CN109942852A - A kind of nano-particles filled base degradable polysaccharide film and preparation method thereof - Google Patents
A kind of nano-particles filled base degradable polysaccharide film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of nano-particles filled base degradable polysaccharide films and preparation method thereof, belong to natural macromolecule amylose membrane material, environmental protection and Material Field.The present invention is added nano silica, alkaline solution is added after physical mixed, is stirred evenly using konjaku glucomannan as raw material, casting film-forming, sprays hydrophobic layer in film surface, efficient hydrophobic stretch-proof degradable films are obtained after dry.The present invention solves the problems, such as that natural polymer film is difficult to reach high-quality hydrophobic effect and strong tensile strength, according to the film of this law preparation, flat and smooth, moisture-vapor transmission, OTR oxygen transmission rate and light transmittance performance are good, with excellent hydrophobic effect and strong tensile resistance, and can natural fast degradation, it is nontoxic and pollution-free.The present invention may be used as degradable package membrane material, have a extensive future in neighborhoods such as food packaging, daily chemicals packagings.
Description
Technical field
The present invention relates to natural macromolecule amylose membrane material, environmental protection and Material Field, in particular to a kind of excellent hydrophobic performance
And the polysaccharide films that mechanical property is degradable.
Background technique
In recent years, plastic products use more and more in life, but the pollutant for manufacturing plastic products generation is more,
And waste plastic is difficult to degrade, and bring " white pollution " is got worse, and causes the extensive concern of the global people, the whole world is very
Multinational family has put into effect plastic limit successively and has been forbidden to use non-degradable plastics packed relevant laws and regulations.And the system of conventional plastic
Making raw material is petroleum, and petroleum is non-renewable resources, does not meet resource-conserving, environmentally friendly fundamental state policy.So using
Natural polymer is that the degradable films that raw material is made are comparatively ideal R&D directions generally acknowledged at present.
Natural polymer membrane material mainly includes polysaccharide membrane, albuminous membranae, lipid film and composite membrane, but current scale
Industrial product is less, is not able to satisfy the requirement of practical application.In the prior art, it has reported and a variety of has prepared natural polymer
The method of membrane material.Ideal relevant report has at present: a kind of edible film of Protein/polysaccharicomposite composite (patent No.:
201210558612.3), a kind of edible preservative film of fresh fruit (application number: 201310571047.9), a kind of molten egg of polysaccharide/alcohol
White composite membrane and preparation method thereof (patent No.: 201510000725.5), a kind of preparation method of based superhydrophobic thin films (application number:
201710875001.4) a kind of, based superhydrophobic thin films and preparation method thereof (application number: 201711396367.x) etc., but these Shens
Please involved in film have the defects that in hydrophobicity and mechanical property etc. it is certain.
Summary of the invention
For the deficiencies in the prior art, the present invention provide a kind of nano-particles filled base degradable polysaccharide film and
The film of preparation method, this law preparation has excellent hydrophobic performance and mechanical property, and film-forming process of the present invention is simple, behaviour
Facilitate, is suitable for industrialized production.
Inventor passes through a large number of experiments and unremitting effort, and it is thin to be finally obtained a kind of nano-particles filled base degradable polysaccharide
The preparation method of film, the film are made of polysaccharide, hydrophobic layer and packing material, and the polysaccharide is konjaku glucomannan, hydrophobic layer
Material is any one of atoleine, silicone oil or zeins, and packing material is nano silica.
Preferably, a kind of preparation method of nano-particles filled base degradable polysaccharide film as described above, this method packet
Include following steps:
A, alkaline solution is configured, it is spare；The alkaline solution is sodium hydroxide solution or sodium acetate solution or glycine-hydroxide
Sodium buffer；
B, nano silica is weighed, is added to the water, so that silica is formed uniform colloidal sol in water using ultrasonic wave, it is spare；
C, konjaku glucomannan is weighed, is added in the nano silica hydrosol of step B, in 30-90 DEG C of stirring in water bath 30-
150min, revolving speed obtain konjaku glucomannan/nano-silica that total solids content is 0.5-2.5% in 200-2000r/min
The SiClx hydrosol；
The konjaku glucomannan and the mass ratio of nano silica are 0.5-2.0:0.01-0.10；
D, the alkaline solution of step A is added in the colloidal sol that step C is obtained, in 30-90 DEG C of stirring in water bath 0-60min, revolving speed exists
0-1500r/min is sufficiently mixed uniformly, obtains mixed dispersion；Mixed dispersion is cast plastic film mulch, after dry for the first time
Hydrophobic layer is sprayed, then takes off film after carrying out second of drying to get nano-particles filled base degradable polysaccharide film；
The alkaline solution and konjaku glucomannan/nano silica hydrosol volume ratio are as follows: 3-20:100；
The hydrophobic layer is any one of atoleine, silicone oil or zein solution, and wherein zeins is molten
The mass-volume concentration of liquid is 0.5-5%, and wherein solvent is the ethanol solution that concentration of volume percent is 70-90%.
Preferably, a kind of preparation method of nano-particles filled base degradable polysaccharide film as described above, feature exist
In: the water of the step C can be deionized water, ultrapure water, distilled water, distilled water or tap water.
Preferably, a kind of preparation method of nano-particles filled base degradable polysaccharide film as described above, feature exist
In: drying condition described in step E are as follows: dry for the first time: to turn 30-90 DEG C of dry 0-10h after 60-90 DEG C of dry 1-10h；Second
It is dry: 60-100 DEG C of dry 1-10min；It is placed in 20-30 DEG C again, balances 0-2h under 30-80% relative humidities, takes off film, is made
With a thickness of 5-50 microns of film.
Compared with prior art, advantages of the present invention are as follows:
1, nano-particles filled base degradable polysaccharide film surface prepared by the present invention is flat and smooth, moisture-vapor transmission, oxygen
The performances such as transmitance are good, especially have good mechanical property and a hydrophobic performance, and can natural fast degradation, nontoxic no dirt
Dye.
2, the hydrophobic layer of film surface layer spraying, effectively increases the hydrophobic performance of film, answers material satisfaction of the present invention actually
It is required that.The present invention may be used as degradable package membrane material, before the neighborhoods applications such as food packaging, daily chemicals packaging
Scape is wide.
Specific embodiment
For that can understand the technical characterstic for illustrating the present invention program with reference to specific embodiments be illustrated to the present invention.
But protection scope of the present invention is not limited to these examples.It is all equal without departing substantially from the change of present inventive concept or equivalent substitute
Including within protection scope of the present invention.
Embodiment 1
A kind of preparation method of nano-particles filled base degradable polysaccharide film, this method include such as step:
(1) 0.05g nano silica is weighed, is added in 100mL water, ultrasonic dissolution obtains nano silicon dioxide sol.
(2) 1.00g konjaku glucomannan is weighed, is added in nano silicon dioxide sol, 90min is stirred in 60 DEG C of water-baths,
Revolving speed is 1000r/min, is swollen konjaku glucomannan sufficiently, obtains konjaku glucomannan/nano silica hydrosol.
(3) 5mL1% sodium hydroxide solution is taken, is added in konjaku glucomannan/nano silica hydrosol, 60 DEG C of water
5min, revolving speed 300r/min are stirred in bath, obtain mixing film liquid.
(4) by hybrid films liquid casting film-forming, turn 60 DEG C of dry 1.5h after 80 DEG C of dry 1h, according to 2.5mL/100cm2Spraying
The zein solution (solvent is 80% ethyl alcohol) that mass-volume concentration is 2%, is transferred to 80 DEG C of dry 10min, is subsequently placed in
25 DEG C, film is taken off after balancing 15min under 50% relative humidities.
Embodiment 2
A kind of preparation method of nano-particles filled base degradable polysaccharide film, this method include such as step:
(1) 0.03g nano silica is weighed, is added in 100mL water, ultrasonic dissolution obtains nano silicon dioxide sol.
(2) 1.20g konjaku glucomannan is weighed, is added in nano silicon dioxide sol, 90min is stirred in 60 DEG C of water-baths,
Revolving speed 1200r/min, is swollen konjaku glucomannan sufficiently, obtains konjaku glucomannan/nano silica hydrosol.
(3) 5mL1% sodium hydroxide solution is taken, is added in konjaku glucomannan/nano silica hydrosol, 60 DEG C of water
5min, revolving speed 300r/min are stirred in bath, obtain mixing film liquid.
(4) by hybrid films liquid casting film-forming, turn 60 DEG C of dry 1.5h after 80 DEG C of dry 1h, according to 2mL/100cm2Spray coating liquor
Body paraffin is transferred to 80 DEG C of dry 10min, is subsequently placed in 25 DEG C, takes off film after balancing 15min under 50% relative humidities.
Embodiment 3
A kind of preparation method of nano-particles filled base degradable polysaccharide film, this method include such as step:
(1) 0.05g nano silica is weighed, is added in 100mL water, ultrasonic dissolution obtains nano silicon dioxide sol.
(2) 1.20g konjaku glucomannan is weighed, is added in nano silicon dioxide sol, 90min is stirred in 70 DEG C of water-baths,
Revolving speed 1200r/min, is swollen konjaku glucomannan sufficiently, obtains konjaku glucomannan/nano silica hydrosol.
(3) 5mL1% sodium acetate solution is taken, is added in konjaku glucomannan/nano silica hydrosol, 70 DEG C of water
5min, revolving speed 300r/min are stirred in bath, obtain mixing film liquid.
(4) by hybrid films liquid casting film-forming, turn 60 DEG C of dry 1.5h after 80 DEG C of dry 1h, according to 2.5mL/100cm2Spraying
Silicone oil is transferred to 90 DEG C of dry 5min, is subsequently placed in 25 DEG C, takes off film after balancing 15min under 50% relative humidities.
Embodiment 4
A kind of preparation method of nano-particles filled base degradable polysaccharide film, this method include such as step:
(1) 0.10g nano silica is weighed, is added in 100mL water, ultrasonic dissolution obtains nano silicon dioxide sol.
(2) 1.20g konjaku glucomannan is weighed, is added in nano silicon dioxide sol, 90min is stirred in 60 DEG C of water-baths,
Revolving speed 1000r/min, is swollen konjaku glucomannan sufficiently, obtains konjaku glucomannan/nano silica hydrosol.
(3) 5mL pH10 Glycine-NaOH solution is taken, it is water-soluble to be added to konjaku glucomannan/nano silica
In glue, 5min, revolving speed 600r/min are stirred in 60 DEG C of water-baths, obtain mixing film liquid.
(4) by hybrid films liquid casting film-forming, turn 60 DEG C of dry 1.5h after 80 DEG C of dry 1h, according to 4mL/100cm2Spray matter
The zein solution (solvent is 80% ethyl alcohol) that volumetric concentration is 2.5% is measured, 90 DEG C of dry 10min is transferred to, is subsequently placed in
25 DEG C, film is taken off after balancing 15min under 50% relative humidities.
Embodiment 5
A kind of preparation method of nano-particles filled base degradable polysaccharide film, this method include such as step:
(1) 0.03g nano silica is weighed, is added in 100mL water, ultrasonic dissolution obtains nano silicon dioxide sol.
(2) 0.80g konjaku glucomannan is weighed, is added in nano silicon dioxide sol, 90min is stirred in 50 DEG C of water-baths,
Revolving speed 900r/min, is swollen konjaku glucomannan sufficiently, obtains konjaku glucomannan/nano silica hydrosol.
(3) 5mL pH10 Glycine-NaOH solution is taken, it is water-soluble to be added to konjaku glucomannan/nano silica
In glue, 5min, revolving speed 600r/min are stirred in 50 DEG C of water-baths, obtain mixing film liquid.
(4) by hybrid films liquid casting film-forming, turn 60 DEG C of dry 2.5h after 70 DEG C of dry 1h, according to 1.5mL/100cm2Spraying
Atoleine is transferred to 90 DEG C of dry 8min, is subsequently placed in 25 DEG C, takes off film after balancing 15min under 50% relative humidities.
Embodiment 6
A kind of preparation method of nano-particles filled base degradable polysaccharide film, this method include such as step:
(1) 0.05g nano silica is weighed, is added in 100mL water, ultrasonic dissolution obtains nano silicon dioxide sol.
(2) 1.20g konjaku glucomannan is weighed, is added in nano silicon dioxide sol, 90min is stirred in 60 DEG C of water-baths,
Revolving speed 1200r/min, is swollen konjaku glucomannan sufficiently, obtains konjaku glucomannan/nano silica hydrosol.
(3) 10mL pH10 Glycine-NaOH solution is taken, it is water-soluble to be added to konjaku glucomannan/nano silica
In glue, 5min, revolving speed 600r/min are stirred in 60 DEG C of water-baths, obtain mixing film liquid.
(4) by hybrid films liquid casting film-forming, turn 60 DEG C of dry 2.5h after 70 DEG C of dry 1h, according to 1.5mL/100cm2Spraying
Silicone oil is transferred to 85 DEG C of dry 8min and is subsequently placed in 25 DEG C, takes off film after balancing 15min under 50% relative humidities.
Embodiment 7
A kind of preparation method of nano-particles filled base degradable polysaccharide film, this method include such as step:
(1) 0.10g nano silica is weighed, is added in 100mL water, ultrasonic dissolution obtains nano silicon dioxide sol.
(2) 0.80g konjaku glucomannan is weighed, is added in nano silicon dioxide sol, 90min is stirred in 70 DEG C of water-baths,
Revolving speed 1200r/min, is swollen konjaku glucomannan sufficiently, obtains konjaku glucomannan/nano silica hydrosol.
(3) 8mL pH10 Glycine-NaOH solution is taken, it is water-soluble to be added to konjaku glucomannan/nano silica
In glue, 5min, revolving speed 600r/min are stirred in 70 DEG C of water-baths, obtain mixing film liquid.
(4) by hybrid films liquid casting film-forming, turn 60 DEG C of dry 2.5h after 70 DEG C of dry 1h, according to 4.5mL/100cm2Spraying
The zein solution (solvent is 75% ethyl alcohol) that mass-volume concentration is 2%, is transferred to 100 DEG C of dry 5min, is subsequently placed in
25 DEG C, film is taken off after balancing 15min under 50% relative humidities.
The sample that we select embodiment 1 to prepare, has carried out quality comparison with delicatessen food grade preservative film, result is such as
Under:
The performance of each film sample of table 1 compares
Claims (4)
1. a kind of preparation method of nano-particles filled base degradable polysaccharide film, it is characterised in that: the film is by polysaccharide, hydrophobic
Layer and packing material are made, and the polysaccharide is konjaku glucomannan, and packing material is nano silica, and hydrophobic layer material is liquid
Any one of body paraffin, silicone oil or zeins.
2. a kind of preparation method of nano-particles filled base degradable polysaccharide film as described in claim 1, it is characterised in that:
This method comprises the following steps:
A, alkaline solution is configured, spare, the alkaline solution is sodium hydroxide solution or sodium acetate solution or glycine-hydroxide
Sodium buffer；
B, nano silica is weighed, is added to the water, so that silica is formed uniform colloidal sol in water using ultrasonic wave, it is spare；
C, konjaku glucomannan is weighed, is added in the nano silica hydrosol of step B, in 30-90 DEG C of stirring in water bath 30-
150min, revolving speed obtain konjaku glucomannan/nano-silica that total solids content is 0.5-2.5% in 200-2000r/min
The SiClx hydrosol；
The mass ratio of the konjaku glucomannan and nano silica hydrosol is 0.5-2.0:0.01-0.10；
D, the alkaline solution of step A is added in the colloidal sol that step C is obtained, in 30-90 DEG C of stirring in water bath 0-60min, revolving speed exists
0-1500r/min is sufficiently mixed uniformly, obtains mixed dispersion；Mixed dispersion is cast plastic film mulch, after dry for the first time
Hydrophobic layer is sprayed, then takes off film after carrying out second of drying to get nano-particles filled base degradable polysaccharide film；
The alkaline solution and konjaku glucomannan/nano silica hydrosol volume ratio are as follows: 3-20:100；
The hydrophobic layer is any one of atoleine, silicone oil or zein solution, and wherein zeins is molten
The mass-volume concentration of liquid is 0.5-5%, and wherein solvent is the ethanol solution that concentration of volume percent is 70-90%.
3. a kind of preparation method of nano-particles filled base degradable polysaccharide film as described in claim 1, it is characterised in that:
The water of the step B is deionized water, ultrapure water, distilled water, distilled water or tap water.
4. a kind of preparation method of nano-particles filled base degradable polysaccharide film as described in claim 1, it is characterised in that:
Drying condition described in step D are as follows: it is 60-90 DEG C dry for the first time, turn 30-90 DEG C of dry 0-10h after dry 1-10h；Second dry
It is dry: 60-100 DEG C of dry 1-10min；It is placed in 20-30 DEG C again, balances 0-2h under 30-80% relative humidities, takes off film, thickness is made
The film that degree is 5-50 microns.
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Cited By (2)
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| CN113651983A (en) * | 2021-08-23 | 2021-11-16 | 陕西科技大学 | Biomass high polymer material based photothermal conversion super-hydrophobic film and preparation method thereof |
| CN116333575A (en) * | 2023-03-27 | 2023-06-27 | 上海云谈科技有限公司 | Green multi-substrate universal rainproof and stain-resistant light-transmitting coating for solar power supply wireless communication system and preparation method thereof |
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Application publication date: 20190628 |