CN108285603A - A kind of degradable high-barrier composite material and preparation method thereof - Google Patents
A kind of degradable high-barrier composite material and preparation method thereof Download PDFInfo
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- CN108285603A CN108285603A CN201810187093.1A CN201810187093A CN108285603A CN 108285603 A CN108285603 A CN 108285603A CN 201810187093 A CN201810187093 A CN 201810187093A CN 108285603 A CN108285603 A CN 108285603A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of degradable high-barrier composite materials and preparation method thereof, and composite material includes the following steps：6.0 grams of tapiocas are dissolved in 100ml distilled water, is maintained in 80 DEG C of water-baths and stirs 30min to get to tapioca solution；9.0 grams of polyvinyl alcohol are dissolved in 100ml distilled water, maintains and stirs 30min in 95 DEG C of water-baths to get to poly-vinyl alcohol solution；Chitosan is dissolved in the acetum of 100ml5% concentration for 3.0 grams, and in ultrasonic cleaner ultrasonic disperse 30min to get to chitosan solution.Above-mentioned poly-vinyl alcohol solution and chitosan solution are added in tapioca solution, and 10mL ethanol solutions are added and carry out defoaming treatment, solution ph is transferred to 4.0,30min is stirred in 90 DEG C of water-baths, a certain amount of plasticizer and crosslinking agent is added, Fruit storage is carried out to film liquid after being stirred to react, terminates degassing process after bubble-free in solution, obtains tapioca/thin composite material of polyvinyl alcohol/chitosan.The high-barrier composite material of the present invention has many advantages, such as that barrier property is good, degradable, is a kind of ideal composite material.
Description
Technical field
The invention belongs to barrier property composite material synthesis technical fields, especially relate to a kind of degradable high barrier
Composite material and preparation method.
Background technology
Environment, population, resource are to restrict three big main problems of China's 21 century sustainable development.It economizes on resources, protect
Environment has been the basic strategy that sustainable development is realized in countries in the world.Since half a century, chemical synthesis plastic products are extensive
Exactly because applied to food packaging and preservation field its abundance, light, product is beautiful, easy to process, hygienic, price is low
Honest and clean, property is stablized, nevertheless, due to the high molecular not biodegradable of plastics and non-fully reproducible utilization；Consumption is more
More petroleum resources：It is seriously polluted to environmental emission in the life cycles overall processes such as production, transport；It is disposable also to cause
Waste is more：Waste can neither degrade and be not easy to recycling；In plastics hazardous compound may to food migrate to
The shortcomings of influencing food security, therefore, nowadays each state all strictly limits the use of plastics.With the sustainable growth of China's economy with
And the national great attention for food security, more and more new packaging materials apply to food packaging, while with complete
Growing, the environmentally friendly Biodegradable high molecular based on renewable resource of nodularization environmental protection and energy saving demand
" nano-packaging ", " green package " and " functional activity packaging " etc. are increasingly paid close attention to by food packaging applications, this kind of material
Material not only considers the conventional factors such as function, performance, material, structure, appearance, cost, while also considering product in life cycle
Influence to the energy, environment, natural resources.Purpose is influence of the conduct monitoring at all levels product to environment, reduces the destruction to environment,
Improve the environmental performance of product.And renewable resource natural macromolecular material is because meeting current energy development and environmental protection
It is required that and have historically been a concern, this kind of high molecular material mainly include starch, protein, cellulose, lignin, crust
Element etc., because their abundances, derive from a wealth of sources, wherein starch occupies very important status in this kind of renewable resource,
This is because starch resource is abundant, cheap, phenanthrene is often suitable as exploitation can be again
The basic natural polymer of raw biological degradation packaging material product, so be considered as being applied to biodegradation always
One of most promising macromolecule of plastics.
Cassava is one of three big potato of the world (cassava, potato and sweet potato), is to produce per year to surpass one of 100,000,000 tons 7 big crops,
Be known as " underground granary ", " king of starch ", cassava introduces China the twenties in 19th century, due to cassava have adapt to victory it is strong,
The advantages that pest and disease damage few, of high quality and at a reasonable price, excellent drought-enduring high yield, cassava cultural area constantly expand, using continuous extension.Tapioca
Free from extraneous odour, the product (such as food or cosmetics) suitable for needing accurate adjustment smell, the ratio of viscosities of tapioca other starch are (such as
Cornstarch) it is high, penetration is strong, good film-forming property, and then to compare other starch low for protein, content of ashes, therefore tapioca
There is its distinctive irreplaceable characteristic in physics and chemistry aspect of performance, and tapioca source is wide, price is low.
Polyvinyl alcohol is a kind of Crystalline plastics generated after polyvinyl acetate resins alcoholysis, the same alcoholysis of performance
Degree, water content, the degree of polymerization are related, are the importances of its non-fiber application as packaging material, and polyvinyl alcohol film has excellent
The different transparency and glossiness, antistatic property, high-tensile and tearing strength, good oil resistivity, excellent gas barrier property, heat
Conjunction property and good cementability, penetrability are big, and release performance and metal deposition are good, and have under certain condition it is water-soluble and
Biodegradable.
Chitosan is led as the important derivatives of chitin in medicine, food, agricultural, cosmetics, weaving, papermaking etc. more
Domain plays an important role, and a large amount of hydroxyl is contained in chitosan molecule, can be combined with the amino in protein, utilize this
Characteristic can be with purification of protein, and chitosan easily forms a film, it has excellent performance after film forming, tensile strength height, good toughness, resistance to organic molten
Agent and alkaline-resisting, the chitosan film after crosslinking is acidproof.
Therefore, the present invention with tapioca with can be by the degradable synthesising macromolecule copolymer polyvinyl alcohol and tool of biology
Have the natural biologic material chitosan of specific function property and potential using value be filmogen carry out be blended prepare it is degradable
Green high-barrier composite material.
Invention content
The purpose of the present invention is to provide a kind of degradable high-barrier composite materials and preparation method thereof.
The present invention is achieved through the following technical solutions above-mentioned purpose：
A kind of degradable high-barrier composite material and preparation method thereof, which is characterized in that composite material includes following
Step：
(1) preparation of solution：
Tapioca solution：6.0 grams of tapiocas are dissolved in 100ml distilled water, is maintained in 80 DEG C of water-baths and stirs
30min is mixed to get to tapioca solution；
Poly-vinyl alcohol solution：9.0 grams of polyvinyl alcohol are dissolved in 100ml distilled water, maintains and is stirred in 95 DEG C of water-baths
30min is mixed to get to poly-vinyl alcohol solution；
Chitosan solution：Chitosan is dissolved in the acetum of 100ml5% concentration for 3.0 grams, and in ultrasonic cleaning
Ultrasonic disperse 30min is to get to chitosan solution in device.
(2) prepared by the thin composite material of tapioca/polyvinyl alcohol/chitosan：
Above-mentioned poly-vinyl alcohol solution and chitosan solution are added in tapioca solution, and 10mL absolute ethyl alcohols are added
Solution carries out defoaming treatment, and solution ph is transferred to 4.0,30min is stirred in 90 DEG C of water-baths, a certain amount of plasticizer is added
With crosslinking agent, Fruit storage is carried out to film liquid after being stirred to react, terminates degassing process after bubble-free in solution, obtains
Obtain tapioca/thin composite material of polyvinyl alcohol/chitosan.
Preferably, tapioca starch present is 2.0% in the tapioca/thin composite material of polyvinyl alcohol/chitosan, is gathered
Vinyl alcohol content 3.0%, chitosan content 1.0%.
Preferably, the preferred pentaerythrite glyceride of the plasticizer, polyglycereol, polyethylene glycol 400 and 1,1,1- tri- hydroxyl first
The additive amount of one or more of base propane, the plasticizer is 2-3%.
Preferably, the preferred sodium trimetaphosphate of the crosslinking agent makees multiple crosslinking agent with boric acid, wherein sodium trimetaphosphate and boron
The mass ratio of acid is 1:1, the additive amount of the crosslinking agent is 1-2%.
Advantageous effect：
The invention is intended to provide a kind of degradable high-barrier composite material and preparation method thereof.The present invention is formed sediment using potato
Powder, polyvinyl alcohol, chitosan are that major ingredient prepares high-barrier composite material, and raw material is renewable, resourceful, cheap, and
Preparation method is simple, is easy to mass produce.The high-barrier composite material of the present invention has barrier property good, degradable etc.
Advantage is a kind of ideal composite material.
Description of the drawings
Fig. 1 is the preparation technology flow chart of composite material of the present invention；
Fig. 2 is the zero-g aircraft that soil buries material in Degrading experiment in composite material room of the present invention.
Specific implementation mode
The following examples are that the present invention is expanded on further, however, the present invention is not limited thereto.
Embodiment 1
A kind of degradable high-barrier composite material and preparation method thereof, composite material includes the following steps：
(1) preparation of solution：
Tapioca solution：6.0 grams of tapiocas are dissolved in 100ml distilled water, is maintained in 80 DEG C of water-baths and stirs
30min is mixed to get to tapioca solution；
Poly-vinyl alcohol solution：9.0 grams of polyvinyl alcohol are dissolved in 100ml distilled water, maintains and is stirred in 95 DEG C of water-baths
30min is mixed to get to poly-vinyl alcohol solution；
Chitosan solution：Chitosan is dissolved in the acetum of 100ml5% concentration for 3.0 grams, and in ultrasonic cleaning
Ultrasonic disperse 30min is to get to chitosan solution in device.
(2) prepared by the thin composite material of tapioca/polyvinyl alcohol/chitosan：
Above-mentioned poly-vinyl alcohol solution and chitosan solution are added in tapioca solution, and 10mL absolute ethyl alcohols are added
Solution carries out defoaming treatment, and solution ph is transferred to 4.0,30min is stirred in 90 DEG C of water-baths, 2% pentaerythrite is added
Glyceride and 1% sodium trimetaphosphate and boric acid make multiple crosslinking agent, are carried out at vacuum outgas to film liquid after being stirred to react
Reason terminates degassing process after bubble-free in solution, obtains tapioca/thin composite material of polyvinyl alcohol/chitosan.
Embodiment 2
A kind of degradable high-barrier composite material and preparation method thereof, composite material includes the following steps：
(1) preparation of solution：
Tapioca solution：6.0 grams of tapiocas are dissolved in 100ml distilled water, is maintained in 80 DEG C of water-baths and stirs
30min is mixed to get to tapioca solution；
Poly-vinyl alcohol solution：9.0 grams of polyvinyl alcohol are dissolved in 100ml distilled water, maintains and is stirred in 95 DEG C of water-baths
30min is mixed to get to poly-vinyl alcohol solution；
Chitosan solution：Chitosan is dissolved in the acetum of 100ml5% concentration for 3.0 grams, and in ultrasonic cleaning
Ultrasonic disperse 30min is to get to chitosan solution in device.
(2) prepared by the thin composite material of tapioca/polyvinyl alcohol/chitosan：
Above-mentioned poly-vinyl alcohol solution and chitosan solution are added in tapioca solution, and 10mL absolute ethyl alcohols are added
Solution carries out defoaming treatment, and solution ph is transferred to 4.0,30min is stirred in 90 DEG C of water-baths, is added the 1 of 3%, and 1,1- tri-
Hydroxymethyl-propane and 2% sodium trimetaphosphate and boric acid make multiple crosslinking agent, and it is de- to carry out vacuum to film liquid after being stirred to react
Gas disposal terminates degassing process after bubble-free in solution, obtains tapioca/thin composite material of polyvinyl alcohol/chitosan.
Gas barrier property is tested：
The high-barrier composite material that embodiment 1-2 is synthesized carries out gas barrier property test comparison, and test result is such as
Described in table 1.
1 high-barrier composite material gas barrier property of table is tested
Wherein, OTR oxygen transmission rate test is measured at 25 DEG C of temperature and relative humidity 60；
Moisture-vapor transmission test is measured at 25 DEG C of temperature and relative humidity 80.
Degradability is tested:The high-barrier composite material that embodiment 1-2 is synthesized is subjected to indoor soil and buries degradation test,
It is carried out in the constant-humidity constant-temperature case of ambient stable indoors.Test result is as described in Figure of description 2.It can be seen from the figure that, in room
Under the conditions of interior constant temperature and humidity, the aggregate performance of tapioca/polyvinyl alcohol/Chitosan Composites degradation property be early period compared with
Soon, the later stage tends to be steady, and slowly rises, the weight-loss ratio at the 3rd, 6,9,12 day respectively reached 41.20%, 50.80%,
58.32%, 61.17%, the weight-loss ratio of 12 days rear films of Degrading experiment is slowly increased, at the 56th day, tapioca/polyethylene
Alcohol/chitosan film weight-loss ratio was up to 65.0%, the 131st day, after film weight-loss ratio has reached 66.1 ‰ 131 days, the mistake of film
Rate tends towards stability again, but still is degrading.
Claims (4)
1. a kind of degradable high-barrier composite material and preparation method thereof, which is characterized in that composite material includes following step
Suddenly：
(1) preparation of solution：
Tapioca solution：6.0 grams of tapiocas are dissolved in 100ml distilled water, is maintained in 80 DEG C of water-baths and stirs
30min is to get to tapioca solution；
Poly-vinyl alcohol solution：9.0 grams of polyvinyl alcohol are dissolved in 100ml distilled water, maintains and is stirred in 95 DEG C of water-baths
30min is to get to poly-vinyl alcohol solution；
Chitosan solution：Chitosan is dissolved in the acetum of 100ml5% concentration for 3.0 grams, and in ultrasonic cleaner
Ultrasonic disperse 30min is to get to chitosan solution.
(2) prepared by the thin composite material of tapioca/polyvinyl alcohol/chitosan：
Above-mentioned poly-vinyl alcohol solution and chitosan solution are added in tapioca solution, and 10mL ethanol solutions are added
Defoaming treatment is carried out, solution ph is transferred to 4.0,30min is stirred in 90 DEG C of water-baths, a certain amount of plasticizer is added and hands over
Join agent, Fruit storage is carried out to film liquid after being stirred to react, terminate degassing process after bubble-free in solution, obtains wood
Sweet potato starch/thin the composite material of polyvinyl alcohol/chitosan.
2. a kind of degradable high-barrier composite material according to claim 1 and preparation method thereof, which is characterized in that
Tapioca starch present is 2.0% in the tapioca/thin composite material of polyvinyl alcohol/chitosan, polyvinyl alcohol content
3.0%, chitosan content 1.0%.
3. a kind of degradable high-barrier composite material according to claim 1 and preparation method thereof, which is characterized in that
The preferred pentaerythrite glyceride of the plasticizer, polyglycereol, polyethylene glycol 400 and one kind in 1,1,1- trimethylolpropanes or
Person is a variety of, and the additive amount of the plasticizer is 2-3%.
4. a kind of degradable high-barrier composite material according to claim 1 and preparation method thereof, which is characterized in that
The preferred sodium trimetaphosphate of crosslinking agent makees multiple crosslinking agent with boric acid, wherein the mass ratio of sodium trimetaphosphate and boric acid is 1:
1, the additive amount of the crosslinking agent is 1-2%.
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| CN201810187093.1A CN108285603A (en) | 2018-03-07 | 2018-03-07 | A kind of degradable high-barrier composite material and preparation method thereof |
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| CN201810187093.1A CN108285603A (en) | 2018-03-07 | 2018-03-07 | A kind of degradable high-barrier composite material and preparation method thereof |
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Cited By (3)
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| CN112609262A (en) * | 2020-11-25 | 2021-04-06 | 龙帛生物科技有限公司 | Environment-friendly degradable fiber and preparation process thereof |
| CN114479199A (en) * | 2022-01-20 | 2022-05-13 | 四川大学 | Full-biodegradable bionic bait and preparation method thereof |
| CN115572511A (en) * | 2022-10-11 | 2023-01-06 | 宝鸡文理学院 | Fruit bag-free film solution with controllable decomposition time and application thereof |
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| CN112609262A (en) * | 2020-11-25 | 2021-04-06 | 龙帛生物科技有限公司 | Environment-friendly degradable fiber and preparation process thereof |
| CN114479199A (en) * | 2022-01-20 | 2022-05-13 | 四川大学 | Full-biodegradable bionic bait and preparation method thereof |
| CN115572511A (en) * | 2022-10-11 | 2023-01-06 | 宝鸡文理学院 | Fruit bag-free film solution with controllable decomposition time and application thereof |
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