CN104479162A - Graphene-based biodegradable composite thin film for garden - Google Patents
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Abstract
The invention discloses a graphene-based biodegradable composite thin film for a garden. The thin film is prepared by the following steps: comprehensively carrying out graphenization on the thin film by compounding oxidized graphene two times; meanwhile, adding 10-20 parts of fine starch, 20-30 parts of cellulose and 5-10 parts of an oxidized graphene suspension into 50-100 parts of a caprolactam benzenesulfonic acid ionic liquid; and then dropwise adding 30-40 parts of a polylactic acid solution which is dissolved in chloroform to obtain the thin film. The thin film material has the advantages of good mechanical property, high thermal stability, degradability, good biocompatibility and the like and can be used in the field of gardens.
Description
Technical field
The invention belongs to biodegradable material technical field, particularly a kind of gardens use graphene-based biodegradable compound film.
Background technology
In prior art, field, gardens is very large for the demand of film, and especially resistance to acids and bases and erosion resistance, in use, the performances such as the mechanics of film and machinery are also extremely important simultaneously.It is that main raw material is produced that present degradable films all adopts with polyvinyl alcohol, due to the melt temperature of polyvinyl alcohol and decomposition temperature very close, so general all by steel plate type curtain coating or extrude T connector casting method to realize.No matter wet-dry change curtain coating, all there is production efficiency low, energy consumption is high, and cost remains high, and lacks the shortcoming of the market competitiveness.At present, the domestic water-solube and biodegradable film also not occurring prepared by suitable method special material out.
Graphene is star's material quite concerned in decades recently, the Graphene of functionalization, be as the criterion two-dimensional layered structure, containing many activity functional groups such as hydroxyl, carboxyl, epoxy group(ing) and carbonyls, there is higher specific surface energy, good wetting ability and mechanical property, and it is better dispersed in polar organic solvent, by graphene oxide is prepared functional high-polymer nano composite material as new packing, can be used for improving the comprehensive physical performance such as mechanics, heat conduction, conduction of nano composite material.
Meanwhile, the material such as cellulose materials, starch has extraordinary degradability, biocompatibility and wide material sources, but film prepared by single degradation material out, the non-constants of performance such as its mechanics and machinery; Poly(lactic acid) is then the polymkeric substance that this field routine uses, and it has excellent mechanical strength and toughness.
How above Material cladding can be got up, to prepare one and meet gardens demand, and the laminated film with excellent physical and chemical performance is a difficult problem for research now.
Summary of the invention
The object of the invention is for the problems referred to above, develop a kind of gardens and use graphene-based biodegradable compound film,
Preparation process is as follows:
A, 1-5g Graphite Powder 99 is put into round-bottomed flask, then the 98% appropriate vitriol oil is added successively, potassium permanganate and SODIUMNITRATE, 4-6h is incubated under the condition of ice bath, be warming up to room temperature subsequently, stir 1-2h, add appropriate deionized water subsequently, be warming up to 60-80 DEG C, stir 1-2h, add appropriate hydrogen peroxide again, continuing to be stirred to solution presents orange-yellow, standing at room temperature 24h subsequently, pass through centrifugation, dilute hydrochloric acid and deionized water repetitive scrubbing 2-3 time successively, obtain pure graphene oxide, and this graphene oxide is dissolved in deionized water, ultrasonic 5-8h, prepare the graphene oxide suspension that concentration is 1.5mg/ml,
B, 10-20 weight part refinement starch, 20-30 part by weight of cellulose and 5-10 weight part graphene oxide suspension are joined in 50-100 part by weight of caprolactam Phenylsulfonic acid class ionic liquid, constantly 1-3h is stirred at 60-70 DEG C, obtain homogeneous mixed solution A, subsequently the 30-40 weight part PLA solution being dissolved in chloroform is slowly added dropwise in mixed solution A, and under the condition of high speed magnetic stirring, poly(lactic acid) and mixed solution A are mixed, leaves standstill, obtain mixing solutions B;
C, mixing solutions B is injected in masking mould, even curtain coating, leaves standstill 16h, be placed on subsequently in loft drier, at temperature is 30 DEG C ~ 50 DEG C dry 12 ~ 72 hours, take out, be cooled to room temperature, take off film, obtained composite membrane A;
D, composite membrane A is cleaned 2-4h in the solution of ethanol/water (volume ratio is 1:5), then clean up with distilled water, subsequently composite membrane A is immersed in amination 1-2h in the polymine PEI solution of 1mg/ml, take out film, dry, and with 5% dilute hydrochloric acid and washed with de-ionized water, dry, obtain pretreated composite membrane A;
E, pretreated composite membrane A is immersed in 10-30min in graphene oxide suspension, at room temperature dry subsequently, washed with de-ionized water, dry, then 10-30min in the polymine PEI solution being immersed in 1mg/ml, continue at room temperature dry after taking out, washed with de-ionized water, dry, repeat above step 5-10 time, obtain gardens and use graphene-based biodegradable compound film;
Described laminated film acid-proof alkaline is good, soak 15min in the strong acid or strong base solution of 1mol/L after, the corrosion rate of its resistance to strong acid is 4-12%, the corrosion rate of resistance to highly basic is 2-9%, laminated film is after the natural degradation landfill of 10d, sample quality wastage rate are 5-12%, and after the natural degradation landfill of 25d, sample is degraded to many small shredss.
As preferably, in step b, the weight part of graphene oxide is 7 parts;
As preferably, described graphene oxide more than 50% is single-layer graphene oxide.
Beneficial effect of the present invention:
(1) the present invention is by twice combined oxidation Graphene, is once that Graphene can be cross-linked fully with raw material by itself and raw material mixing; Be once LBL self-assembly, can make film outside surface also can graphite alkylene completely;
(2) refinement starch, Mierocrystalline cellulose and graphene oxide suspension join in hexanolactam Phenylsulfonic acid class ionic liquid by the present invention, and then drip the PLA solution being dissolved in chloroform, the thin-film material obtained has the advantages such as good mechanical property, thermostability are high, degradable, good biocompatibility, and can be used as field, gardens uses;
(3) preparation method of composite film of the present invention is simple, is convenient to suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, and comparable data describes in further detail the present invention.Should be understood that these embodiments just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Embodiment 1:
A kind of gardens use graphene-based biodegradable compound film,
Preparation process is as follows:
A, 1g Graphite Powder 99 is put into round-bottomed flask, then the 98% appropriate vitriol oil is added successively, potassium permanganate and SODIUMNITRATE, 4h is incubated under the condition of ice bath, be warming up to room temperature subsequently, stir 1h, add appropriate deionized water subsequently, be warming up to 60 DEG C, stir 1h, add appropriate hydrogen peroxide again, continuing to be stirred to solution presents orange-yellow, standing at room temperature 24h subsequently, pass through centrifugation, dilute hydrochloric acid and deionized water repetitive scrubbing 2 times successively, obtain pure graphene oxide, and this graphene oxide is dissolved in deionized water, ultrasonic 5-8h, prepare the graphene oxide suspension that concentration is 1.5mg/ml,
B, 10 weight part refinement starch, 20 part by weight of cellulose and 5 weight part graphene oxide suspension are joined in 50 part by weight of caprolactam Phenylsulfonic acid class ionic liquids, constantly 1h is stirred at 60 DEG C, obtain homogeneous mixed solution A, subsequently the 30 weight part PLA solution being dissolved in chloroform are slowly added dropwise in mixed solution A, and under the condition of high speed magnetic stirring, poly(lactic acid) and mixed solution A are mixed, leaves standstill, obtain mixing solutions B;
C, mixing solutions B is injected in masking mould, even curtain coating, leaves standstill 16h, be placed on subsequently in loft drier, at temperature is 30 DEG C dry 12 hours, take out, be cooled to room temperature, take off film, obtained composite membrane A;
D, composite membrane A is cleaned 2h in the solution of ethanol/water (volume ratio is 1:5), then clean up with distilled water, subsequently composite membrane A is immersed in amination 1h in the polymine PEI solution of 1mg/ml, take out film, dry, and with 5% dilute hydrochloric acid and washed with de-ionized water, dry, obtain pretreated composite membrane A;
E, pretreated composite membrane A is immersed in 10min in graphene oxide suspension, at room temperature dry subsequently, washed with de-ionized water, dry, then 10min in the polymine PEI solution being immersed in 1mg/ml, continue at room temperature dry after taking out, washed with de-ionized water, dry, repeat above step 5 time, obtain gardens and use graphene-based biodegradable compound film;
Described laminated film acid-proof alkaline is good, soak 15min in the strong acid or strong base solution of 1mol/L after, the corrosion rate of its resistance to strong acid is 12%, the corrosion rate of resistance to highly basic is 9%, laminated film is after the natural degradation landfill of 10d, sample quality wastage rate are 5%, and after the natural degradation landfill of 25d, sample is degraded to many small shredss.
Embodiment 2:
A kind of gardens use graphene-based biodegradable compound film,
Preparation process is as follows:
A, 5g Graphite Powder 99 is put into round-bottomed flask, then the 98% appropriate vitriol oil is added successively, potassium permanganate and SODIUMNITRATE, 6h is incubated under the condition of ice bath, be warming up to room temperature subsequently, stir 2h, add appropriate deionized water subsequently, be warming up to 80 DEG C, stir 2h, add appropriate hydrogen peroxide again, continuing to be stirred to solution presents orange-yellow, standing at room temperature 24h subsequently, pass through centrifugation, dilute hydrochloric acid and deionized water repetitive scrubbing 3 times successively, obtain pure graphene oxide, and this graphene oxide is dissolved in deionized water, ultrasonic 8h, prepare the graphene oxide suspension that concentration is 1.5mg/ml,
B, 20 weight part refinement starch, 30 part by weight of cellulose and 10 weight part graphene oxide suspension are joined in 100 part by weight of caprolactam Phenylsulfonic acid class ionic liquids, constantly 3h is stirred at 70 DEG C, obtain homogeneous mixed solution A, subsequently the 40 weight part PLA solution being dissolved in chloroform are slowly added dropwise in mixed solution A, and under the condition of high speed magnetic stirring, poly(lactic acid) and mixed solution A are mixed, leaves standstill, obtain mixing solutions B;
C, mixing solutions B is injected in masking mould, even curtain coating, leaves standstill 16h, be placed on subsequently in loft drier, at temperature is 50 DEG C dry 72 hours, take out, be cooled to room temperature, take off film, obtained composite membrane A;
D, composite membrane A is cleaned 4h in the solution of ethanol/water (volume ratio is 1:5), then clean up with distilled water, subsequently composite membrane A is immersed in amination 2h in the polymine PEI solution of 1mg/ml, take out film, dry, and with 5% dilute hydrochloric acid and washed with de-ionized water, dry, obtain pretreated composite membrane A;
E, pretreated composite membrane A is immersed in 30min in graphene oxide suspension, at room temperature dry subsequently, washed with de-ionized water, dry, then 30min in the polymine PEI solution being immersed in 1mg/ml, continue at room temperature dry after taking out, washed with de-ionized water, dry, repeat above step 10 time, obtain gardens and use graphene-based biodegradable compound film;
Described laminated film acid-proof alkaline is good, soak 15min in the strong acid or strong base solution of 1mol/L after, the corrosion rate of its resistance to strong acid is 4%, the corrosion rate of resistance to highly basic is 2%, laminated film is after the natural degradation landfill of 10d, sample quality wastage rate are 5%, and after the natural degradation landfill of 25d, sample is degraded to many small shredss.
Embodiment 3:
A kind of gardens use graphene-based biodegradable compound film,
Preparation process is as follows:
A, 5g Graphite Powder 99 is put into round-bottomed flask, then the 98% appropriate vitriol oil is added successively, potassium permanganate and SODIUMNITRATE, 6h is incubated under the condition of ice bath, be warming up to room temperature subsequently, stir 2h, add appropriate deionized water subsequently, be warming up to 80 DEG C, stir 2h, add appropriate hydrogen peroxide again, continuing to be stirred to solution presents orange-yellow, standing at room temperature 24h subsequently, pass through centrifugation, dilute hydrochloric acid and deionized water repetitive scrubbing 3 times successively, obtain pure graphene oxide, and this graphene oxide is dissolved in deionized water, ultrasonic 8h, prepare the graphene oxide suspension that concentration is 1.5mg/ml,
B, 20 weight part refinement starch, 30 part by weight of cellulose and 7 weight part graphene oxide suspension are joined in 100 part by weight of caprolactam Phenylsulfonic acid class ionic liquids, constantly 3h is stirred at 70 DEG C, obtain homogeneous mixed solution A, subsequently the 40 weight part PLA solution being dissolved in chloroform are slowly added dropwise in mixed solution A, and under the condition of high speed magnetic stirring, poly(lactic acid) and mixed solution A are mixed, leaves standstill, obtain mixing solutions B;
C, mixing solutions B is injected in masking mould, even curtain coating, leaves standstill 16h, be placed on subsequently in loft drier, at temperature is 50 DEG C dry 72 hours, take out, be cooled to room temperature, take off film, obtained composite membrane A;
D, composite membrane A is cleaned 4h in the solution of ethanol/water (volume ratio is 1:5), then clean up with distilled water, subsequently composite membrane A is immersed in amination 2h in the polymine PEI solution of 1mg/ml, take out film, dry, and with 5% dilute hydrochloric acid and washed with de-ionized water, dry, obtain pretreated composite membrane A;
E, pretreated composite membrane A is immersed in 30min in graphene oxide suspension, at room temperature dry subsequently, washed with de-ionized water, dry, then 30min in the polymine PEI solution being immersed in 1mg/ml, continue at room temperature dry after taking out, washed with de-ionized water, dry, repeat above step 10 time, obtain gardens and use graphene-based biodegradable compound film;
Described laminated film acid-proof alkaline is good, soak 15min in the strong acid or strong base solution of 1mol/L after, the corrosion rate of its resistance to strong acid is 4%, the corrosion rate of resistance to highly basic is 2%, laminated film is after the natural degradation landfill of 10d, sample quality wastage rate are 5%, and after the natural degradation landfill of 25d, sample is degraded to many small shredss.
Embodiment 4:
A kind of gardens use graphene-based biodegradable compound film,
Preparation process is as follows:
A, 2g Graphite Powder 99 is put into round-bottomed flask, then the 98% appropriate vitriol oil is added successively, potassium permanganate and SODIUMNITRATE, 6h is incubated under the condition of ice bath, be warming up to room temperature subsequently, stir 2h, add appropriate deionized water subsequently, be warming up to 80 DEG C, stir 2h, add appropriate hydrogen peroxide again, continuing to be stirred to solution presents orange-yellow, standing at room temperature 24h subsequently, pass through centrifugation, dilute hydrochloric acid and deionized water repetitive scrubbing 3 times successively, obtain pure graphene oxide, and this graphene oxide is dissolved in deionized water, ultrasonic 8h, prepare the graphene oxide suspension that concentration is 1.5mg/ml,
B, 20 weight part refinement starch, 30 part by weight of cellulose and 7 weight part graphene oxide suspension are joined in 100 part by weight of caprolactam Phenylsulfonic acid class ionic liquids, constantly 3h is stirred at 70 DEG C, obtain homogeneous mixed solution A, subsequently the 40 weight part PLA solution being dissolved in chloroform are slowly added dropwise in mixed solution A, and under the condition of high speed magnetic stirring, poly(lactic acid) and mixed solution A are mixed, leaves standstill, obtain mixing solutions B;
C, mixing solutions B is injected in masking mould, even curtain coating, leaves standstill 16h, be placed on subsequently in loft drier, at temperature is 50 DEG C dry 72 hours, take out, be cooled to room temperature, take off film, obtained composite membrane A;
D, composite membrane A is cleaned 4h in the solution of ethanol/water (volume ratio is 1:5), then clean up with distilled water, subsequently composite membrane A is immersed in amination 2h in the polymine PEI solution of 1mg/ml, take out film, dry, and with 5% dilute hydrochloric acid and washed with de-ionized water, dry, obtain pretreated composite membrane A;
E, pretreated composite membrane A is immersed in 30min in graphene oxide suspension, at room temperature dry subsequently, washed with de-ionized water, dry, then 30min in the polymine PEI solution being immersed in 1mg/ml, continue at room temperature dry after taking out, washed with de-ionized water, dry, repeat above step 10 time, obtain gardens and use graphene-based biodegradable compound film;
Described laminated film acid-proof alkaline is good, soak 15min in the strong acid or strong base solution of 1mol/L after, the corrosion rate of its resistance to strong acid is 4%, the corrosion rate of resistance to highly basic is 2%, laminated film is after the natural degradation landfill of 10d, sample quality wastage rate are 5%, and after the natural degradation landfill of 25d, sample is degraded to many small shredss.
Embodiment 5:
A kind of gardens use graphene-based biodegradable compound film,
Preparation process is as follows:
A, 1g Graphite Powder 99 is put into round-bottomed flask, then the 98% appropriate vitriol oil is added successively, potassium permanganate and SODIUMNITRATE, 4h is incubated under the condition of ice bath, be warming up to room temperature subsequently, stir 1h, add appropriate deionized water subsequently, be warming up to 60 DEG C, stir 1h, add appropriate hydrogen peroxide again, continuing to be stirred to solution presents orange-yellow, standing at room temperature 24h subsequently, pass through centrifugation, dilute hydrochloric acid and deionized water repetitive scrubbing 2 times successively, obtain pure graphene oxide, and this graphene oxide is dissolved in deionized water, ultrasonic 5-8h, prepare the graphene oxide suspension that concentration is 1.5mg/ml,
B, 10 weight part refinement starch, 20 part by weight of cellulose and 7 weight part graphene oxide suspension are joined in 50 part by weight of caprolactam Phenylsulfonic acid class ionic liquids, constantly 1h is stirred at 60 DEG C, obtain homogeneous mixed solution A, subsequently the 30 weight part PLA solution being dissolved in chloroform are slowly added dropwise in mixed solution A, and under the condition of high speed magnetic stirring, poly(lactic acid) and mixed solution A are mixed, leaves standstill, obtain mixing solutions B;
C, mixing solutions B is injected in masking mould, even curtain coating, leaves standstill 16h, be placed on subsequently in loft drier, at temperature is 30 DEG C dry 12 hours, take out, be cooled to room temperature, take off film, obtained composite membrane A;
D, composite membrane A is cleaned 2h in the solution of ethanol/water (volume ratio is 1:5), then clean up with distilled water, subsequently composite membrane A is immersed in amination 1h in the polymine PEI solution of 1mg/ml, take out film, dry, and with 5% dilute hydrochloric acid and washed with de-ionized water, dry, obtain pretreated composite membrane A;
E, pretreated composite membrane A is immersed in 10min in graphene oxide suspension, at room temperature dry subsequently, washed with de-ionized water, dry, then 10min in the polymine PEI solution being immersed in 1mg/ml, continue at room temperature dry after taking out, washed with de-ionized water, dry, repeat above step 5 time, obtain gardens and use graphene-based biodegradable compound film;
Described laminated film acid-proof alkaline is good, soak 15min in the strong acid or strong base solution of 1mol/L after, the corrosion rate of its resistance to strong acid is 12%, the corrosion rate of resistance to highly basic is 9%, laminated film is after the natural degradation landfill of 10d, sample quality wastage rate are 5%, and after the natural degradation landfill of 25d, sample is degraded to many small shredss.
Comparative example 1:
A kind of gardens use graphene-based biodegradable compound film,
Preparation process is as follows:
A, 1g Graphite Powder 99 is put into round-bottomed flask, then the 98% appropriate vitriol oil is added successively, potassium permanganate and SODIUMNITRATE, 4h is incubated under the condition of ice bath, be warming up to room temperature subsequently, stir 1h, add appropriate deionized water subsequently, be warming up to 60 DEG C, stir 1h, add appropriate hydrogen peroxide again, continuing to be stirred to solution presents orange-yellow, standing at room temperature 24h subsequently, pass through centrifugation, dilute hydrochloric acid and deionized water repetitive scrubbing 2 times successively, obtain pure graphene oxide, and this graphene oxide is dissolved in deionized water, ultrasonic 5-8h, prepare the graphene oxide suspension that concentration is 1.5mg/ml,
B, 10 weight part refinement starch and 5 weight part graphene oxide suspension are joined in 50 part by weight of caprolactam Phenylsulfonic acid class ionic liquids, constantly 1h is stirred at 60 DEG C, obtain homogeneous mixed solution A, subsequently the 30 weight part PLA solution being dissolved in chloroform are slowly added dropwise in mixed solution A, and under the condition of high speed magnetic stirring, poly(lactic acid) and mixed solution A are mixed, leaves standstill, obtain mixing solutions B;
C, mixing solutions B is injected in masking mould, even curtain coating, leaves standstill 16h, be placed on subsequently in loft drier, at temperature is 30 DEG C dry 12 hours, take out, be cooled to room temperature, take off film, obtained composite membrane A;
D, composite membrane A is cleaned 2h in the solution of ethanol/water (volume ratio is 1:5), then clean up with distilled water, subsequently composite membrane A is immersed in amination 1h in the polymine PEI solution of 1mg/ml, take out film, dry, and with 5% dilute hydrochloric acid and washed with de-ionized water, dry, obtain pretreated composite membrane A;
E, pretreated composite membrane A is immersed in 10min in graphene oxide suspension, at room temperature dry subsequently, washed with de-ionized water, dry, then 10min in the polymine PEI solution being immersed in 1mg/ml, continue at room temperature dry after taking out, washed with de-ionized water, dry, repeat above step 5 time, obtain gardens and use graphene-based biodegradable compound film;
Described laminated film acid-proof alkaline is good, soak 15min in the strong acid or strong base solution of 1mol/L after, the corrosion rate of its resistance to strong acid is 62%, the corrosion rate of resistance to highly basic is 59%, laminated film is after the natural degradation landfill of 10d, sample quality wastage rate are 14%, and after the natural degradation landfill of 15d, sample is degraded to many small shredss.
Comparative example 2:
A kind of gardens use graphene-based biodegradable compound film,
Preparation process is as follows:
A, 1g Graphite Powder 99 is put into round-bottomed flask, then the 98% appropriate vitriol oil is added successively, potassium permanganate and SODIUMNITRATE, 4h is incubated under the condition of ice bath, be warming up to room temperature subsequently, stir 1h, add appropriate deionized water subsequently, be warming up to 60 DEG C, stir 1h, add appropriate hydrogen peroxide again, continuing to be stirred to solution presents orange-yellow, standing at room temperature 24h subsequently, pass through centrifugation, dilute hydrochloric acid and deionized water repetitive scrubbing 2 times successively, obtain pure graphene oxide, and this graphene oxide is dissolved in deionized water, ultrasonic 5-8h, prepare the graphene oxide suspension that concentration is 1.5mg/ml,
B, 10 weight part refinement starch, 20 part by weight of cellulose and 5 weight part graphene oxide suspension to be joined in 50 part by weight of caprolactam Phenylsulfonic acid class ionic liquids, at 60 DEG C, constantly stir 1h, obtain homogeneous mixing solutions B;
C, mixing solutions B is injected in masking mould, even curtain coating, leaves standstill 16h, be placed on subsequently in loft drier, at temperature is 30 DEG C dry 12 hours, take out, be cooled to room temperature, take off film, obtained composite membrane A;
D, composite membrane A is cleaned 2h in the solution of ethanol/water (volume ratio is 1:5), then clean up with distilled water, subsequently composite membrane A is immersed in amination 1h in the polymine PEI solution of 1mg/ml, take out film, dry, and with 5% dilute hydrochloric acid and washed with de-ionized water, dry, obtain pretreated composite membrane A;
E, pretreated composite membrane A is immersed in 10min in graphene oxide suspension, at room temperature dry subsequently, washed with de-ionized water, dry, then 10min in the polymine PEI solution being immersed in 1mg/ml, continue at room temperature dry after taking out, washed with de-ionized water, dry, repeat above step 5 time, obtain gardens and use graphene-based biodegradable compound film;
Described laminated film acid-proof alkaline is good, soak 15min in the strong acid or strong base solution of 1mol/L after, the corrosion rate of its resistance to strong acid is 6%, the corrosion rate of resistance to highly basic is 7%, laminated film is after the natural degradation landfill of 10d, sample quality wastage rate are 2%, and after the natural degradation landfill of 55d, sample is degraded to many small shredss.
Claims (3)
1. gardens use a graphene-based biodegradable compound film, it is characterized in that:
Preparation process is as follows:
A, 1-5g Graphite Powder 99 is put into round-bottomed flask, then the 98% appropriate vitriol oil is added successively, potassium permanganate and SODIUMNITRATE, 4-6h is incubated under the condition of ice bath, be warming up to room temperature subsequently, stir 1-2h, add appropriate deionized water subsequently, be warming up to 60-80 DEG C, stir 1-2h, add appropriate hydrogen peroxide again, continuing to be stirred to solution presents orange-yellow, standing at room temperature 24h subsequently, pass through centrifugation, dilute hydrochloric acid and deionized water repetitive scrubbing 2-3 time successively, obtain pure graphene oxide, and this graphene oxide is dissolved in deionized water, ultrasonic 5-8h, prepare the graphene oxide suspension that concentration is 1.5mg/ml,
B, 10-20 weight part refinement starch, 20-30 part by weight of cellulose and 5-10 weight part graphene oxide suspension are joined in 50-100 part by weight of caprolactam Phenylsulfonic acid class ionic liquid, constantly 1-3h is stirred at 60-70 DEG C, obtain homogeneous mixed solution A, subsequently the 30-40 weight part PLA solution being dissolved in chloroform is slowly added dropwise in mixed solution A, and under the condition of high speed magnetic stirring, poly(lactic acid) and mixed solution A are mixed, leaves standstill, obtain mixing solutions B;
C, mixing solutions B is injected in masking mould, even curtain coating, leaves standstill 16h, be placed on subsequently in loft drier, at temperature is 30 DEG C ~ 50 DEG C dry 12 ~ 72 hours, take out, be cooled to room temperature, take off film, obtained composite membrane A;
D, composite membrane A is cleaned 2-4h in the solution of ethanol/water (volume ratio is 1:5), then clean up with distilled water, subsequently composite membrane A is immersed in amination 1-2h in the polymine PEI solution of 1mg/ml, take out film, dry, and with 5% dilute hydrochloric acid and washed with de-ionized water, dry, obtain pretreated composite membrane A;
E, pretreated composite membrane A is immersed in 10-30min in graphene oxide suspension, at room temperature dry subsequently, washed with de-ionized water, dry, then 10-30min in the polymine PEI solution being immersed in 1mg/ml, continue at room temperature dry after taking out, washed with de-ionized water, dry, repeat above step 5-10 time, obtain gardens and use graphene-based biodegradable compound film;
Described laminated film acid-proof alkaline is good, soak 15min in the strong acid or strong base solution of 1mol/L after, the corrosion rate of its resistance to strong acid is 4-12%, the corrosion rate of resistance to highly basic is 2-9%, laminated film is after the natural degradation landfill of 10d, sample quality wastage rate are 5-12%, and after the natural degradation landfill of 25d, sample is degraded to many small shredss.
2. gardens as claimed in claim 1 use a graphene-based biodegradable compound film, it is characterized in that the weight part of graphene oxide in step b is 7 parts.
3. gardens as claimed in claim 1 or 2 use a graphene-based biodegradable compound film, it is characterized in that described graphene oxide more than 50% is single-layer graphene oxide.
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| CN110684263A (en) * | 2019-10-15 | 2020-01-14 | 福建船政交通职业学院 | Degradable film material and preparation method thereof |
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