CN106905565A - A kind of preparation method of carragheen konjaku glucomannan graphene oxide film - Google Patents
A kind of preparation method of carragheen konjaku glucomannan graphene oxide film Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of carragheen konjaku glucomannan graphene oxide film, belongs to composite film material technical field.The preparation method is that κ carragheens and konjaku glucomannan are added in graphene oxide water solution, is poured into glass mold after agitated, dispersion degassing, is placed at room temperature mould after being completely dried, and takes off film and obtains final product laminated film of the present invention.Carragheen konjaku glucomannan graphene composite thin film prepared by the present invention, its is simple to operate, and cost is relatively low, and obtained thin-film material regularity is good, degradable, good biocompatibility.Preparation method of the present invention resets to graphene oxide in konjaku glucomannan matrix, uniform through the modified film of carragheen.Obtained carragheen konjaku glucomannan graphene composite thin film of the invention, its heat endurance and high mechanical strength, degradable, good biocompatibility, can be widely applied to the fields such as packaging, organizational project and biomaterial.
Description
Technical field
The invention belongs to composite film material technical field, specially a kind of carragheen-konjaku glucomannan-graphite oxide
The preparation method of alkene film.
Background technology
Furtherd investigate with to biological structure, bionic structure material recently becomes a new focus of investigation of materials.Hai Jing
Shell be of considerable interest as natural mother of pearl.The excellent mechanical property of extra large mirror shell comes from its orderly stratiform knot
The advantage both interface zone enriched between structure and inorganic platelet and organic matrix is combined.The art of composite is to find
Effective combination between opposite attribute.Mother of pearl is to make possible outstanding representative using layer structure.It is subject to
The inspiration of natural mixed structure and its very good mechanical properties, researchers are attempted simulating natural peral mother by various methods
Rotating fields, prepare the composite of imitative mother-of-pearl layer structure.Recently, flat double-walled carbon nano-tube (FDWCNTs), Al2O3Piece
Crystalline substance, graphene oxide (GO) and other materials are the new high-performance of development as the new inorganic module and organic polymer of constructing
Bionic laminar artificial material provides more choices.
GO is used as preparing the presoma of chemical modification Graphene (CMG) in the synthesis of new material.Graphene oxide
It is the Graphene of functionalization, be defined two-dimensional layered structure, contains many active function groups such as hydroxyl, carboxyl, epoxy radicals and carbonyl
Group, with specific surface energy higher, good hydrophily and mechanical performance, and dispersiveness is preferable in polar organic solvent,
Its cost is even more more much lower than CNT, and functional high-polymer nanometer is prepared as new packing by using graphene oxide
Composite, to improve the comprehensive physical performance such as mechanics, heat conduction, conduction of nano composite material because Graphene possesses than other
The all excellent performance of any material, some are even up to the limit of theoretical prediction, and graphene composite material has become one newly
Study hotspot.Although Graphene is highly inert material, graphene oxide (GO) is easy to that chemistry functional is nearest to be ground
Study carefully that to show that feature that multilayer graphene oxide is measured under the speed of 600 metre per second (m/s)s is penetrated can be nearly the ten of document report light plate
Times it is evident that, stannic oxide/graphene nano piece is used as imitative mother of pearl material preferable inorganic, and to construct module imitative
Mother of pearl graphene oxide (GO)-organic polymer composite material shows excellent mechanical performance.
Compared with synthetic polymer, the polymer of natural origin is in biocompatibility, biodegradability and hypotoxicity
Requirement aspect advantageously.Carragheen (CAR) is a kind of raw polymer in sea of the polysaccharide extracted from the middle of red algae, is gala
Sugar and Anhydrogalactose unit are formed via glycosidic bond composition.Kappa-carrageenan (κ-CAR) is two classes tool with Iota-Carraginan (i-CAR)
There is the carragheen of gelling ability.Than Iota-Carraginan, kappa-carrageenan gel has more preferable stability, elasticity and flexibility.In addition
κ-CAR show more preferable film forming.Due to its good pharmacology performance and bioactivity, κ-CAR are existing business applications
Most wide carragheen.Research finds that the usable carragheens of GO carry out functionalization.GO- carragheens composite (GO-Car) of preparation
Further apply the cell medium of bionical base material and hydroxyapatite (HA) biomineralization.GO-Car mixtures are also recognized simultaneously
To be the material that great expectations is sent in osteanagenesis and bone collection field.In addition to these advantages, κ-CAR have low-viscosity cause
Life defect, this causes it that quality of forming film, and its composite machinery performance are difficult to control in the method for solvent evaporation film forming
It is poor.
Konjaku glucomannan (KGM) is another natural polymer, and source is sufficient, biodegradable, with hydrophily, gel
Multifrequency nature and some special physiological functions such as property, film forming, antibiotic property, low heat value, and chemical modifiable function
Group, can be widely applied to food, medicine, chemical industry and biological field.Its gelatification, film forming (dura mater), antibiotic property and
Therefore low heat value aspect has very big advantage, can prepare a kind of composition polymer with κ-CAR and KGM, promising as having
Component prepares superpower biomimetic material together with GO, due to there is substantial amounts of hydroxyl on polymer chain and GO nanometer sheets, thus it is speculated that two
There should be Hydrogenbond between person.
At present, many scientists are more combined using synthetic organic polymers with graphene oxide, rather than natural polymerization
Thing.However, the raw material of synthetic organic polymers, such as oil and coal, are all nonrenewable resourceses.Therefore, using natural organic poly-
Compound prepares the inevitable direction that the new material with excellent properties is material science research.
The content of the invention
It is an object of the invention to provide a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film.
By the present invention in that being prepared for imitating with two kinds of cheap natural polymer kappa-carrageenans (κ-CAR) and konjaku glucomannan (KGM)
The GO- polymer composites of mother of pearl structure.Enhancing κ-CAR and KGM each advantage improving film forming controllability and machine
While tool performance, its good pharmacology performance and bioactivity is maintained, extend composite in biomedical sector
Can range of application.
The object of the invention is realized by following technical proposals：
A kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film, it is by κ-OK a karaoke club to state preparation method
Glue and konjaku glucomannan are added in graphene oxide water solution, are poured into glass mold after agitated, dispersion degassing, completely
Mould is placed at room temperature after drying, is taken off film and is obtained final product laminated film of the present invention.
As a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film of the present invention, the κ-
The mass ratio of carragheen and konjaku glucomannan is 1~10 ﹕ 1~5.
As a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film of the present invention, the oxygen
The concentration of graphene oxide is 0.25~1mg/mL in graphite aqueous solution.
As a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film of the present invention, the oxygen
The quality of graphite alkene is the 2.5~10% of kappa-carrageenan and konjaku glucomannan gross mass.
As a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film of the present invention, the glass
Glass mould is pre-processed by the way of face coat or pad pasting in advance；Wherein, face coat uses silane coupler to glass
Glass die surface is coated, and pad pasting is used and pastes one layer of polytetrafluoroethylene film in surface of glass die.
It is described to stir as a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film of the present invention
Mix and use mechanical agitation, churned mechanically temperature is 50~100 DEG C, rotating speed is 245~650rpm；Time is 20~60min；Institute
The time for stating dispersion degassing is 20~60min；The drying temperature is 20~50 DEG C, and the time is 1~24h, and the room temperature is placed
Time is 5~24h.
Specifically, the preparation method of a kind of carragheen-konjaku glucomannan-graphene oxide film of the present invention,
Comprise the following steps：
1) add graphene oxide into deionized water solution, ultrasonic agitation obtains graphene oxide water solution；
2) kappa-carrageenan and konjaku glucomannan are added in above-mentioned graphene oxide water solution, are obtained after mechanical agitation
Film forming mixed liquor；
3) poured into above-mentioned in the glass mold anticipated after ultrasonic disperse degassing into film liquid, curtain coating is paved, in
1~24h is dried at 20~50 DEG C, mould is placed in after being completely dried after placing 5~24h at room temperature and is taken off film and obtain final product carragheen-evil spirit
Taro Glucomannan-graphene composite thin film.
The present invention also provides described carragheen-konjaku glucomannan-graphene composite thin film, the laminated film
Prepared using above-mentioned preparation method.
The present invention also provides the application of described carragheen-konjaku glucomannan-graphene composite thin film, described multiple
Close application of the film in packaging material, organizational project and biomaterial.
Beneficial effects of the present invention：
1st, natural polymer carragheen-konjaku glucomannan-graphene composite thin film prepared by the present invention, its preparation
Process is simple, and cost is relatively low, and obtained thin-film material regularity is good, degradable, good biocompatibility.
2nd, it is modified by carragheen during graphene oxide is reset to konjaku glucomannan matrix by preparation method of the present invention
Film it is uniform, high mechanical strength.
3rd, the obtained natural polymer/carragheen-konjaku glucomannan-graphene composite thin film of the present invention, its heat
Stability and high mechanical strength, degradable, good biocompatibility can be widely applied to packaging, organizational project and biomaterial
Deng field.
Brief description of the drawings
Fig. 1 is for embodiment 1 to 4 and without the thin-film material tensile stress strain curve figure prepared by graphene oxide.
Fig. 2 is different carragheens bent with the tensile stress-strain of the thin-film material of preparation under the Glucomannan adding proportion of magic domain
Line chart.
Fig. 3 is the thermogravimetric curve figure of embodiment 3 and the thin-film material prepared without graphene oxide.
Fig. 4 is thin-film material parameter in bio kinetic model proliferative cell quantity comparison diagram prepared by embodiment 3.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
A kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film, it is by κ-OK a karaoke club to state preparation method
Glue and konjaku glucomannan are added in graphene oxide water solution, are poured into glass mold after agitated, dispersion degassing, completely
Mould is placed at room temperature after drying, is taken off film and is obtained final product laminated film of the present invention.
Inventor is prepared for the stratiform knot with clear-cut of different GO additions by blow-off liquor self-assembly method
Carragheen-konjaku glucomannan-graphene composite thin film the material of structure.Test shows between GO and κ-CAR, KGM molecules
Connected with strong intermolecular hydrogen bonding.After being destroyed to hydrogen bond, film mechanical performance has certain decline.Cytotoxicity test shows nontoxic
CKG (carragheen-konjaku glucomannan-graphene oxide) film of high intensity has good cell biological compatibility, there is uncommon
The superior substrate material of the support material as organizational project is hoped, has been applied in biomedical articles field, while in food
Also there is good application prospect in the fields such as packaging.
Kappa-carrageenan gel has more preferable stability, elasticity, flexibility and more preferable film forming.Due to its good medicine
Performance of science and bioactivity, in addition to these advantages, κ-CAR have low-viscosity critical defect, and this causes it in solvent
Quality of forming film, and its composite machinery poor-performing are difficult to control in the method for evaporating film forming.Konjaku glucomannan (KGM)
It is another natural polymer, it has very big excellent in terms of gelatification, film forming (dura mater), antibiotic property and low heat value
Gesture.Therefore, a kind of composition polymer can be prepared with κ-CAR and KGM, thin-film material is prepared together with GO, GO nanometer sheets effectively increase
The mechanical performance of strong composite.Enhancing κ-CAR and KGM each advantage improving the same of film forming controllability and mechanical performance
When, its good pharmacology performance and bioactivity is maintained, extend Ying Yong model of the composite in biomedical sector
Enclose.
As a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film of the present invention, the κ-
The mass ratio of carragheen and konjaku glucomannan is 1~10 ﹕ 1~5.Gel is caused knot of reuniting occur if mass ratio crosses conference
Block, it is impossible to film forming；Mass ratio is too small to cause gel stickiness not enough, poor mechanical properties after film forming.
As a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film of the present invention, the oxygen
The concentration of graphene oxide is 0.25~1mg/mL in graphite aqueous solution.Gel is suitably formed in the volume for ensuring aqueous solvent
Under conditions of, the concentration of graphene oxide is too high to cause it to reunite, and have harmful effect to the mechanical property of materials.
As a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film of the present invention, the oxygen
The quality of graphite alkene is the 2.5~10% of kappa-carrageenan and konjaku glucomannan gross mass.The graphite oxide that the present invention is limited
Alkene addition is optimum addition, and its addition is too many and can all cause the degradation of the mechanical property of materials very little.
As a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film of the present invention, the glass
Glass mould is pre-processed by the way of face coat or pad pasting in advance；Wherein, face coat uses silane coupler to glass
Glass die surface is coated, and pad pasting is used and pastes one layer of polytetrafluoroethylene film in surface of glass die.The present invention is to glass molds
Tool is pre-processed, and can be taken off from glass mold the convenient thin-film material for preparing in subsequently membrane process is taken off, and ensure glass
The integrality of glass, can cause the thin-film material cannot to take off completely, it is impossible to prepare with a scale if not carrying out pretreatment
Very little material.
It is described to stir as a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film of the present invention
Mix and use mechanical agitation, churned mechanically temperature is 50~100 DEG C, rotating speed is 245~650rpm, the time is 20~60min；Institute
The time for stating dispersion degassing is 20~60min；The drying temperature is 20~50 DEG C, and the time is 1~24h, and the room temperature is placed
Time is 5~24h.In preparation process of the present invention parameters selection be all carried out according to reactant characteristic and experimental result it is pre-
If with summary, being had undesirable effect to the thin-film material performance for preparing not in the range of.
Specifically, the preparation method of a kind of carragheen-konjaku glucomannan-graphene oxide film of the present invention,
Comprise the following steps：
1) add graphene oxide into deionized water solution, ultrasonic agitation obtains graphene oxide water solution；
2) kappa-carrageenan and konjaku glucomannan are added in above-mentioned graphene oxide water solution, are obtained after mechanical agitation
Film forming mixed liquor；
3) poured into above-mentioned in the glass mold anticipated after ultrasonic disperse degassing into film liquid, curtain coating is paved, in
1~24h is dried at 20~50 DEG C, mould is placed in after being completely dried after placing 5~24h at room temperature and is taken off film and obtain final product carragheen-evil spirit
Taro Glucomannan-graphene composite thin film.
The present invention also provides described carragheen-konjaku glucomannan-graphene composite thin film, the laminated film
Prepared using above-mentioned preparation method.
The present invention also provides the application of described carragheen-konjaku glucomannan-graphene composite thin film, described multiple
Close application of the film in packaging material, organizational project and biomaterial.
Carragheen-konjaku glucomannan-graphene composite thin film of the present invention is carried out with reference to specific embodiment
It is specifically described and illustrates.
Embodiment 1
The specific preparation process of the present embodiment carragheen-konjaku glucomannan-graphene composite thin film is as follows：
50mg graphene oxides are added in 200ml deionized water solutions, ultrasonic agitation 20min obtains graphite oxide
Alkene solution.The KGM powder for weighing the κ-CAR and 0.9g of 1.1g is added in above-mentioned graphene oxide water solution, at 60 DEG C,
Mechanical agitation 20min obtains film forming mixed solution under 245rpm；Gained is poured into advance into film liquid after ultrasonic disperse degassing 20min
In treated glass mold, curtain coating is paved, and in about 18h is dried at 30 DEG C, mould is placed into 15h at room temperature after being completely dried
Carefully take off afterwards, that is, obtain the present embodiment CKG (κ-CAR-KGM-GO) laminated film.
Wherein, glass mold is coated to its surface using silane coupler and anticipated.
Embodiment 2
50mg graphene oxides are added in 100ml deionized water solutions, ultrasonic agitation 30min obtains graphite oxide
Alkene solution.The KGM for weighing the κ-CAR and 0.45g of 0.55g is added in above-mentioned graphene oxide water solution, in 70 DEG C, 345rpm
Lower mechanical agitation 20min obtains film forming mixed solution；Gained pours into what is anticipated after deaerating 30min into film liquid ultrasonic disperse
In glass mold, curtain coating is paved, and in 10h is dried at 40 DEG C, is carefully taken off after mould is placed into 12h at room temperature after being completely dried
Under, that is, obtain the present embodiment CKG (κ-CAR-KGM-GO) laminated film.
Wherein, glass mold is coated to its surface using silane coupler and anticipated.
Embodiment 3
200mg graphene oxides are added in 200ml deionized water solutions, ultrasonic agitation 20min obtains graphite oxide
Alkene solution.Weigh 1.1g κ-CAR and 0.9g KGM powder to be added in above-mentioned graphene oxide water solution, in 80 DEG C, 445rpm
Lower mechanical agitation 20min obtains film forming mixed solution, and gained pours into what is anticipated after deaerating 40min into film liquid ultrasonic disperse
In glass mold, curtain coating is paved, and in about 20h is dried at 30 DEG C, is carefully taken off after mould is placed into 20h at room temperature after being completely dried
Under, that is, obtain the present embodiment CKG (κ-CAR-KGM-GO) laminated film.
Embodiment 4
150mg graphene oxides are added in 200ml deionized water solutions, ultrasonic agitation 20min obtains graphite oxide
Alkene solution.Weigh 1.1g κ-CAR and 0.9g KGM powder to be added in above-mentioned graphene oxide water solution, in 80 DEG C, 500rpm
Lower mechanical agitation 20min obtains film forming mixed solution；Gained pours into what is anticipated after deaerating 50min into film liquid ultrasonic disperse
In glass mold, curtain coating is paved, and in 12h is dried at 35 DEG C, is carefully taken off after mould is placed into 18h at room temperature after being completely dried
Under, that is, obtain the present embodiment CKG (κ-CAR-KGM-GO) laminated film.
Performance test is carried out to composite film material prepared by embodiment 1 to 4, detailed process and result are as follows：
1st, the tensile stress of composite film material
According to the standard method of test in GB GB-T 1040.3 2006 to the thin-film material prepared by embodiment 1 to 4
Tensile strength (TS) test is carried out, its tensile stress strain curve is as shown in Figure 1.Wherein 1 represents the (addition of GO of embodiment 1
For κ-CAR-KGM gross masses 2.5%)；2 represent embodiment 2 (addition of GO is the 5% of κ-CAR-KGM gross masses)；3 tables
Show embodiment 3 (addition of GO is the 7.5% of κ-CAR-KGM gross masses)；4 represent that (addition of GO is κ-CAR- to embodiment 4
KGM gross masses 10%)；5 is that comparative example ((addition of GO be 0) is other preparation processes and embodiment 3 one without GO
Sample.
From figure 1 it appears that the tensile stress of composite film material that the embodiment of the present invention 1 to 4 is prepared is substantially high
In comparative example (without GO), illustrating the addition of graphene oxide can be remarkably reinforced the tensile stress of composite film material.Meanwhile,
The tensile stress of thin-film material prepared by embodiment 3 is substantially better than other embodiment, illustrates that the addition for working as graphene oxide is
κ-CAR-KGM gross masses 7.5% when the tensile strength of the thin-film material of preparation can be made to reach maximum, be 128MPa.
In addition, being also tested for the drawing of the thin-film material prepared under different carragheens and magic domain Glucomannan adding proportion
Stress is stretched, its tensile stress strain curve is as shown in Figure 2.Wherein 1 represent without konjaku glucomannan, 2 represent κ-CAR and
KGM adding proportions are 5.5：4.5,3 represent that κ-CAR and KGM adding proportions are 5：5.
From figure 2 it can be seen that the tensile stress of the composite film material prepared without konjaku glucomannan is obvious
Less than the thin-film material of addition konjaku glucomannan, illustrate that the addition of konjaku glucomannan helps to increase the machinery of laminated film
Intensity and tensile stress.Meanwhile, when κ-CAR and KGM adding proportions are 5.5：The tensile stress of 4.5 thin-film materials prepared is bright
It is aobvious higher, illustrate when κ-CAR and KGM adding proportions are 5.5：When 4.5 the tensile strength of the thin-film material of preparation can reach most
It is good.
2nd, the thermogravimetric test of composite film material
N2Under atmosphere, within the temperature range of about 40-900 DEG C, with 20 DEG C/min of rate of heat addition test thermogravimetric (TG/
DTG).This thermogravimetric test experiments be preferably draw high thin-film material prepared by the optimal embodiment 3 of stress with without GO (other
Step is in the same manner as in Example 3) thin-film material for preparing, the thermogravimetrics of thin-film material prepared by two kinds of distinct methods of contrast
Can, so as to study graphene oxide to the role of thin-film material performance of the present invention.Its thermogravimetric test result is as shown in Figure 3.
Wherein 1 represents without GO, and 2 represent embodiment 3.
From figure 3, it can be seen that changing basically identical in both low-temperature space and high-temperature thermogravimetric, show clearly in center section part and see
The weight loss rate for going out the thin-film material of the preparation of embodiment 3 is less than the CN101565356A thin-film materials prepared without GO,
Illustrating the addition of GO contributes to the heat endurance of enhanced film material.
3rd, composite film material cytotoxicity test
Mouse peritoneal macrophages RAW264.7 uses cell culture medium (DMEM, 10% penicillin of cow's serum+1%
And streptomysin) containing 5%CO2, cultivated in 37 DEG C of incubator.The CKG film samples that in advance prepared by the embodiment 3 of sterilization
Product carry out culture 24 hours in being placed on 24 orifice plates for adding 1mL DMEM.Concentration is 2 × 106Every milliliter of RAW264.7 cells
Adding 2mL DMEM carries out culture 72h to being placed in incubator after similar face.Then increased by observing RAW264.7 cells
Speed is grown, the cytotoxicity of CKG films is judged.Observed, MTT side by inverted microscope (Nikon, ECLIPSETi-S)
Method (colorimetric analysis of MTT cells) carries out cell measurement, for detecting good cell propagation.And comparative example is set, treatment is not added with
Enter CKG film samples other as aforesaid operations, observe RAW264.7 cell proliferation rates.Cell breeds knot with incubation time
Fruit is as shown in Figure 4.Wherein, 1 addition CKG film cell proliferative conditions are represented, 2 represent without addition CKG films cell propagation feelings
Condition.
From fig. 4, it can be seen that before cultivating 48 hours mouse peritoneal macrophages RAW264.7, adding CKG films
CKG films cell culture propagation quantity is almost suitable with being added without, and illustrates the CKG films of present invention preparation and does not influence the life of cell
It is long, there is no toxicity.When incubation time reaches 72h, although cell proliferating number amount is than being added without the quantity that CKG templates cell is bred
It is few, but compared to 48h, the quantity that cell is bred is almost 5~6 times during 48h, illustrates cell still with the speed of rapid growth
In propagation, the CKG for further illustrating present invention preparation does not have toxicity.It is to be understood that carrying out cell training using different materials
Support, proliferation results carrying out over time, gap can be more and more obvious, therefore, CKG film cell proliferating number amounts are added during 72h
Being normal phenomenon be added without CKG film cell proliferating number amounts to have gap, the avirulent knot of CKG films of the present invention can't be influenceed
Really.
Natural polymer carragheen-konjaku glucomannan-graphene composite thin film prepared by the present invention, it was prepared
Journey is simple, and cost is relatively low, and obtained thin-film material regularity is good, degradable, good biocompatibility.Preparation method of the present invention is by oxygen
Graphite alkene is reset in konjaku glucomannan matrix, uniform by the modified film of carragheen, high mechanical strength.The present invention
Obtained natural polymer/carragheen-konjaku glucomannan-graphene composite thin film, its heat endurance and mechanical strength
Height, degradable, good biocompatibility can be widely applied to the fields such as packaging, organizational project and biomaterial.
Comparative example 1
Churned mechanically temperature in embodiment 3 is changed to 30 DEG C or 120 DEG C respectively, other operations are constant, research reaction
The influence of composite film material performance of the temperature to preparing.Should declare, other temperature not in the range of whipping temp of the present invention
Degree can reach and 30 DEG C and 120 DEG C of identical effects, do not do specifically enumerate herein.
Carragheen and konjaku glucomannan cannot be dissolved completely in water at 30 DEG C, thus cannot form the gel of stabilization,
Material prepares unsuccessful.Due to temperature influence carragheen higher and the combination of konjaku glucomannan at 120 DEG C, result in
Thin film material mechanics poor-performing, tensile strength only has 80.2MPa, thin-film material tensile stress prepared by not enough embodiment 3
2/3rds.
Comparative example 2
Churned mechanically rotating speed in embodiment 3 is changed to 200rpm or 800rpm respectively, other operations are constant, and research is stirred
The influence of composite film material performance of the rotating speed mixed to preparing.Should declare, other are not in the range of speed of agitator of the present invention
Temperature can up to and 200rpm and 800rpm identical effects, do not do specifically enumerate herein.
The rotating speed of 200rpm can cause gel-forming uneven, have a small amount of caking and occur.It is prepared by the rotating speed of 800rpm
Thin film material mechanics performance it is suitable with the material prepared in embodiment, there is no essential difference, but understand under this rotating speed and exist
The phenomenon of liquid splash is produced during preparation, is unfavorable for that experiment prepares control.
Comparative example 3
Drying temperature in embodiment 3 is changed to 10 DEG C or 70 DEG C respectively, other operations are constant, research drying temperature is to system
The influence of standby composite film material performance.Should declare, other temperature not in the range of drying temperature of the present invention can reach
With 10 DEG C and 70 DEG C of identical effects, do not do specifically enumerate herein.
10 DEG C or 70 DEG C of drying temperature mainly influences the dry time, and the time is oversize at 10 DEG C, extends manufacturing cycle；70
DEG C when the time can shorten compared with embodiment, but prepare thin-film material can harden, mechanical property can decline, the degree of decline
Probably 20% or so.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film, it is characterised in that the preparation side
Method is that kappa-carrageenan and konjaku glucomannan are added in graphene oxide water solution, and glass is poured into after agitated, dispersion degassing
In glass mould, mould is placed at room temperature after being completely dried, takes off film and obtain final product laminated film of the present invention.
2. as claimed in claim 1 a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film, its feature
It is that the mass ratio of the kappa-carrageenan and konjaku glucomannan is 1~10 ﹕ 1~5.
3. as claimed in claim 1 a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film, its feature
It is that the concentration of graphene oxide is 0.25~1mg/mL in the graphene oxide water solution.
4. as claimed in claim 4 a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film, its feature
It is that the quality of the graphene oxide is kappa-carrageenan and the 2.5~10% of konjaku glucomannan gross mass.
5. as claimed in claim 1 a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film, its feature
It is that the glass mold is pre-processed by the way of face coat or pad pasting in advance；Wherein, face coat uses silane
Coupling agent is coated to surface of glass die, and pad pasting is used and pastes one layer of polytetrafluoroethylene film in surface of glass die.
6. as claimed in claim 1 a kind of preparation method of carragheen-konjaku glucomannan-graphene oxide film, its feature
It is that the stirring uses mechanical agitation, churned mechanically temperature is 50~100 DEG C, and rotating speed is 245~650rpm；Time is
20~60min；The time of the dispersion degassing is 20~60min；The drying temperature is 20~50 DEG C, and the time is 1~24h,
The room temperature standing time is 5~24h.
7. a kind of preparation side of carragheen-konjaku glucomannan-graphene oxide film as described in any one of claim 1 to 6
Method, it is characterised in that comprise the following steps：
1) add graphene oxide into deionized water solution, ultrasonic agitation obtains graphene oxide water solution；
2) kappa-carrageenan and konjaku glucomannan are added in above-mentioned graphene oxide water solution, film forming is obtained after mechanical agitation
Mixed liquor；
3) by it is above-mentioned deaerated through ultrasonic disperse into film liquid after pour into the glass mold anticipated, curtain coating is paved, in 20~
1~24h is dried at 50 DEG C, mould is placed in after being completely dried after placing 5~24h at room temperature and is taken off film and obtain final product carragheen-konjaku Portugal
Sweet glycan-graphene composite thin film.
8. a kind of carragheen-konjaku glucomannan-graphene composite thin film, it is characterised in that the laminated film is used
Preparation method described in the claims 1 to 7 is prepared.
9. a kind of application of carragheen-konjaku glucomannan-graphene composite thin film as claimed in claim 8, its feature
It is, application of the laminated film in packaging material, organizational project and biomaterial.
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| CN110548496A (en) * | 2019-09-04 | 2019-12-10 | 广东石油化工学院 | Preparation method and application of carragheen-graphene oxide super-macroporous hydrogel |
| CN114350033A (en) * | 2022-01-11 | 2022-04-15 | 成都大学 | Bletilla gum-galactomannan-graphene oxide film and preparation method and application thereof |
| CN114605715A (en) * | 2022-03-25 | 2022-06-10 | 成都大学 | Propolis-cyclodextrin-graphene oxide film and preparation method and application thereof |
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| CN108690226A (en) * | 2018-06-05 | 2018-10-23 | 宁波沸柴机器人科技有限公司 | A kind of degradable biological radiation prevention film and its preparation and application |
| CN110548496A (en) * | 2019-09-04 | 2019-12-10 | 广东石油化工学院 | Preparation method and application of carragheen-graphene oxide super-macroporous hydrogel |
| CN114350033A (en) * | 2022-01-11 | 2022-04-15 | 成都大学 | Bletilla gum-galactomannan-graphene oxide film and preparation method and application thereof |
| CN114605715A (en) * | 2022-03-25 | 2022-06-10 | 成都大学 | Propolis-cyclodextrin-graphene oxide film and preparation method and application thereof |
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