and 3~10 parts of bromopropenes, vacuum drying filtering, and uses acetone
Wash residue；
E, by acquired solution by Rotary Evaporators, 40~70 DEG C of temperature, revolving speed 20~40rpm vacuum fractionation removes third
Use ethyl alcohol recrystallization after ketone, filtering for crystallizing body be placed in vacuum oven dry 12~24 hours it is spare；Gains are 7- alkene
Propoxyl group cumarin；
F, dry nitrogen is blown into the 70~100 of 2~5 parts of 7-Allyloxycoumarin and 1~5 part of triethoxysilane
After ten minutes, 0.01~0.1 part of catalyst platinum (0) -1,3- divinyl -1,1,3,3- tetramethyls two are added in part toluene solution
Silicone complex, obtained solution are stirred at room temperature 12~24 hours, and gained grease is cumarin after vacuum distillation
Derivative.
Further, process meso-porous nano silica-base material being modified using coumarin derivative in step (1) by
Mass parts meter, specific as follows:
G, by dry 0.1~1 part of nano-carrier and 0.01~1 part of 7- [(3- triethoxysilyl) third oxygen
Base] cumarin is stirred at room temperature 7 hours in 20~50 parts of toluene solution, filtered with sand core funnel, in 60 DEG C of forced air dryings
Drying overnight, obtains the meso-porous nano carrier of cumarin modification in case；
H, by the meso-porous nano carrier of 2~5 parts of cumarins modification 60~80 in 50~100mL ethyl alcohol containing 2~4mL
DEG C reflux 4~6 hours, solid was reduced, and with ethanol washing, this process is ensured to remove completely from meso-porous nano carrier twice
Remove surfactant；
I, obtained solid is filtered, is washed with ethyl alcohol or deionized water, finally holding 8~12 is small in 60~80 DEG C of drying boxes
When, as stimulating responsive nano material.
Further, step (2) preparation process is specific as follows: by the antioxidant butyl anisole of 0.4-0.6mmol
BHA is dissolved in 10mL dehydrated alcohol, and nano-carrier of the 0.1-0.2g with stimulating responsive is added into solution, is stirred at room temperature
After mixing 2-4 hours, mixture is filtered, 2-4d is saved in 35-45 DEG C of vacuum oven, and carried out with the ultraviolet light of 310nm
It irradiates, the cumarin on mesoporous supports aperture is closed, and antioxidant is locked in hole.
Further, step (3) preparation process is as follows:
J, the PVA colloidal sol that mass fraction of solids is 10%-15% is prepared, stirring at normal temperature is until solid is completely dissolved；Then
The finely dispersed nano molecular sieve in dehydrated alcohol is added, heating water bath to 65-75 DEG C, wave completely to dehydrated alcohol by stirring
Hair；
K, the casting film-forming on poly (methyl methacrylate) plate is dried in 48-52 DEG C of air dry oven, and film is taken off in cooling.
Further, the application with stimulating responsive polyvinyl alcohol oxidation-resistant film places 1-2d in external environment,
After being carried out ultraviolet light, antioxidant starts to discharge, to solve the excitation mode of its control release.
Further, the ultraviolet light is specially the ultraviolet light of 250nm.
Mesoporous silica nano-particle (MSN) have large specific surface area, Kong Rong great, mesoporous pore size is adjustable, bio-compatible
Property good and Thermodynamically stable many advantages, such as, can be used as ideal nano container storage.By the cumarin with stimuli responsive
The stimuli responsive effect of " entrance guard " may be implemented at the edge in aperture in derivatives graft, to be the intelligence of additive in the film
It can discharge and a kind of excitation mechanism is provided.
PVA has excellent barrier properties for gases, film forming, safety and water solubility and certain biological degradability, is
A kind of degradable green packaging material.After there be the corresponding assembly of stimulation to be added, compound film inner layer can be not only used for
Moisture absorption layer can also realize the intelligence release of antioxidant after carrying out illumination, have the double effects to food.
Beneficial effects of the present invention: the present invention prepare it is resulting have stimulating responsive polyvinyl alcohol oxidation-resistant film can lead to
The release for crossing the irradiation control antioxidant of ultraviolet light, to solve the excitation mode of its control release.
Detailed description of the invention
Fig. 1 is the silicon dioxide modified front and back nitrogen adsorption-desorption isotherm schematic diagram of meso-porous nano.
Fig. 2 is the silicon dioxide modified front and back pore size distribution curve schematic diagram of meso-porous nano.
Fig. 3 is meso-porous nano silica transmission electron microscope schematic diagram；A is 20nm, b 100nm.
Specific embodiment
Embodiment 1
(1) preparation of stimulating responsive nano material:
The preparation of meso-porous nano silica:
A, the gel component molar ratio in parts by mass, preparing Si-MCM-41 is SiO2: C14TMABr:TMAOH:Na2O:
H2SO4: H2O=1.0:0.5:0.67:0.39:0.57:80.
By 6.18 parts of tetradecyl trimethyl ammonium chloride (C14TMABr, 98%) and 4.40 parts of tetramethylammonium hydroxide
(TMAOH, 25% aqueous solution) is dissolved in 900 parts of deionized water.
B, after solid is completely dissolved, 3.79 parts of tetraethoxysilanes (TEOS, 99%) is added, stirs the solution 30 minutes,
The NaOH solution of 62 parts of 0.003mol/L is added and stirs one hour, milk white gel is changed into clear aqueous solution, with dilute sulphur
The pH to 10.5 of acid-conditioning solution, solution become emulsion from clarifying, and pH remains unchanged two hours of stirring.Gel is transferred to
In polypropylene vial, solidifies one day at room temperature, be heated to 100 DEG C and continue three days.
C, products therefrom is centrifugated, filter, in air dry oven 80 DEG C it is drying for one day, be placed in sealed bag and keep away
Light saves stand-by.
Preparation gained meso-porous nano silica nitrogen adsorption-desorption isotherm is as shown in Figure 1, pore size distribution curve such as figure
Shown in 2.
Transmission electron microscope is as shown in Figure 3, wherein a is 20nm electron microscope, and b is 100nm electron microscope.
The preparation of 7- [(3- triethoxysilyl) propoxyl group] cumarin:
Main experimental materials: umbelliferone, acetone, potassium carbonate, bromopropene, dehydrated alcohol, triethoxysilane, first
Benzene, Pt (dvs) [platinum (0) -1,3- divinyl -1,1,3,3- tetramethyl disiloxane complex compounds].
D, in parts by mass, using Williamson ether synthetic method: halide acts on hydrocarbon negative oxygen ion and generates the anti-of ether
It answers, is the effective ways for synthesizing mixed ether.Composite formula are as follows:
2.5 parts of potassium carbonate (insoluble matter) and 4 parts of bromines third are added into 60 parts of acetone solns containing 3 parts of umbelliferones
Acquired solution is placed in 70 DEG C and flowed back 12 hours by alkene, vacuum filter, and with acetone washing residue.
E, acquired solution is passed through into Rotary Evaporators, temperature 60 C, revolving speed 30rpm vacuum fractionation uses second after removing acetone
Alcohol recrystallization, filtering for crystallizing body be placed in vacuum oven dry 12 hours it is spare.Gains are 7-Allyloxycoumarin.
F, dry nitrogen is blown into 80 parts of toluene of 3.5 parts of 7-Allyloxycoumarin and 2.5 parts of triethoxysilanes
After ten minutes, 0.03 part of Pt (dvs) [platinum (0) -1,3- divinyl -1,1,3,3- tetramethyl disiloxane networks are added in solution
Close object], obtained solution is stirred at room temperature 12 hours, and gained grease is used for the modification of mesoporous supports after vacuum distillation, closes
At formula are as follows:
The preparation of stimulating responsive meso-porous nano carrier
G, by dry 0.3 part of nano-carrier and 0.03 part of 7- [(3- triethoxysilyl) propoxyl group] tonka-bean
Element is stirred at room temperature 7 hours in 30 parts of toluene solution, is filtered with sand core funnel, dries in 60 DEG C of air dry ovens
Night.
H, by the meso-porous nano carrier of 2.5 parts of cumarins modification, 80 DEG C of reflux 4 are small in the 50mL ethyl alcohol containing 2mL hydrochloric acid
When, solid is reduced, and uses ethanol washing.This process is ensured to completely remove surface-active from meso-porous nano carrier twice
Agent.
I, obtained solid is filtered, is washed with ethyl alcohol or deionized water, it is finally 8 hours dry at 60 DEG C.As stimuli responsive
Property nano material.
The stimulating responsive nano material nitrogen adsorption-desorption isotherm is as shown in Figure 1, pore size distribution curve such as Fig. 2
It is shown.
Nitrogen adsorption-detachment assays test is carried out to the mesoporous silicon oxide of modification front and back, as shown in Figure 2, two classes are mesoporous
The shape and trend of the adsorption-desorption isothermal of material are almost the same.As 0 < P/Po < 0.25, curve trend slowly, this be because
The lower progress single-layer or multi-layer absorption inside hole is being divided for nitrogen；As 0.25 < P/Po < 0.4, nitrogen aggregation increases, point
Pressure is gradually increased, and an apparent kip phenomenon occurs in curve, this is because capillary condensation effect causes in hole.Capillary tube condensation
The adsorbance variation of section is more precipitous, shows that pore-size distribution is more uniform；As P/Po > 0.4, curve trend starts to tend towards stability, table
Absorption of the bright nitrogen in aperture reaches saturation state.It will appear Hysteresis loop during the absorption of curve and desorption
Reason is also unintelligible at present, the network effects being generally attributed between Thermodynamics and duct.
The compound IV type isothermal of Langmuir of the shape and trend of the adsorption-desorption isothermal of modification front and back silica is bent
Line shows that the substance is typical mesoporous material.The pore size distribution curve of mesopore silicon oxide when the curve of the right Fig. 2, as seen from the figure,
The even aperture distribution of modification front and back silica, the aperture of the MCM-41 of synthesis is 2.710nm or so, and specific surface area is
1030.191m2/ g, pore volume 1.059cm3g-1, the aperture of the mesopore silicon oxide after coumarin derivative modification is 2.384nm
Left and right, specific surface area 989.155m2/g, pore volume 0.778cm3g-1.
(2) antioxidant carries the preparation of stimulating responsive meso-porous nano carrier: by the butyl anisole of 0.5mmol
(BHA) it is dissolved in 10mL dehydrated alcohol, and nano-carrier of the 0.1g with stimulating responsive is added into solution, stir at room temperature
After 3 hours, mixture is filtered with sand core funnel, is saved three days in 40 DEG C of vacuum oven.
(3) preparation of polyvinyl alcohol (PVA) oxidation-resistant film:
J, the PVA colloidal sol that mass fraction of solids is 13% is prepared, stirring at normal temperature is until solid is completely dissolved.Then it is added
Finely dispersed nano molecular sieve in dehydrated alcohol, heating water bath to 70 DEG C, volatilize completely to dehydrated alcohol by stirring.
K, the casting film-forming on poly (methyl methacrylate) plate is dried in 50 DEG C of air dry ovens, and film is taken off in cooling.
Embodiment 2
(1) preparation of meso-porous nano silica:
A, the gel component molar ratio in parts by mass, preparing Si-MCM-41 is SiO2: C14TMABr:TMAOH:Na2O:
H2SO4: H2O=1.0:0.5:0.67:0.39:0.57:80.
By 10.30 parts of tetradecyl trimethyl ammonium chloride (C14TMABr, 98%) and 7.32 parts of tetramethylammonium hydroxide
(TMAOH, 25% aqueous solution) is dissolved in 1000 parts of deionized water.
B, after solid is completely dissolved, 6.31 parts of tetraethoxysilanes (TEOS, 99%) is added, stirs the solution 30 minutes,
The NaOH solution of 80 parts of 0.003mol/L is added and stirs one hour, milk white gel is changed into clear aqueous solution, with dilute sulphur
The pH to 10.5 of acid-conditioning solution, solution become emulsion from clarifying, and pH remains unchanged two hours of stirring.Gel is transferred to
In polypropylene vial, solidifies one day at room temperature, be heated to 100 DEG C and continue three days.
C, products therefrom is centrifugated, filter, in air dry oven 80 DEG C it is drying for one day, be placed in sealed bag and keep away
Light saves stand-by.
(2) preparation of 7- [(3- triethoxysilyl) propoxyl group] cumarin:
Main experimental materials: umbelliferone, acetone, potassium carbonate, bromopropene, dehydrated alcohol, triethoxysilane, first
Benzene, Pt (dvs) [platinum (0) -1,3- divinyl -1,1,3,3- tetramethyl disiloxane complex compounds].
D, in parts by mass, using Williamson ether synthetic method: halide acts on hydrocarbon negative oxygen ion and generates the anti-of ether
It answers, is the effective ways for synthesizing mixed ether.Composite formula are as follows:
3 parts of potassium carbonate (insoluble matter) and 4.5 parts of bromines third are added into 60 parts of acetone solns containing 4 parts of umbelliferones
Acquired solution is placed in 70 DEG C and flowed back 12 hours by alkene, vacuum filter, and with acetone washing residue.
E, acquired solution is passed through into Rotary Evaporators, temperature 60 C, revolving speed 30rpm vacuum fractionation uses second after removing acetone
Alcohol recrystallization, filtering for crystallizing body be placed in vacuum oven dry 12 hours it is spare.Gains are 7-Allyloxycoumarin.
F, dry nitrogen is blown into 80 parts of toluene solutions of 7 parts of 7-Allyloxycoumarin and 3 parts of triethoxysilanes
After ten minutes, 0.06 part of Pt (dvs) [platinum (0) -1,3- divinyl -1,1, the complexing of 3,3- tetramethyl disiloxanes is added
Object], obtained solution is stirred at room temperature 12 hours, and gained grease is used for the modification of mesoporous supports, synthesis after vacuum distillation
Formula are as follows:
(3) preparation of stimulating responsive meso-porous nano carrier:
G, by dry 0.3 part of nano-carrier and 0.03 part of 7- [(3- triethoxysilyl) propoxyl group] tonka-bean
Element is stirred at room temperature 7 hours in 40 parts of toluene solution, is filtered with sand core funnel, dries in 60 DEG C of air dry ovens
Night.
H, by the meso-porous nano carrier of 2.5 parts of cumarins modification, 80 DEG C of reflux 4 are small in the 50mL ethyl alcohol containing 2mL hydrochloric acid
When, solid is reduced, and uses ethanol washing.This process is ensured to completely remove surface-active from meso-porous nano carrier twice
Agent.
I, obtained solid is filtered, is washed with ethyl alcohol or deionized water, it is finally 8 hours dry at 60 DEG C.As stimuli responsive
Property nano material.
(4) antioxidant carries stimulating responsive meso-porous nano carrier: the butyl anisole (BHA) of 0.5mmol is dissolved in
In 10mL dehydrated alcohol, and nano-carrier of the 0.1g with stimulating responsive is added into solution, after stirring 3 hours at room temperature,
Mixture is filtered with sand core funnel, is saved three days in 40 DEG C of vacuum oven.
(5) preparation of polyvinyl alcohol (PVA) oxidation-resistant film:
J, the PVA colloidal sol that mass fraction of solids is 13% is prepared, stirring at normal temperature is until solid is completely dissolved.Then it is added
Finely dispersed nano molecular sieve in dehydrated alcohol, heating water bath to 70 DEG C, volatilize completely to dehydrated alcohol by stirring.
K, the casting film-forming on poly (methyl methacrylate) plate is dried in 50 DEG C of air dry ovens, and film is taken off in cooling.
Embodiment 3
(1) preparation of meso-porous nano silica:
A, the gel component molar ratio in parts by mass, preparing Si-MCM-41 is SiO2: C14TMABr:TMAOH:Na2O:
H2SO4: H2O=1.0:0.5:0.67:0.39:0.57:80.
By 12.36 parts of tetradecyl trimethyl ammonium chloride (C14TMABr, 98%) and 8.79 parts of tetramethylammonium hydroxide
(TMAOH, 25% aqueous solution) is dissolved in 1200 parts of deionized water.
B, after solid is completely dissolved, 7.58 parts of tetraethoxysilanes (TEOS, 99%) is added, stirs the solution 30 minutes,
The NaOH solution of 97 parts of 0.003mol/L is added and stirs one hour, milk white gel is changed into clear aqueous solution, with dilute sulphur
The pH to 10.5 of acid-conditioning solution, solution become emulsion from clarifying, and pH remains unchanged two hours of stirring.Gel is transferred to
In polypropylene vial, solidifies one day at room temperature, be heated to 100 DEG C and continue three days.
C, products therefrom is centrifugated, filter, in air dry oven 80 DEG C it is drying for one day, be placed in sealed bag and keep away
Light saves stand-by.
(2) preparation of 7- [(3- triethoxysilyl) propoxyl group] cumarin
Main experimental materials: umbelliferone, acetone, potassium carbonate, bromopropene, dehydrated alcohol, triethoxysilane, first
Benzene, Pt (dvs) [platinum (0) -1,3- divinyl -1,1,3,3- tetramethyl disiloxane complex compounds].
D, in parts by mass, using Williamson ether synthetic method: halide acts on hydrocarbon negative oxygen ion and generates the anti-of ether
It answers, is the effective ways for synthesizing mixed ether.Composite formula are as follows:
4 parts of potassium carbonate (insoluble matter) and 6 parts of bromines third are added into 70 parts of acetone solns containing 4.5 parts of umbelliferones
Acquired solution is placed in 70 DEG C and flowed back 12 hours by alkene, vacuum filter, and with acetone washing residue.
E, acquired solution is passed through into Rotary Evaporators, temperature 60 C, revolving speed 30rpm vacuum fractionation uses second after removing acetone
Alcohol recrystallization, filtering for crystallizing body be placed in vacuum oven dry 12 hours it is spare.Gains are 7-Allyloxycoumarin.
F, 80 parts of toluene for dry nitrogen being blown into 7.5 parts of 7-Allyloxycoumarin and 4 parts of triethoxysilanes are molten
After ten minutes, 0.07 part of Pt (dvs) [platinum (0) -1,3- divinyl -1,1, the complexing of 3,3- tetramethyl disiloxanes is added in liquid
Object], obtained solution is stirred at room temperature 12 hours, and gained grease is used for the modification of mesoporous supports, synthesis after vacuum distillation
Formula are as follows:
(3) preparation of stimulating responsive meso-porous nano carrier
G, by dry 0.5 part of nano-carrier and 0.05 part of 7- [(3- triethoxysilyl) propoxyl group] tonka-bean
Element is stirred at room temperature 7 hours in 40 parts of toluene solution, is filtered with sand core funnel, dries in 60 DEG C of air dry ovens
Night.
H, by the meso-porous nano carrier of 3 parts of cumarins modification, 80 DEG C of reflux 4 are small in the 50mL ethyl alcohol containing 2mL hydrochloric acid
When, solid is reduced, and uses ethanol washing.This process is ensured to completely remove surface-active from meso-porous nano carrier twice
Agent.
I, obtained solid is filtered, is washed with ethyl alcohol or deionized water, it is finally 8 hours dry at 60 DEG C.As stimuli responsive
Property nano material.
(4) antioxidant carries stimulating responsive meso-porous nano carrier: the butyl anisole (BHA) of 0.5mmol is dissolved in
In 10mL dehydrated alcohol, and nano-carrier of the 0.1g with stimulating responsive is added into solution, after stirring 3 hours at room temperature,
Mixture is filtered with sand core funnel, is saved three days in 40 DEG C of vacuum oven.
(5) preparation of polyvinyl alcohol (PVA) oxidation-resistant film:
J, the PVA colloidal sol that mass fraction of solids is 13% is prepared, stirring at normal temperature is until solid is completely dissolved.Then it is added
Finely dispersed nano molecular sieve in dehydrated alcohol, heating water bath to 70 DEG C, volatilize completely to dehydrated alcohol by stirring.
K, the casting film-forming on poly (methyl methacrylate) plate is dried in 50 DEG C of air dry ovens, and film is taken off in cooling.
Claims (8)
1. a kind of preparation method with stimulating responsive polyvinyl alcohol oxidation-resistant film, it is characterized in that steps are as follows:
(1) preparation of stimulating responsive nano material: using meso-porous nano silica-base material as carrier, using with photodimerization
Coumarin derivative is modified, and stimulating responsive nano material is obtained；
(2) antioxidant carry stimulating responsive meso-porous nano carrier preparation: absorption butyl anisole after filtration drying into
Row 310nm ultraviolet light obtains antioxidant and carries stimulating responsive meso-porous nano carrier；
(3) it forms a film: the mesoporous silicon that coumarin derivative is modified being mixed with PVAC polyvinylalcohol solution, is protected in a vacuum drying oven
It forms a film after temperature, there is stimulating responsive polyvinyl alcohol oxidation-resistant film to obtain the final product after dry.
2. as described in claim 1 with the preparation method of stimulating responsive polyvinyl alcohol oxidation-resistant film, it is characterized in that: step
(1) meso-porous nano silica-base material described in be specially meso-porous nano silica Si-MCM-41, by weight preparation method such as
Under:
A, by 6~15 parts of tetradecyl trimethyl ammonium chloride C14The tetramethyl hydrogen that TMABr and 4~10 part of mass concentration is 25%
Oxidation aqueous ammonium is dissolved in 900~1200 parts of deionized water, sufficiently dissolves；
B, be added 2~8 parts of tetraethoxysilane TEOS, stir the solution 30 minutes, then be added 60~100 part 0.001~
The NaOH solution of 0.005mol/L simultaneously stirs until milk white gel is changed into clear aqueous solution；Solution is adjusted with dilute sulfuric acid
PH to 8~11, solution become emulsion from clarifying, and pH remains unchanged two hours of stirring；Gel is transferred in polypropylene vial,
Solidify 1-2d at room temperature, after being heated to 90~120 DEG C, keeps 2-3d curing；
C, step b products therefrom is centrifugated, filtering, 60~100 DEG C of dry 1~3d, are placed on envelope in air dry oven
It is kept in dark place in pocket stand-by.
3. as described in claim 1 with the preparation method of stimulating responsive polyvinyl alcohol oxidation-resistant film, it is characterized in that: step
(1) coumarin derivative in photodimerization is specially 7- [(3- triethoxysilyl) propoxyl group] cumarin；
It is prepared in parts by mass, and steps are as follows:
D, be added in 60~100 parts of acetone solns of 2~5 parts of umbelliferones of Xiang Hanyou 2~7 parts of potassium carbonate or calcium carbonate and
Acquired solution is placed in 60~80 DEG C and flowed back 10~15 hours by 3~10 parts of bromopropenes, vacuum drying filtering, and uses acetone washing
Residue；
E, by acquired solution by Rotary Evaporators, 40~70 DEG C of temperature, revolving speed 20~40rpm vacuum fractionation, after removing acetone
With ethyl alcohol recrystallization, filtering for crystallizing body be placed in vacuum oven dry 12~24 hours it is spare；Gains are 7- allyl oxygen
Butylcoumariii；
F, dry nitrogen is blown into 70~100 parts of first of 2~5 parts of 7-Allyloxycoumarin and 1~5 part of triethoxysilane
After ten minutes, 0.01~0.1 part of catalyst platinum (0) -1,3- divinyl -1,1,3,3- tetramethyl, two silicon oxygen is added in benzole soln
Alkane complex compound, obtained solution are stirred at room temperature 12~24 hours, and gained grease is that cumarin is derivative after vacuum distillation
Object.
4. as described in claim 1 with the preparation method of stimulating responsive polyvinyl alcohol oxidation-resistant film, it is characterized in that: step
(1) process being modified using coumarin derivative to meso-porous nano silica-base material in is in parts by mass, specific as follows:
G, dry 0.1~1 part of nano-carrier and 0.01~1 part of 7- [(3- triethoxysilyl) propoxyl group] is fragrant
Legumin is stirred at room temperature 7 hours in 20~50 parts of toluene solution, is filtered with sand core funnel, dries in 60 DEG C of air dry ovens
It is dry to stay overnight, obtain the meso-porous nano carrier of cumarin modification；
H, the meso-porous nano carrier of 2~5 parts of cumarins modification is returned for 60~80 DEG C in 50~100mL ethyl alcohol containing 2~4mL
Stream 4~6 hours, solid are reduced, and with ethanol washing, this process is ensured to completely remove table from meso-porous nano carrier twice
Face activating agent；
I, obtained solid is filtered, is washed with ethyl alcohol or deionized water, is finally kept for 8~12 hours in 60~80 DEG C of drying boxes,
As stimulating responsive nano material.
5. as described in claim 1 with the preparation method of stimulating responsive polyvinyl alcohol oxidation-resistant film, it is characterized in that: step
(2) preparation process is specific as follows: the antioxidant butyl anisole BHA of 0.4-0.6mmol is dissolved in 10mL dehydrated alcohol,
And the nano-carrier that 0.1-0.2g has stimulating responsive is added into solution, and after stirring 2-4 hours at room temperature, filtering mixing
Object saves 2-4d in 35-45 DEG C of vacuum oven, and is irradiated with the ultraviolet light of 310nm, on mesoporous supports aperture
Cumarin is closed, and antioxidant is locked in hole.
6. as described in claim 1 with the preparation method of stimulating responsive polyvinyl alcohol oxidation-resistant film, it is characterized in that: step
(3) preparation process is as follows:
J, the PVA colloidal sol that mass fraction of solids is 10%-15% is prepared, stirring at normal temperature is until solid is completely dissolved；Then it is added
Finely dispersed nano molecular sieve in dehydrated alcohol, heating water bath to 65-75 DEG C, volatilize completely to dehydrated alcohol by stirring；
K, the casting film-forming on poly (methyl methacrylate) plate is dried in 48-52 DEG C of air dry oven, and film is taken off in cooling.
7. with the application of stimulating responsive polyvinyl alcohol oxidation-resistant film described in one of claim 1-6, it is characterized in that: in the external world
After environment places 1-2d, after being carried out ultraviolet light, antioxidant starts to discharge, to solve the excitation of its control release
Mode.
8. with the application of stimulating responsive polyvinyl alcohol oxidation-resistant film described in claim 7, it is characterized in that: the ultraviolet light has
Body is the ultraviolet light of 250nm.
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