CN107540994A - A kind of preparation method and application of biodegradable plastic film - Google Patents
A kind of preparation method and application of biodegradable plastic film Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and application of biodegradable plastic film, this method is using natural polysaecharides compound and polyalcohols compound as raw material, it is degradation of promoter to introduce fermented type yeast, prepare biodegradable plastic film, whole process is simple to operate, pollution-free, nonhazardous, and energy consumption of reaction is low, the biodegradable plastic film being prepared has uniform composition and good excellent biodegradable and the adsorptivity to dyestuff.The present invention forms gel rubber system using natural macromolecular material with synthesizing high molecular mutually synergy composite, natural environmental-protective biodegradable plastic film is prepared by degradation of promoter of microorganism, required raw material sources are wide and economical and easily available, prepared biodegradable plastic film have biodegradable, natural environmental-protective, can secondary use the characteristics of.
Description
Technical field
The invention belongs to the natural environmental-protective biodegradable polymer containing microorganism, and in particular to one kind biological can drop
Solve the preparation method and application of plastic sheeting.
Background technology
Scientific and technological level continue to develop today, plastic membrane product into people live in institute it is common and can not or
The plastic sheeting such as scarce thing, disposable plastic bag, express packaging bag is seen everywhere.The raw material of conventional plastic film article is mostly
The various derivatives of oil, and it is well known that oil belongs to non-renewable resources, so before petroleum resources exhaustion, find
The suitable even more preferable plastic-substitute of performance is very urgent.On the other hand, with the enhancing of people's environmental consciousness, chase after merely
Ask the epoch of properties of product to pass by, nowadays people with greater need for be the environment friendly of plastic product in itself, so can give birth to
Thing Devlopment of Degradable Plastics product arises at the historic moment.Biodegradable plastics refer to can as existing for nature microorganism such as bacterium, mould
The effect of bacterium (fungi) and algae and cause the plastics of degraded.Existing biodegradable plastic film is mostly by natural polymer
Material is with various polyester blends or copolymerization come what is prepared, and although obtained material is biodegradable to some of which, but it is made
Standby process can use and arrive poisonous and hazardous catalyst, crosslinking agent etc..
Chinese patent CN1916062A discloses a technology, using starch, polyalcohol, vinyl-acrylate copolymer,
The blendings such as additive salt prepare starch-based, biodegradable plastics, and wherein content of starch reaches 30-65%, high content of starch
Promote the biodegradable of the material.
Chinese patent CN103865106A discloses the biodegradable plastic and preparation method of a kind of high-content of starch, this
The biodegradable plastic of high-content of starch is using natural plant starch such as corn, farinas as primary raw material, can give birth to completely
The polyvinyl alcohol of thing degraded is toughener supplemented by main toughener and polyethylene glycol, and adds environmentally friendly class composite elasticizer and processing
Auxiliary agent is kneaded and formed, and content of starch reaches as high as 90wt%.
The content of the invention
To solve the problems, such as that prior art is present, the invention provides a kind of preparation method of biodegradable plastic film
And application, this method introduce fermented type yeast and promoted for degraded using natural polysaecharides compound and polyalcohols compound as raw material
Agent, biodegradable plastic film is prepared, whole process is simple to operate, pollution-free, nonhazardous, and energy consumption of reaction is low, is prepared into
The biodegradable plastic film arrived has uniform composition and excellent biodegradable and to the visible adsorptivity of dyestuff.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of preparation method of biodegradable plastic film, comprises the following steps：
1) 0.1~20 part of polyalcohols compound is added by mass fraction in 10~1000 parts of deionized water, 80
Stirring obtains matrix A, it is standby to be cooled to room temperature up to being completely dissolved at~120 DEG C；0.1~500 part of natural polymer is more
Sugar is added in 10~1000 parts of deionized water, is stirred at 10~100 DEG C up to being completely dissolved, is obtained matrix B, be cooled to room
Warm standby is used；
2) at 60~100 DEG C, 10~20 parts of matrix B are slowly added into 10~50 parts of matrix A, are stirred continuously until
It is even, matrix C is obtained, it is standby to be cooled to room temperature；
3) take 10~20 parts matrix C, 0.5~10 part of microorganism, 0.01~10 part of nutrient solution, 0.05~5 part
PH adjusting agent, temperature are 25~40 DEG C, stirring reaction, are subsequently poured into mould disks, are placed in 50~50 DEG C of ﹣ environment and carry out physics
Cross-linked gel chemical conversion type, drying is taken out, prepares the biodegradable plastic film containing yeast.
As a further improvement on the present invention, described polyalcohols compound is polyethylene glycol, polyvinyl alcohol, polypropylene
One or more mixtures in acid, alginic acid, polyacrylamide.
As a further improvement on the present invention, described natural macromolecule amylose is starch, modified starch, dextrin, ring paste
One or more mixing in essence, polyanion cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose
Thing.
As a further improvement on the present invention, described yeast is fermented type yeast, preferably Saccharomyces cerevisiae.
As a further improvement on the present invention, described nutritional agents is glucose, wheaten starch, farina, sweet potato
The mixture of any one or more in starch, beef extract, bean sprouts leachate, peptone, fruit juice, amino acid.
As a further improvement on the present invention, described pH adjusting agent is citric acid, potassium citrate, lactic acid, tartaric acid, apple
Tartaric acid, sodium citrate, sodium carbonate, potassium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium acid carbonate, dipotassium hydrogen phosphate, di(2-ethylhexyl)phosphate
One kind or a pair of cushioning liquid in hydrogen potassium.
As a further improvement on the present invention, described physical crosslinking gelation be shaped to freeze-thaw, mechanical agitation,
One or more combinations in ultraviolet lighting, heating, microwave radiation.
As a further improvement on the present invention, step 2,3) in, mixing speed is 50~500r/min, and the time is 1~12
Hour.
As a further improvement on the present invention, in step 3), drying temperature is 20~35 DEG C.
A kind of biodegradable plastic film as made from described preparation method is applied in dyestuff is adsorbed, and biological can be dropped
The dyestuff for being used to adsorb after solution plastic sheeting water absorption and swelling includes：Crystal violet, methyl orange, malachite green, methylene blue, alkaline product
One or both of red, basic rhodamine mixture.
Relative to prior art, the present invention has advantages below：
The present invention is used the natural polysaecharides compound containing great amount of hydroxy group such as starch, modified starch, dextrin, cyclodextrin
With the hydrophilic macromolecule such as polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, and fermented type saccharomycete is uniformly altogether
It is mixed, the biodegradable plastic sheeting containing saccharomycete load is made.It is different from traditional preparation method, this preparation method mistake
Any poisonous and harmful property chemical reagent is free of in journey, and energy consumption is low, easy to operate.The film being prepared into has excellent mechanical property
Can, especially in the case of aqueous moistening, mechanical property and the very big difference of dry film generation of film are it in different necks
The application in domain creates condition.On the other hand, the present invention high molecular mutually cooperates with work using natural macromolecular material with synthesis
Gel rubber system is formed with composite, natural environmental-protective biodegradable plastic film, institute are prepared by degradation of promoter of microorganism
Need raw material sources wide and economical and easily available, prepared biodegradable plastic film has biodegradable, natural environmental-protective, can two
The characteristics of secondary utilization.Prepared film has excellent degradability, can Natural Water in 5 days under merely water environment
Solution 70%.Furthermore, it has been found that saccharomycete has the function that adsorption-decomposition function dyestuff, common dyes such as crystal violet, methyl orange, methylene
Blue, malachite green and other dyes can be decomposed removal well by saccharomycete, can be with so plastic film product made from this research institute
The secondary use after its aging, for removing the dyestuff in waste water, and be proved absorption of the plastic foil to dyestuff have can
Cyclicity, can repeatedly it utilize.Because the present invention uses Biodegradable high-molecular as base material, prepared by solvent of water, with yeast
Bacterium is that degradation of promoter prepares biodegradable film, and whole process is simple to operate, pollution-free, nonhazardous, and energy consumption of reaction
Low, the biodegradable plastic film being prepared has uniform composition and excellent biodegradable and visible to dyestuff
Adsorptivity.
Further, natural macromolecule amylose class compound such as cellulose, starch, modified starch, dextrin, cyclodextrin etc. all belongs to
All contain great amount of hydroxy group in the category of biodegradable macromolecular, its molecule, easily with hydrophilic macromolecule such as polyethylene glycol,
Contained hydroxyl, amino, carbonyl etc. form hydrogen bond under conditions of freeze-thaw in polyacrylic acid, polyacrylamide equimolecular
It is cross-linked to form complex three-dimensional structures.Because this process is physical crosslinking process, avoiding crosslinking agent etc. can give birth to plastic foil
The influence of thing degradation property.
The biodegradable films plastics of the present invention have good mechanical performance, biodegradable and normal to some
With the adsorptivity of dyestuff.The film, which is put into water, can hydrolyze 70% naturally in 5 days, film tensile strength is up to 35MP, water suction
Elongation at break is up to 600% in the case of swelling, to the adsorbances of some common dyes up to 70mg/g.
Brief description of the drawings
Fig. 1 is the SEM figures of prepared biodegradable plastic film section.
Embodiment
A kind of preparation method of biodegradable plastic film of the present invention, comprises the following steps：
1) 0.1~20 part of polyvinyl alcohol is added in mass ratio in 10~1000 parts of deionized water, at 80~120 DEG C
Lower stirring is completely dissolved it, obtains matrix A, it is standby to be cooled to room temperature；By the natural polymer that mass fraction is 0.1~500 part
Sub- polysaccharide is added in 10~1000 parts of deionized water, and being stirred at 10~100 DEG C is completely dissolved it, obtains matrix B, cools down
It is standby to room temperature；
2) at 60~100 DEG C, (10~20 parts) B is slowly added into (10~50 parts) A, continues agitating and heating until mixed
Close uniformly, obtain matrix C, it is standby to be cooled to room temperature；Mixing speed is 50~500r/min, and the time is 1~12 hour.
3) take 10~20 parts matrix C, 0.5~20 part of microorganism, 0.01~10 part of nutrient solution and 0.05~5 part
PH adjusting agent mixes, and be 25~40 DEG C in temperature stirs that (mixing speed is 50~500r/min, and the time is small for 1~12
When), mould disks are poured into, -50~50 DEG C is placed in and stirs, mixed liquor is poured into mould and carries out being physical crosslinking gelation shaping
(one or more combinations in freeze-thaw, mechanical agitation, ultraviolet lighting, heating, microwave radiation) 1~3 time, after by mould
Tool taking-up is placed in air dry oven and dried at 20~35 DEG C, produces the biodegradable plastic film D containing yeast.
The preparation method of the present invention is described in further detail with reference to embodiment.
Embodiment 1
Using natural polysaecharides compound and polyvinyl alcohol compound as raw material, it is degradation of promoter to introduce fermented type yeast,
Biodegradable plastic sheeting is prepared, its preparation process is：
The first step, in mass ratio by 0.1 part of polyvinyl alcohol, add in 10 parts of deionized water, 10 are stirred at 80 DEG C
Hour makes its dissolving, obtains matrix A；Starch that mass ratio is 0.1 part, 0.1 part of cyclodextrin are added into 10 parts of deionized water
In, stirred 0.1 hour at 10 DEG C, obtain matrix B.
Second step, at 60 DEG C, 10 parts of B are slowly added into 10 parts of A, continuing agitating and heating makes it uniformly obtain for 3 hours
Matrix C.
3rd step, the matrix C of preparation are cooled to room temperature, take 10 parts of matrix C, 0.5 part of fermented yeast, 0.01 part of Portugal
Grape sugar, 0.01 part of peptone, 0.05 part of apple acid regulator, 0.05 part of sodium acid carbonate, temperature are 25 DEG C, and mixing speed is
260r/min, stir 3 hours, mould disks are poured into after stirring, carry out freeze-thaw cross-linked gel chemical conversion type 1 time, freezing temperature
Spend for -50 DEG C, thaw point is 20 DEG C, and mould is placed in 20 DEG C of air dry ovens by rear taking-up to be dried, to prepare containing yeast
Biodegradable plastic film.
Embodiment 2
Using natural polysaecharides compound and polyvinyl alcohol compound as raw material, it is degradation of promoter to introduce fermented type yeast,
Biodegradable plastic sheeting is prepared, its preparation process is：
The first step, in mass ratio by 0.1 part of polyethylene glycol, 1.5 parts of polyvinyl alcohol, the deionized water of 100 parts of addition
In, stirred 10 hours at 90 DEG C, obtain matrix A；By modified starch of the mass ratio for 1.5 parts, 1.5 parts of hydroxyethyl cellulose
Add in 10 parts of deionized water, stirred 0.6 hour at 70 DEG C, obtain matrix B.
Second step, at 80 DEG C, B is slowly added into A, continues agitating and heating 3 hours, obtain matrix C.
3rd step, the matrix C of preparation are cooled to room temperature, take 15 parts of matrix C, 5 parts of fermented yeast, 0.5 part of grape
Sugar, 0.3 part of powdered beef, 0.2 part of lactic acid, 0.1 part of sodium carbonate, temperature are 32 DEG C, mixing speed 230r/min, and stirring 2 is small
When, after pour into mould disks, carry out freeze-thaw cross-linked gel chemical conversion type 1 time, cryogenic temperature is -10 DEG C, thaw point 25
DEG C, rear take out is placed in biodegradable plastic film of the preparation containing yeast at 25 DEG C.
Embodiment 3
Using natural polysaecharides compound and polyalcohols compound as raw material, it is degradation of promoter to introduce fermented type yeast, system
Standby biodegradable plastic sheeting, its preparation process are：
The first step, in mass ratio by 0.5 part of polyacrylic acid, 1 part of polyvinyl alcohol, add in 100 parts of deionized water,
Stirred 10 hours at 90 DEG C, obtain matrix A；By hydroxypropyl cellulose that mass ratio is 2.5 parts, 0.1 part of cyclodextrin adds to
In 10 parts of deionized water, stirred 0.5 hour at 80 DEG C, obtain matrix B.
Second step, at 80 DEG C, B is slowly added into A, continues agitating and heating 1 hour, obtain matrix C.
3rd step, the matrix C of preparation are cooled to room temperature, take 20 parts matrix C, 8 parts of fermented yeast, 0.5 portion of fruit juice,
0.3 part of amino acid, 0.2 part of citric acid, 0.1 part of dibastic sodium phosphate, temperature are 32 DEG C, mixing speed 260r/min, and stirring 1 is small
When, after pour into mould disks, carry out freeze-thaw cross-linked gel chemical conversion type 1 time, cryogenic temperature is -10 DEG C, thaw point 25
DEG C, rear take out is placed in biodegradable plastic film of the preparation containing yeast at 25 DEG C.
Embodiment 4
Using natural polysaecharides compound and polyalcohols compound as raw material, it is degradation of promoter to introduce fermented type yeast, system
Standby biodegradable plastic sheeting, its preparation process are：
The first step, in mass ratio by 0.5 part of polyvinyl alcohol, 1 part of alginic acid, add in 100 parts of deionized water,
Stirred 10 hours at 90 DEG C, obtain matrix A；Carboxymethyl cellulose that mass ratio is 2.5 parts, 0.1 part of dextrin are added to 10 parts
Deionized water in, stirred 0.5 hour at 80 DEG C, obtain matrix B.
Second step, at 80 DEG C, B is slowly added into A, continues agitating and heating 1 hour, obtain matrix C.
3rd step, the matrix C of preparation are cooled to room temperature, take 10 parts of matrix C, 0.8 part of fermented yeast, 0.5 part of bean sprouts
Extract, 0.3 portion of wheaten starch, 0.2 part of sodium dihydrogen phosphate, 0.1 part of dibastic sodium phosphate, temperature are 30 DEG C, and mixing speed is
220r/min, stir 2 hours, after pour into mould disks, carry out freeze-thaw cross-linked gel chemical conversion type 1 time, cryogenic temperature is -10
DEG C, thaw point is 25 DEG C, and rear take out is placed in biodegradable plastic film of the preparation containing yeast at 25 DEG C.
Embodiment 5
Using natural polysaecharides compound and polyalcohols compound as raw material, it is degradation of promoter to introduce fermented type yeast, system
Standby biodegradable plastic sheeting, its preparation process are：
The first step, in mass ratio by 20 parts of polyacrylamide, 20 parts of alginic acid, add in 100 parts of deionized water,
Being stirred 3 hours at 120 DEG C is completely dissolved it, obtains matrix A；The hydroxyethyl cellulose that mass ratio is 500 parts is added to
In 1000 parts of deionized water, being stirred 0.5 hour at 100 DEG C makes it stir, and obtains matrix B.
Second step, at 100 DEG C, 20 parts of B are slowly added into 20 parts of A, continuing agitating and heating makes its mixing equal for 1 hour
It is even, obtain matrix C.
3rd step, the matrix C of preparation are cooled to room temperature, take 20 parts of matrix C, 20 parts of fermented yeast, 10 parts of bean sprouts leachings
Go out thing, 5 parts of glucose, 5 parts of potassium dihydrogen phosphate, 5 parts of dipotassium hydrogen phosphates, temperature is 40 DEG C, mixing speed 180r/min, is stirred
Mix makes to pour into mould disks after it is well mixed for 2 hours, carries out freeze-thaw cross-linked gel chemical conversion type 1 time, and cryogenic temperature is -50
DEG C, thaw point be 25 DEG C, after by mould take out be placed in air dry oven, at 25 DEG C dry prepare containing yeast can biology dropping
Solve plastic sheeting.
In a word, the present invention is made by drying after physical crosslinking gelation is carried out in water solution system；Water solution system
By mass fraction by 10~20 parts of polyalcohols compound water solutions, 10~50 parts of waterborne nature water-soluble polymers, 0.5~20
Part microorganism, 0.01~10 part of nutrient solution is made with 0.05~5 part of pH adjusting agent；Polyalcohols compound water solution by
The deionized water that 0.1~20 part of polyvinyl alcohol adds 10~1000 parts is made；Waterborne nature water-soluble polymers by 0.1~
The deionized water that 500 parts of waterborne nature macromolecule adds 10~1000 parts is made.The present invention using natural macromolecular material with
Synthesize high molecular mutually synergy composite and form gel rubber system, natural environmental-protective is prepared by degradation of promoter of microorganism
Biodegradable plastic film, required raw material sources are wide and economical and easily available, and prepared biodegradable plastic film has can
Biodegradation, natural environmental-protective, can secondary use the characteristics of.
There is good mechanical performance using biodegradable films plastics made from preparation method of the present invention, biological can drop
Xie Xing and the adsorptivity to some common dyes.
Verification experimental verification
70% can be hydrolyzed in 5 days naturally in film input water prepared by embodiment 1~5, film tensile strength is reachable
35MP, elongation at break is up to 600% in the case of water absorption and swelling, to the adsorbances of some common dyes up to 70mg/g.It is conventional
Dyestuff includes：One or both of crystal violet, methyl orange, malachite green, methylene blue, basic fuchsin, basic rhodamine are mixed
Compound.
As shown in figure 1, the SEM figures of biodegradable plastic film section are prepared for the present invention, it is as seen from the figure, made
Standby biodegradable plastic film dense materials, without obvious boundary, and thin-membrane section more flat smooth, illustrate institute
The main reason for compatibility is good between two or more materials used, and this is the higher mechanical performance of institute's made membrane；And can
Find out that saccharomycete is uniformly dispersed in inside film, when this makes film degradation, saccharomycete can equably play rush inside film
Enter the effect of degraded, accelerate film degradation.
Presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every substantive to the above according to inventive technique
Any simple modification, change and equivalence change that embodiment is made, are still within the scope of the technical scheme of the invention.
Claims (10)
1. a kind of preparation method of biodegradable plastic film, it is characterised in that comprise the following steps：
1) 0.1~20 part of polyalcohols compound is added by mass fraction in 10~1000 parts of deionized water, 80~120
Stirring obtains matrix A, it is standby to be cooled to room temperature up to being completely dissolved at DEG C；0.1~500 part of natural macromolecule amylose is added
Into 10~1000 parts of deionized waters, stirred at 10~100 DEG C up to being completely dissolved, obtain matrix B, it is standby to be cooled to room temperature
With；
2) at 60~100 DEG C, 10~20 parts of matrix B are slowly added into 10~50 parts of matrix A, are stirred continuously until uniformly,
Matrix C is obtained, it is standby to be cooled to room temperature；
3) take 10~20 parts matrix C, 0.5~10 part of microorganism, 0.01~10 part of nutrient solution, 0.05~5 part of pH adjusts
Agent is saved, temperature is 25~40 DEG C, stirring reaction, is subsequently poured into mould disks, is placed in 50~50 DEG C of ﹣ environment and is physical crosslinking
Gelation is molded, and is taken out drying, is prepared the biodegradable plastic film containing yeast.
2. the preparation method of biodegradable plastic film according to claim 1, it is characterised in that described polyalcohols
Compound is one or more mixtures in polyethylene glycol, polyvinyl alcohol, polyacrylic acid, alginic acid, polyacrylamide.
3. the preparation method of biodegradable plastic film according to claim 1, it is characterised in that described natural height
Molecular polysaccharide be starch, modified starch, dextrin, cyclodextrin, polyanion cellulose, hydroxypropyl cellulose, carboxymethyl cellulose,
One or more mixtures in hydroxyethyl cellulose.
4. the preparation method of biodegradable plastic film according to claim 1, it is characterised in that described yeast is
Fermented type yeast, preferably Saccharomyces cerevisiae.
5. the preparation method of biodegradable plastic film according to claim 1, it is characterised in that described nutritional agents
For in glucose, wheaten starch, farina, starch from sweet potato, beef extract, bean sprouts leachate, peptone, fruit juice, amino acid
The mixture of any one or more.
6. the preparation method of biodegradable plastic film according to claim 1, it is characterised in that described pH regulations
Agent is citric acid, potassium citrate, lactic acid, tartaric acid, malic acid, sodium citrate, sodium carbonate, potassium carbonate, disodium hydrogen phosphate, phosphoric acid
One kind or a pair of cushioning liquid in sodium dihydrogen, sodium acid carbonate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate.
7. the preparation method of biodegradable plastic film according to claim 1, it is characterised in that described physics is handed over
Connection gelation is shaped to one or more combinations in freeze-thaw, mechanical agitation, ultraviolet lighting, heating, microwave radiation.
8. the preparation method of biodegradable plastic film according to claim 1, it is characterised in that：Step 2,3) in,
Mixing speed is 50~500r/min, and the time is 1~12 hour.
9. the preparation method of biodegradable plastic film according to claim 1, it is characterised in that：In step 3), do
Dry temperature is 20~35 DEG C.
10. biodegradable plastic film made from a kind of preparation method as described in claim 1 to 9 any one is adsorbing
Applied in dyestuff, it is characterised in that：The dyestuff for being used to adsorb after biodegradable plastic film water absorption and swelling includes：Crystal violet,
One or both of methyl orange, malachite green, methylene blue, basic fuchsin, basic rhodamine mixture.
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| CN110367249A (en) * | 2019-07-24 | 2019-10-25 | 陕西科技大学 | A kind of degradable medicine carrying membrane material and its preparation method and application with slow-release function step by step |
| CN110746673A (en) * | 2019-10-30 | 2020-02-04 | 河南晖睿智能科技有限公司 | Easily-degradable environment-friendly plastic material |
| CN112080155A (en) * | 2020-09-21 | 2020-12-15 | 正业包装（中山）有限公司 | Recycled paperboard fiber-based composite molded product and preparation method thereof |
| CN112300433A (en) * | 2020-11-04 | 2021-02-02 | 西北师范大学 | Preparation method of cheap degradable polymer composite membrane |
| CN114929794A (en) * | 2019-11-27 | 2022-08-19 | 由农业部长代表的美利坚合众国 | Natural packaging composition |
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