CN106893122A - PLA base medical thin-film material containing nanometer carbon crystal and preparation method thereof - Google Patents
PLA base medical thin-film material containing nanometer carbon crystal and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to medical film field, specifically related to a kind of PLA base medical thin-film material containing nanometer carbon crystal and preparation method thereof, matched with PLA by by nanometer carbon crystal, it is prepared from using the method for film or electrostatic spinning, plasticity and toughness of the invention are strong, biocompatibility, biological degradability are good, degradation time is fast and bactericidal effect is lasting.
Description
Technical field
The invention belongs to medical film field, and in particular to a kind of PLA base medical thin-film material containing nanometer carbon crystal and
Its preparation method.
Background technology
The body of people is often subject to wound because of accident in daily life, when by wound, wound dressing
As necessary article, traditional wound dressing such as gauze etc., it is isolated bacterium, prevents the effect of infection general, particularly large area
Wound, it is difficult to meet use demand, therefore people are badly in need of a kind of high-performance, multi-functional dressing.
PLA has excellent biocompatibility and good biodegradable, can be utilized by human body cell, most
Water and carbon dioxide are degraded to eventually, it is nontoxic, do not produce stimulation to human body, and also the synthesis material of PLA is that starch etc. can
Regenerated resources, environmental protection, wide material sources are widely used as bio-medical film in recent years, but PLA is existed
Pliability is poor, and degradation speed is slow in itself for material, does not have the defects such as the effect of anti-inflammation, therefore must carry out as medical film
It is modified.
Polylactic acid modified method is more, and conventional at present has：Modification by copolymerization, structurally-modified, fiber blend, with other high scores
Son blending and with inorganic filler blending etc..But modification by copolymerization and it is structurally-modified be chemical modification, process is complicated, not economic enough ring
Protect, and easily entrain harmful substance；The modified method of fiber blend, fiber and PLA poor compatibility, are directly blended effect
It is bad, and the degradation speed of fiber is slower, is not suitable for medical material；Can be biological with other polymer blended can only selecting
Degraded, it is used alone, enhancing effect is bad；Inorganic nano material has in the modified enhancing of macromolecular material widely should
With, but biocompatibility is poor, therefore need further improvement for the method for modifying of PLA.
The content of the invention
It is an object of the invention to provide a kind of plasticity and toughness it is strong, biocompatibility, biological degradability are good, degradation time is fast,
The lasting PLA base medical thin-film material containing nanometer carbon crystal of bactericidal effect.
Based on above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of preparation method of the PLA base medical thin-film material containing nanometer carbon crystal, is prepared by following steps and constituted：
（1）Under a nitrogen atmosphere, nanometer carbon crystal is added to while stirring in organic solvent and is stirred at normal temperatures, stirred
Speed is 1500-2000rpm, and it is 25-30KHz to be then placed in the supersonic wave cleaning machine equipped with deionized water in supersonic frequency,
After ultrasonic disperse 2-3h, then PLA is added while stirring, mixing speed is 1500-2000rpm, stirring at normal temperature 1-2h, obtains poly-
Lactyl composite solution.
（2）Electrospun fibers are prepared using the method for film or electrostatic spinning using polylactic acid-base composite material solution thin
Film；
（3）Drying：Obtained fiber membrane is put into baking oven, 45-55 DEG C is raised to the speed of 1-2 DEG C/min, heat preservation and dryness,
Untill electrospun fibers film content of organics is less than 0.01%；
（4）Sterilization packaging：The laminated film of drying is carried out into sterilizing, then vacuum packaging storage；
The weight ratio of described PLA, nanometer carbon crystal and organic solvent is PLA：Nanometer carbon crystal：Organic solvent： =100:
3-8:500-800。
Further, described nanometer carbon crystal is modified nanometer carbon crystal, and its method of modifying is as follows：
A. ultrasonic wave alkali cleaning：Nanometer carbon crystal is put into stirring and washing in the supersonic wave cleaning machine equipped with alkali lye, ultrasonic frequency is
30-40KHz, alkali lye is the NaOH solution of 10-12wt%, and alkali cleaning temperature is 50-60 DEG C, and mixing speed is 25-30rpm, cleaning
20-30min；
B. ultrasonic wave pickling：Nanometer carbon crystal after alkali cleaning is put into acid solution and is cleaned, acid solution is dense H2SO4With dense HNO3Mixing
Liquid, described dense H2SO4With dense HNO3The weight ratio of mixed liquor is dense H2SO4：Dense HNO3=2-4:1, pickling temperature is 60-80 DEG C,
Precipitated with the centrifugation of 1500-2000rpm after pickling 8-12h, remove solution.
C. ultrasonic wave water washing：Nanometer carbon crystal after pickling is put into normal temperature in the supersonic wave cleaning machine equipped with deionized water to stir
Cleaning is mixed, ultrasonic frequency is 30-45KHz, and mixing speed is 20-25rpm, stir 8-10min, take supernatant liquor measurement pH
Value, until stand-by after pH=7, the ratio for then adjusting nanometer carbon crystal and deionized water is 5-15 for cleaning repeatedly:100, and by this
Dispersion liquid is transferred in reactor, and stirring is stopped after dispersion liquid is warmed up into 60-80 DEG C under the mixing speed of 300-500rpm,
It is made nanometer carbon crystal dispersion liquid.
D. coupling modifier:The stirring of silane coupler side is added in absolute ethyl alcohol, acetic acid is added, pH value of solution is adjusted
It is 4-5, coupling agent pre-dispersed liquid is obtained after stirring, is then dropwise added drop-wise in the reactor in step c, after completion of dropping
Continue to stir, 10-50min is reacted at 60-80 DEG C, wherein coupling agent pre-dispersed liquid is that coupling agent is pre- with nanometer carbon crystal weight ratio
Dispersion liquid：Nanometer carbon crystal=1-3:100, described silane coupler and the weight ratio of absolute ethyl alcohol is 1-5:100；
E. dry：Reacted solution in step d is precipitated with the centrifugation of 1500-2000rpm, solution is removed, then
Cleaning, up to pH=7, the nanometer carbon crystal after cleaning is progressively warmed up to the speed of 3-5 DEG C/min repeatedly in deionized water
100-120 DEG C, cooled down with furnace temperature after insulation 2-4h, sealed storage is stand-by.
Further, described organic solvent is chloroform or ethyl acetate or DMF.
Further, described silane coupler is KH-570.
Further, obtained by the preparation method of the described PLA base medical thin-film material containing nanometer carbon crystal containing nanometer
The brilliant PLA base medical thin-film material of carbon.
Compared with prior art, technique effect of the invention is：
1. nanometer carbon crystal is good polymer reinforcing material, and its addition overcomes PLA and moulds tough as medical thin-film material
Property difference defect；
2. modified nanometer carbon crystal has hydrophily, can effectively improve composite degradation speed and with tissue
Affinity；
3. nanometer carbon crystal has good antibacterial and bacteriostasis, and it is uniformly to be mixed into PLA, and it can be with thin
The degraded slow release of film, bactericidal effect is lasting；
4. preparation method of the present invention is simple, can reduce the introducing of harmful substance, and this product has a wide range of application, except for people
Outside the cladding of external body damaged skin, can be also used for preventing in tissue adhesion in vivo.
Brief description of the drawings
Fig. 1：Elongation at break of the present invention is with nanometer carbon crystal changes of contents relation；
Fig. 2：The water absorption rate of 120h of the present invention with nanometer carbon crystal changes of contents graph of a relation.
Specific embodiment
Embodiment 1：
A kind of preparation method of the PLA base medical thin-film material containing nanometer carbon crystal, is prepared by following steps and constituted：
（1）Under a nitrogen atmosphere, the nanometer carbon crystal that parts by weight are 3 parts is added in 500 parts of chloroform while stirring
Stir at normal temperatures, mixing speed is 1500rpm, be then placed in the supersonic wave cleaning machine equipped with deionized water in super
Acoustic frequency is 25KHz, after ultrasonic disperse 2h, then adds PLA while stirring, and mixing speed is 1500rpm, stirring at normal temperature 1h,
Obtain polylactic acid-base composite material solution.
（2）Using polylactic acid-base composite material solution, electrospun fibers are prepared using the method for film or electrostatic spinning
Film；
（3）Drying：Obtained fiber membrane is put into baking oven, 45 DEG C are raised to the speed of 1 DEG C/min, heat preservation and dryness, until
Untill electrospun fibers film content of organics is less than 0.01%；
（4）Sterilization packaging：The laminated film of drying is carried out into sterilizing, then vacuum packaging storage；
The weight ratio of described PLA, nanometer carbon crystal and organic solvent is PLA：Nanometer carbon crystal：Chloroform=100:3:
500。
Above-mentioned nanometer carbon crystal is modified nanometer carbon crystal, and its method of modifying is as follows：
A. ultrasonic wave alkali cleaning：Nanometer carbon crystal is put into stirring and washing in the supersonic wave cleaning machine equipped with alkali lye, ultrasonic frequency is
30KHz, alkali lye is the NaOH solution of 10wt%, and alkali cleaning temperature is 50 DEG C, and mixing speed is 25rpm, cleans 20min；
B. ultrasonic wave pickling：Nanometer carbon crystal after alkali cleaning is put into acid solution and is cleaned, acid solution is dense H2SO4With dense HNO3Mixing
Liquid, described dense H2SO4With dense HNO3The weight ratio of mixed liquor is dense H2SO4：Dense HNO3=2:1, pickling temperature is 60 DEG C, pickling
Precipitated with the centrifugation of 1500rpm after 8h, remove solution.
C. ultrasonic wave water washing：Nanometer carbon crystal after pickling is put into normal temperature in the supersonic wave cleaning machine equipped with deionized water to stir
Cleaning is mixed, ultrasonic frequency is 30KHz, and mixing speed is 20rpm, stir 8min, take supernatant liquor pH value determination, cleaned repeatedly
Until stand-by after pH=7, it is 5 then to adjust nanometer carbon crystal with the weight ratio of deionized water:100, and this dispersion liquid is transferred to
In reactor, stirring is stopped after dispersion liquid is warmed up into 60-80 DEG C under the mixing speed of 300rpm, be made nanometer carbon crystal dispersion
Liquid.
D. coupling modifier:The stirring of KH-570 sides is added in absolute ethyl alcohol, acetic acid is added, regulation pH value of solution is 4,
Coupling agent pre-dispersed liquid is obtained after stirring, is then dropwise added drop-wise in the reactor in step c, continue to stir after completion of dropping
Mix, 10min is reacted at 60 DEG C, wherein coupling agent pre-dispersed liquid and nanometer carbon crystal weight ratio is 1:100, described KH-570 with
The weight ratio of absolute ethyl alcohol is 1:100；
E. dry：Reacted solution in step d is precipitated with the centrifugation of 1500rpm, solution is removed, then gone
The nanometer carbon crystal after cleaning, up to pH=7, is progressively warmed up to 100 DEG C by cleaning with the speed of 3 DEG C/min repeatedly in ionized water, is protected
Cooled down with furnace temperature after warm 2h, sealed storage is stand-by.
Embodiment 2
A kind of preparation method of the PLA base medical thin-film material containing nanometer carbon crystal, is prepared by following steps and constituted：
（1）Under a nitrogen atmosphere, nanometer carbon crystal is added to while stirring in ethyl acetate and is stirred at normal temperatures, stirred
Speed is 1750rpm, and it is 27KHz, ultrasonic disperse to be then placed in the supersonic wave cleaning machine equipped with deionized water in supersonic frequency
After 2.5h, then PLA is added while stirring, mixing speed is 1750rpm, stirring at normal temperature 1.5h, obtains polylactic acid-base composite material
Solution.
（2）Using polylactic acid-base composite material solution, electrospun fibers are prepared using the method for film or electrostatic spinning
Film；
（3）Drying：Obtained fiber membrane is put into baking oven, is raised between 50 DEG C with the speed of 1.5 DEG C/min, insulation is dry
It is dry, untill electrospun fibers film content of organics is less than 0.01%；
（4）Sterilization packaging：The laminated film of drying is carried out into sterilizing, then vacuum packaging storage；
Described PLA, nanometer carbon crystal and organic solvent weight ratio are PLA：Nanometer carbon crystal：Ethyl acetate 100:5:
650。
Above-mentioned nanometer carbon crystal is modified nanometer carbon crystal, and its method of modifying is as follows：
A. ultrasonic wave alkali cleaning：Nanometer carbon crystal is put into stirring and washing in the supersonic wave cleaning machine equipped with alkali lye, ultrasonic frequency is
35KHz, alkali lye is the NaOH solution of 11wt%, and alkali cleaning temperature is 55 DEG C, and mixing speed is 27rpm, cleans 25min；
B. ultrasonic wave pickling：Nanometer carbon crystal after alkali cleaning is put into acid solution and is cleaned, acid solution is dense H2SO4With dense HNO3Mixing
Liquid, described dense H2SO4With dense HNO3The weight ratio of mixed liquor is dense H2SO4：Dense HNO3=3:1, pickling temperature is 70 DEG C, pickling
Precipitated with the centrifugation of 1750rpm after 10h, remove solution.
C. ultrasonic wave water washing：Nanometer carbon crystal after pickling is put into normal temperature in the supersonic wave cleaning machine equipped with deionized water to stir
Cleaning is mixed, ultrasonic frequency is 37KHz, and mixing speed is 22rpm, stir 9min, take supernatant liquor pH value determination, cleaned repeatedly
Until stand-by after pH=7, it is 10 then to adjust nanometer carbon crystal with the weight ratio of deionized water:100, and this dispersion liquid is transferred to
In reactor, stirring is stopped after dispersion liquid is warmed up into 60-80 DEG C under the mixing speed of 400rpm, be made nanometer carbon crystal dispersion
Liquid.
D. coupling modifier:The stirring of KH-570 sides is added in absolute ethyl alcohol, acetic acid is added, regulation pH value of solution is
4.5, coupling agent pre-dispersed liquid is obtained after stirring, then dropwise it is added drop-wise in the reactor in step c, completion of dropping is follow-up
Continuous stirring, reacts 30min at 70 DEG C, and wherein coupling agent pre-dispersed liquid and nanometer carbon crystal weight ratio is coupling agent pre-dispersed liquid：
Nanometer carbon crystal=2:100, described KH-570 and the weight ratio of absolute ethyl alcohol is 3:100；
E. dry：Reacted solution in step d is precipitated with the centrifugation of 1750rpm, solution is removed, then gone
The nanometer carbon crystal after cleaning, up to pH=7, is progressively warmed up to 110 DEG C by cleaning with the speed of 4 DEG C/min repeatedly in ionized water, is protected
Cooled down with furnace temperature after warm 3h, sealed storage is stand-by.
Embodiment 3：
A kind of preparation method of the PLA base medical thin-film material containing nanometer carbon crystal, is prepared by following steps and constituted：
（1）Under a nitrogen atmosphere, stirring at normal temperatures is equal during nanometer carbon crystal to be added to DMF while stirring
Even, mixing speed is 2000rpm, and it is 30KHz to be then placed in the supersonic wave cleaning machine equipped with deionized water in supersonic frequency,
After ultrasonic disperse 3h, then PLA is added while stirring, mixing speed is 2000rpm, stirring at normal temperature 2h, obtain PLA base and be combined
Material solution.
（2）Electrospun fibers are prepared using the method for film or electrostatic spinning using polylactic acid-base composite material solution thin
Film；
（3）Drying：Obtained fiber membrane is put into baking oven, is raised between 55 DEG C with the speed of 2 DEG C/min, heat preservation and dryness,
Untill electrospun fibers film content of organics is less than 0.01%；
（4）Sterilization packaging：The laminated film of drying is carried out into sterilizing, then vacuum packaging storage；
The weight ratio of described nanometer PLA, modified Nano carbon crystalline substance and organic solvent is PLA：Nanometer carbon crystal：N, N- diformazan
Base formamide=100: 8: 800.
Above-mentioned nanometer carbon crystal is modified nanometer carbon crystal, and its method of modifying is as follows：
A. ultrasonic wave alkali cleaning：Nanometer carbon crystal is put into stirring and washing in the supersonic wave cleaning machine equipped with alkali lye, ultrasonic frequency is
40KHz, alkali lye is the NaOH solution of 12wt%, and alkali cleaning temperature is 60 DEG C, and mixing speed is 30rpm, cleans 30min；
B. ultrasonic wave pickling：Nanometer carbon crystal after alkali cleaning is put into acid solution and is cleaned, acid solution is dense H2SO4With dense HNO3Mixing
Liquid, described dense H2SO4With dense HNO3The weight ratio of mixed liquor is dense H2SO4：Dense HNO3=4:1, pickling temperature is 80 DEG C, pickling
Precipitated with the centrifugation of 2000rpm after 12h, remove solution.
C. ultrasonic wave water washing：Nanometer carbon crystal after pickling is put into normal temperature in the supersonic wave cleaning machine equipped with deionized water to stir
Cleaning is mixed, ultrasonic frequency is 45KHz, and mixing speed is 25rpm, stir 10min, take supernatant liquor pH value determination, repeatedly clearly
Wash until stand-by after pH=7, it is 15 then to adjust nanometer carbon crystal with the weight ratio of deionized water:100, and this dispersion liquid is shifted
To in reactor, stirring is stopped after dispersion liquid to be warmed up to 80 DEG C under the mixing speed of 500rpm, be made nanometer carbon crystal dispersion
Liquid.
D. coupling modifier:The stirring of KH-570 sides is added in absolute ethyl alcohol, acetic acid is added, regulation pH value of solution is 5,
Coupling agent pre-dispersed liquid is obtained after stirring, is then dropwise added drop-wise in the reactor in step c, continue to stir after completion of dropping
Mix, 50min is reacted at 80 DEG C, wherein coupling agent pre-dispersed liquid and nanometer carbon crystal weight ratio is coupling agent pre-dispersed liquid：Nanometer
Carbon crystalline substance=3:100, described KH-570 and the weight ratio of absolute ethyl alcohol is 5:100；
E. dry：Reacted solution in step d is precipitated with the centrifugation of 2000rpm, solution is removed, then gone
The nanometer carbon crystal after cleaning, up to pH=7, is progressively warmed up to 120 DEG C by cleaning with the speed of 5 DEG C/min repeatedly in ionized water, is protected
Cooled down with furnace temperature after warm 4h, sealed storage is stand-by.
Test example 1：
Only remained in the finished product of the PLA base medical film containing nanometer carbon crystal prepared by method in embodiment 1 PLA and
Two kinds of raw materials of nanometer carbon crystal, therefore nanometer carbon crystal is used for variable relative to the weight percent shared by PLA, use mechanics
When testing machine determines the percentage by weight of nanometer carbon crystal between 0-10Wt%, the change of the elongation at break of medical film is such as schemed
Shown in 1, the elongation at break of the medical film after addition nanometer carbon crystal is raised, and its plasticity and toughness is high, in the weight of addition nanometer carbon crystal
Amount percentage is in 7 wt%, and the plasticity and toughness of medical film are best, when the percentage by weight of nanometer carbon crystal is added more than 7 wt%,
The plasticity and toughness of medical film start to reduce, therefore are adding the percentage by weight of nanometer carbon crystal in 3-8 wt%, its medical film
Plasticity and toughness are most appropriate.
Test example 2：
Only remained in the finished product of the PLA base medical film containing nanometer carbon crystal prepared by method in embodiment 1 PLA and
Two kinds of raw materials of nanometer carbon crystal, therefore nanometer carbon crystal is used for variable relative to the weight percent shared by PLA, will prepare
Medical film elder generation load-bearing, reuse deionized water immersion 120h rear load-bearings, water absorption rate is measured, to the weight percent of nanometer carbon crystal
During than between 0-10Wt%, the water absorption rate of medical film is tested, as shown in Figure 2, the medical film after addition nanometer carbon crystal
Increase relative to the water absorption rate for being not added with medical film, as nanometer carbon crystal addition increases, the water absorption rate of its medical film is not
Disconnected enhancing, therefore when the percentage by weight of nanometer carbon crystal is added in 7 wt%, the water absorption rate of medical film is most appropriate, water suction
Rate is higher, and biodegradable speed is faster, is conducive to the combination of medical film and biological tissue, reduces and repels.
Test example 3：
To using the medical film prepared by the preparation method of the PLA base medical thin-film material containing nanometer carbon crystal in embodiment 1
Antibacterial tests are carried out, the medical film without nanometer carbon crystal element is taken and is set it to No. 1 sample with nanometer carbon crystal of the present invention element
Medical film sets it to No. 2 samples, and sample cuts out the print of 3 × 3cm sizes, takes the agar block culture bacterium of 3 × 3 × 3cm
Fall, bacterium to bacterium colony is cultivated on agar block and is occurred, the sample after then cutting out is placed on observation sample and agar on agar block
The change of bacterium colony, as a result as shown in table 1 below on block；
Table 1：The antibacterial bacteriostatic effect contrast test of different medical films
From upper table 1：The PLA base medical thin-film material of nanometer carbon crystal is added relative to the poly- breast for being not added with nanometer carbon crystal
Acidic group medical thin-film material antibacterial effect is strong.
Claims (5)
1. a kind of preparation method of the PLA base medical thin-film material containing nanometer carbon crystal, it is characterised in that by following steps system
Standby composition：
（1）Nanometer carbon crystal is added to while stirring in organic solvent and stirred at normal temperatures, mixing speed is 1500-
2000rpm, it is 25-30KHz, ultrasonic disperse 2-3h to be then placed in the supersonic wave cleaning machine equipped with deionized water in supersonic frequency
Afterwards, then while stirring PLA is added, mixing speed is 1500-2000rpm, stirring at normal temperature 1-2h, obtains PLA base composite wood
Material solution；
（2）Electrospun fibers film is prepared using the method for film or electrostatic spinning using polylactic acid-base composite material solution；
（3）Drying：Obtained fiber membrane is put into baking oven, 45-55 DEG C is raised to the speed of 1-2 DEG C/min, heat preservation and dryness,
Untill electrospun fibers film content of organics is less than 0.01%；
（4）Sterilization packaging：The laminated film of drying is carried out into sterilizing, then vacuum packaging storage；
The weight ratio of described PLA, nanometer carbon crystal and organic solvent is PLA：Nanometer carbon crystal：Organic solvent： =100:
3-8:500-800。
2. the preparation method of the PLA base medical thin-film material containing nanometer carbon crystal according to claim 1, its feature exists
In described nanometer carbon crystal is modified nanometer carbon crystal, and its method of modifying is as follows：
A. ultrasonic wave alkali cleaning：Nanometer carbon crystal is put into stirring and washing in the supersonic wave cleaning machine equipped with alkali lye, ultrasonic frequency is
30-40KHz, alkali lye is the NaOH solution of 10-12wt%, and alkali cleaning temperature is 50-60 DEG C, and mixing speed is 25-30rpm, cleaning
20-30min；
B. ultrasonic wave pickling：Nanometer carbon crystal after alkali cleaning is put into acid solution and is cleaned, acid solution is dense H2SO4With dense HNO3Mixing
Liquid, described dense H2SO4With dense HNO3The weight ratio of mixed liquor is dense H2SO4：Dense HNO3=2-4:1, pickling temperature is 60-80 DEG C,
Precipitated with the centrifugation of 1500-2000rpm after pickling 8-12h, remove solution；
C. ultrasonic wave water washing：Nanometer carbon crystal after pickling is put into stirring at normal temperature in the supersonic wave cleaning machine equipped with deionized water clear
Wash, ultrasonic frequency is 30-45KHz, mixing speed is 20-25rpm, stir 8-10min, take supernatant liquor pH value determination, instead
Until stand-by after pH=7, the ratio for then adjusting nanometer carbon crystal and deionized water is 5-15 for multiple cleaning:100, and by this dispersion liquid
It is transferred in reactor, stirring is stopped after dispersion liquid is warmed up into 60-80 DEG C under the mixing speed of 300-500rpm, is made and receives
Rice carbon crystalline substance dispersion liquid；
D. coupling modifier:The stirring of silane coupler side is added in absolute ethyl alcohol, acetic acid is added, regulation pH value of solution is 4-
5, coupling agent pre-dispersed liquid is obtained after stirring, then dropwise it is added drop-wise in the reactor in step c, continue after completion of dropping
Stirring, reacts 10-50min at 60-80 DEG C, and wherein coupling agent pre-dispersed liquid is that coupling agent is pre-dispersed with nanometer carbon crystal weight ratio
Liquid：Nanometer carbon crystal=1-3:100, described silane coupler and the weight ratio of absolute ethyl alcohol is 1-5:100；
E. dry：Reacted solution in step d is precipitated with the centrifugation of 1500-2000rpm, solution is removed, then
Cleaning, up to pH=7, the nanometer carbon crystal after cleaning is progressively warmed up to the speed of 3-5 DEG C/min repeatedly in deionized water
100-120 DEG C, cooled down with furnace temperature after insulation 2-4h, sealed storage is stand-by.
3. according to PLA base medical thin-film material of the claim 1 containing nanometer carbon crystal, it is characterised in that described organic solvent
It is chloroform or ethyl acetate or N,N-dimethylformamide.
4. the preparation method of the PLA base medical thin-film material containing nanometer carbon crystal according to claim 1, its feature exists
In described silane coupler is KH-570.
5. obtained by the preparation method of the PLA base medical thin-film material containing nanometer carbon crystal according to claim 1 containing receiving
The brilliant PLA base medical thin-film material of rice carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710110604.5A CN106893122A (en) | 2017-02-28 | 2017-02-28 | PLA base medical thin-film material containing nanometer carbon crystal and preparation method thereof |
Applications Claiming Priority (1)
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| CN108893871A (en) * | 2018-06-20 | 2018-11-27 | 北京服装学院 | A kind of high-performance biology group compound film and preparation method thereof |
| CN108975955A (en) * | 2018-07-12 | 2018-12-11 | 郑州人造金刚石及制品工程技术研究中心有限公司 | With the preparation method of the nanometer carbon crystal coating of Yu Haiyang sealing material and the nanometer carbon crystal coating of preparation |
| CN109401016A (en) * | 2018-10-31 | 2019-03-01 | 郑州人造金刚石及制品工程技术研究中心有限公司 | A kind of surface is loaded with polyethylene antibiotic film of nanometer carbon crystal and preparation method thereof |
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| CN105271173A (en) * | 2015-09-25 | 2016-01-27 | 郑州华晶金刚石股份有限公司 | Preparation process of nano carbon crystals |
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| CN108893871A (en) * | 2018-06-20 | 2018-11-27 | 北京服装学院 | A kind of high-performance biology group compound film and preparation method thereof |
| CN108975955A (en) * | 2018-07-12 | 2018-12-11 | 郑州人造金刚石及制品工程技术研究中心有限公司 | With the preparation method of the nanometer carbon crystal coating of Yu Haiyang sealing material and the nanometer carbon crystal coating of preparation |
| CN108975955B (en) * | 2018-07-12 | 2021-03-19 | 郑州人造金刚石及制品工程技术研究中心有限公司 | Preparation method of nano carbon crystal coating for marine sealing material and prepared nano carbon crystal coating |
| CN109401016A (en) * | 2018-10-31 | 2019-03-01 | 郑州人造金刚石及制品工程技术研究中心有限公司 | A kind of surface is loaded with polyethylene antibiotic film of nanometer carbon crystal and preparation method thereof |
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