CN105646920B - A kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane - Google Patents
A kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane Download PDFInfo
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- CN105646920B CN105646920B CN201610149918.1A CN201610149918A CN105646920B CN 105646920 B CN105646920 B CN 105646920B CN 201610149918 A CN201610149918 A CN 201610149918A CN 105646920 B CN105646920 B CN 105646920B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The present invention relates to a kind of preparation methods based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane.Super hydrophobic surface has having been widely used in real life.The super hydrophobic surface extremely low to drop adhesion strength has self-cleaning function, such as the surface of lotus leaf；The super hydrophobic surface extremely strong to drop adhesion strength is often used for the transport of micro drop, such as the surface of roseleaf.The chemical composition and roughness of material surface are to influence the key factor of its interface wetting property.For the material of certain restriction, usually its hydrophobicity is improved by way of in the multiple dimensioned micro-nano structure of surface construction.The present invention can form Stereocomplex crystalline substance using l-lactic acid and dextrorotation polylactic acid, the phenomenon that micron order ball and nano-scale groove are formed during solvent-induced inversion of phases, in the multiple dimensioned micro-nano structure of polylactic acid membrane surface construction, to obtain super-hydrophobic, adhesion strength is controllable polylactic acid membrane interface.
Description
Technical field
The invention belongs to bionical interface tech fields, are related to a kind of based on super-hydrophobic, the controllable adherency of Stereocomplex crystalline substance structure
The preparation method on the polylactic acid membrane surface of power.
Background technology
Many of nature has the organism surface of special wetting property.What is be widely known is the surface of lotus leaf,
Water is dropped in its surface and can tumble rapidly, shows self-cleaning effect, is referred to as " lotus leaf effect ".Unlike this, rose
There is water droplet on the surface of valve extremely strong adhesion strength, rain to be dropped in petal surface, keeps drop shape and is firmly attached to petal table
Face is glittered under sunlight, is attracted bee butterfly, is referred to as " petal effect ".In addition to lotus leaf surface and petal surface, also Rice Leaf
Son, Chinese scholartree leaf, the leg of water skipper, gecko foot etc. all show special wetting property, the microscopic appearance on their surfaces point
Do not show micron-sized spherical, column, needle-shaped, fibrous or mastoid process etc., at the same have concurrently nano level protrusion, groove, spiral,
Cilium etc..It is inspired by this multi-stage micro-nano structure, various bionics techniques rapidly develop, and prepare different morphologies and function
Interface with special wellability, and special effect is played in life, for example, glass of building antifouling, hull drag reduction
Deng.Wherein template duplicating method is method the most traditional, the special construction built with fresh organism surface or nano-particle
As template, by the cast, sizing, demoulding of polymer and etc. obtain on pattern and function with nature biotechnology body surface face
Highly similar interface.Then, the means such as laser ablation, chemical etching, plasma etching are introduced into, directly to the table of material
Face carries out patterned process, can also obtain multiple dimensioned micro-nano structure.
The method that phase inversion is the multiple dimensioned micro-nano structure of a kind of structure that occurs recently to obtain ultra-hydrophobicity.It is
It is thermotropic or non-molten by a step using principles such as micellar copolymerization, spherocrystal growth, the dissolubility difference of multiple polymers in a solvent
The method of agent induction allows polymer to be detached from solvent, and micron order or nano level special knot are spontaneously formed during cured
Structure.Phase inversion overcome template duplicating method and surface etch method there are the problem of, i.e., complex steps, it is expensive, be limited to it is small
Size etc..Currently, it is sparser to generate micro-nano and pattern polymer during inversion of phases, and have to have
The surface of " lotus leaf effect " did not obtain the surface with " petal effect ", is more not carried out the controllable of height adhesion strength and turns
Become.In addition, the usually inclined hydrophily in polylactic acid membrane surface, hydrophobic surface is rarely reported.Prepare the polylactic acid of super-hydrophobicity
Film surface, and realize the controllable of its adhesion strength, there is highly important science and practical significance.
Invention content
It is the problems of above-mentioned the purpose of the present invention is being directed to, a kind of simple effective method is provided and prepares roseleaf
Bionic surface improves the hydrophobicity on polylactic acid membrane surface.
The method of the present invention comprises the concrete steps that：
Organic solvent, polylactic acid are added to the container stirring and dissolving by step (1), whipping temp is 75~95 DEG C, stirring when
Between for 4~for 24 hours, obtain preliminary finely dispersed casting solution；In casting solution by mass percentage contain 16~25 ﹪ of polylactic acid,
75~84 ﹪ of solvent；
Preferably, mixing time is 8~20h, mixing speed is 120~480rpm；
Preferably, the mass percent of polylactic acid is 16~22 ﹪, the mass percent of solvent is 78~84 ﹪；
The polylactic acid is the mixture of l-lactic acid (PLLA) and dextrorotation polylactic acid (PDLA), wherein left-handed poly- breast
Acid accounts for 60~95 ﹪ of polylactic acid gross mass, and dextrorotation polylactic acid accounts for 5~40 ﹪ of polylactic acid gross mass；
The solvent is dimethylformamide, dimethylacetylamide, methyl pyrrolidone, dimethyl sulfoxide (DMSO) and 1,4- bis-
Six ring of oxygen is one such or arbitrary two kinds of mixture；
Step (2) handles obtained uniform casting solution deaeration, is poured on the frosted glass of dry cleansing, with scraper striking
At primary membrane, in the coagulating bath for being 10~45 DEG C by primary membrane merging temperature in 10s, form a film after curing 10~50min；
Preferably, coagulation bath temperature is 15~35 DEG C, hardening time is 15~40min；
The thickness of the primary membrane is 100~500 μm；
The coagulating bath is the mixture of deionized water and organic solvent methyl pyrrolidone, and methyl pyrrolidone accounts for always
The volume ratio of coagulating bath is 0~30 ﹪；
Step (3) takes the polylactic acid membrane of completion of cure off from glass plate, impregnates in deionized water for 24 hours, after dry
Obtain the polylactic acid membrane interface with super-hydrophobicity；
The polylactic acid membrane interface with super-hydrophobicity is the face contacted with frosted glass；
It is 1~8 μm of microballoon that the polylactic acid membrane interface distributions with super-hydrophobicity, which have size, is had on each microballoon
Gap is the groove of 50~200nm；
The polylactic acid membrane hydrophobic contact angle is>140o, the adhesion strength to water droplet are 30 μ of μ N~140 N.
The polylactic acid membrane interface with super-hydrophobicity can be used for micro drop free of losses transport, security pattern is set
The fields such as meter, information transmission.
In the method for the present invention, the polylactic acid for providing multiple dimensioned micro-nano structure is constructed by the solvent-induced phase inversion of a step
Film surface shows super-hydrophobicity.Polylactic acid is a kind of chiral polymer, is divided into l-lactic acid and dextrorotation polylactic acid.Two kinds
The polylactic acid of optical activity is mixed with certain proportion, can form Stereocomplex crystalline substance in the solution.During inversion of phases, it is multiple to found structure
The presence of synthetic can greatly improve crystallinity, and casting solution is made to be easy to gel, form microballoon.Finally, the polylactic acid membrane surface obtained
A large amount of micron order sphere is distributed with, while having nano-scale groove on sphere.Such micro-nano structure is that water droplet is prevented to sprawl leaching
Profit provides enough roughness.The speed that solidification process is controlled by adjusting the thickness of primary membrane, with nascent film thickness
Increase, be fully cured and need longer time, more times are provided to crystallize and being formed gel.Microballoon quantity is with first
The thickness of filming increases and increases, and film surface is continuously decreased the adhesion strength of water droplet by high.
Description of the drawings
Fig. 1 is the super-hydrophobic polylactic acid membrane surface micro-nano structure pattern of the present invention.
Specific implementation mode
With reference to specific embodiment, the present invention is further analyzed.
Embodiment 1.
9.6g l-lactic acid, 6.4g dextrorotation polylactic acid (total 16g) are dissolved in 84g methyl pyrrolidones by step (1)
In, 12h, mixing speed 200rpm are stirred at 80 DEG C, obtain uniform initial casting solution；
Then the initial casting solution vacuumizing and defoaming that step (2) will be obtained is poured on clean clean frosted glass surface, uses
Scraper striking immerses primary membrane in 10s in 25 DEG C of coagulating bath pure water, submergence 10min allows poly- at the primary membrane of 100 μ m thicks
Lactic acid fully precipitates；
Step (3) takes the polylactic acid membrane being fully cured in step (2) off from frosted glass, impregnates in deionized water
For 24 hours, remaining solvent is removed, is then dried spare；
The polylactic acid membrane obtained with this condition, the face hydrophobic contact angle with contact glass sheet is 148o, to water droplet
Adhesion strength be 140 μ N.
It is 1~8 μm of microballoon that the polylactic acid membrane interface distributions with super-hydrophobicity, which have size, has gap on each microballoon
For the groove (as shown in Fig. 1) of 50~200nm.
Embodiment 2.
12.6g l-lactic acid, 5.4g dextrorotation polylactic acid (total 18g) are dissolved in 82g dimethylacetylamides by step (1)
In, 14h, mixing speed 120rpm are stirred at 85 DEG C, obtain uniform initial casting solution；
Then the initial casting solution vacuumizing and defoaming that step (2) will be obtained is poured on clean clean frosted glass surface, uses
Scraper striking is at the primary membrane of 200 μ m thicks, and in the interior coagulating baths that primary membrane is immersed to 15 DEG C of 10s, coagulating bath is water/methyl pyrrole
Pyrrolidone mixture, volume ratio 9：1, submergence 35min allows polylactic acid fully to precipitate；
Step (3) takes the polylactic acid membrane being fully cured in step (2) off from frosted glass, impregnates in deionized water
For 24 hours, remaining solvent is removed, is then dried spare；
The polylactic acid membrane obtained with this condition, the face hydrophobic contact angle with contact glass sheet is 149o, to water droplet
Adhesion strength be 132 μ N.The polylactic acid membrane interface is also as shown in Figure 1.
Embodiment 3
14.4g l-lactic acid, 3.6g dextrorotation polylactic acid (total 18g) are dissolved in 82g crassitudes by step (1)
Ketone/dimethylacetylamide in the mixed solvent stirs 8h, mixing speed 220rpm at 75 DEG C, obtains uniform initial casting solution；
Then the initial casting solution vacuumizing and defoaming that step (2) will be obtained is poured on clean clean frosted glass surface, uses
Scraper striking is at the primary membrane of 300 μ m thicks, and in the interior coagulating baths that primary membrane is immersed to 28 DEG C of 10s, coagulating bath is water/methyl pyrrole
Pyrrolidone mixture, volume ratio 8：2, submergence 40min allows polylactic acid fully to precipitate；
Step (3) takes the polylactic acid membrane being fully cured in step (2) off from frosted glass, impregnates in deionized water
For 24 hours, remaining solvent is removed, is then dried spare；
The polylactic acid membrane obtained with this condition, the face hydrophobic contact angle with contact glass sheet is 146o, to water droplet
Adhesion strength be 97 μ N.The polylactic acid membrane interface is also as shown in Figure 1.
Embodiment 4
12g l-lactic acid, 8g dextrorotation polylactic acid (total 20g) are dissolved in the mixing of 80g dimethylformamides by step (1)
In solvent, 18h, mixing speed 300rpm are stirred at 90 DEG C, obtain uniform initial casting solution；
Then the initial casting solution vacuumizing and defoaming that step (2) will be obtained is poured on clean clean frosted glass surface, uses
Scraper striking immerses primary membrane in 10s in 35 DEG C of coagulating bath pure water, submergence 15min allows poly- at the primary membrane of 400 μ m thicks
Lactic acid fully precipitates；
Step (3) takes the polylactic acid membrane being fully cured in step (2) off from frosted glass, impregnates in deionized water
For 24 hours, remaining solvent is removed, is then dried spare；
The polylactic acid membrane obtained with this condition, the face hydrophobic contact angle with contact glass sheet is 151o, to water droplet
Adhesion strength be 60 μ N.The polylactic acid membrane interface is also as shown in Figure 1.
Embodiment 5
19.8g l-lactic acid, 2.2g dextrorotation polylactic acid (total 22g) are dissolved in 78g Isosorbide-5-Nitraes-dioxy six by step (1)
In ring, 20h, mixing speed 400rpm are stirred at 75 DEG C, obtain uniform initial casting solution；
Then the initial casting solution vacuumizing and defoaming that step (2) will be obtained is poured on clean clean frosted glass surface, uses
Scraper striking is at the primary membrane of 300 μ m thicks, and in the interior coagulating baths that primary membrane is immersed to 15 DEG C of 10s, coagulating bath is water/methyl pyrrole
Pyrrolidone mixture, volume ratio 9：1, submergence 25min allows polylactic acid fully to precipitate；
Step (3) takes the polylactic acid membrane being fully cured in step (2) off from frosted glass, impregnates in deionized water
For 24 hours, remaining solvent is removed, is then dried spare；
The polylactic acid membrane obtained with this condition, the face hydrophobic contact angle with contact glass sheet is 151 °, to water droplet
Adhesion strength be 72 μ N.The polylactic acid membrane interface is also as shown in Figure 1.
Embodiment 6
14g l-lactic acid, 6g dextrorotation polylactic acid (total 20g) are dissolved in 80g dimethyl sulfoxide (DMSO)s, 95 by step (1)
15h, mixing speed 480rpm are stirred at DEG C, obtain uniform initial casting solution；
Then the initial casting solution vacuumizing and defoaming that step (2) will be obtained is poured on clean clean frosted glass surface, uses
Scraper striking is at the primary membrane of 500 μ m thicks, and in the interior coagulating baths that primary membrane is immersed to 30 DEG C of 10s, coagulating bath is water/methyl pyrrole
Pyrrolidone mixture, volume ratio 7：3, submergence 40min allows polylactic acid fully to precipitate；
Step (3) takes the polylactic acid membrane being fully cured in step (2) off from frosted glass, impregnates in deionized water
For 24 hours, remaining solvent is removed, is then dried spare；
The polylactic acid membrane obtained with this condition, the face hydrophobic contact angle with contact glass sheet is 152 °, to water droplet
Adhesion strength be 65 μ N.The polylactic acid membrane interface is also as shown in Figure 1.
Embodiment 7
23.75g l-lactic acid, 1.25g dextrorotation polylactic acid (total 25g) are dissolved in 75g dimethyl sulfoxide (DMSO)s by step (1)
In, 8h, mixing speed 300rpm are stirred at 95 DEG C, obtain uniform initial casting solution；
Then the initial casting solution vacuumizing and defoaming that step (2) will be obtained is poured on clean clean frosted glass surface, uses
Scraper striking is at the primary membrane of 300 μ m thicks, and in the interior coagulating baths that primary membrane is immersed to 10 DEG C of 10s, coagulating bath is water/methyl pyrrole
Pyrrolidone mixture, volume ratio 7：1, submergence 50min allows polylactic acid fully to precipitate；
Step (3) takes the polylactic acid membrane being fully cured in step (2) off from frosted glass, impregnates in deionized water
For 24 hours, remaining solvent is removed, is then dried spare；
The polylactic acid membrane obtained with this condition, the face hydrophobic contact angle with contact glass sheet is 141 °, to water droplet
Adhesion strength be 105 μ N.The polylactic acid membrane interface is also as shown in Figure 1.
Comparative example 1：(dextrorotation polylactic acid is added not in casting solution)
20g l-lactic acid is dissolved in 80g methyl pyrrolidones by step (1), and 20h, mixing speed are stirred at 80 DEG C
For 120rpm, uniform initial casting solution is obtained；
Then the initial casting solution vacuumizing and defoaming that step (2) will be obtained is poured on clean clean frosted glass surface, uses
Scraper striking is at the primary membrane of 400 μ m thicks, and in the interior coagulating baths that primary membrane is immersed to 20 DEG C of 10s, coagulating bath is water/methyl pyrrole
Pyrrolidone mixture, volume ratio 8：2, submergence 20min allows polylactic acid fully to precipitate；
Step (3) takes the polylactic acid membrane being fully cured in step (2) off from frosted glass, impregnates in deionized water
For 24 hours, remaining solvent is removed, is then dried spare；
The polylactic acid membrane obtained with this condition, the face hydrophobic contact angle with contact glass sheet is 75 °, is not super thin
Water termination, therefore water droplet adhesion strength cannot be measured.
Above-described embodiment is not for the limitation of the present invention, and the present invention is not limited only to above-described embodiment, as long as meeting
The present invention claims all belong to the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane, the polylactic acid membrane is hydrophobic to be connect
Feeler is>140 °, the adhesion strength to water droplet is 30 μ of μ N~140 N, it is characterised in that this approach includes the following steps：
Organic solvent, polylactic acid are added to the container stirring and dissolving by step (1), and whipping temp is 75~95 DEG C, mixing time is
4~for 24 hours, obtain preliminary finely dispersed casting solution；Contain 16~25 ﹪ of polylactic acid, solvent in casting solution by mass percentage
75~84 ﹪；
The polylactic acid is the mixture of l-lactic acid (PLLA) and dextrorotation polylactic acid (PDLA), and wherein l-lactic acid accounts for
60~95 ﹪ of polylactic acid gross mass, dextrorotation polylactic acid account for 5~40 ﹪ of polylactic acid gross mass；
Step (2) handles obtained uniform casting solution deaeration, is poured on the frosted glass of dry cleansing, with scraper striking at first
Filming forms a film in the interior coagulating baths for being 10~45 DEG C by primary membrane merging temperature of 10s after curing 10~50min；
Step (3) takes the polylactic acid membrane of completion of cure off from glass plate, impregnates in deionized water for 24 hours, is obtained after dry
Polylactic acid membrane interface with super-hydrophobicity.
2. a kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane as described in claim 1,
It is characterized in that step (1) mixing time is 8~20h, mixing speed is 120~480rpm.
3. a kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane as described in claim 1,
It is characterized in that the mass percent of step (1) polylactic acid is 16~22 ﹪, the mass percent of solvent is 78~84 ﹪.
4. a kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane as described in claim 1,
It is characterized in that the solvent described in step (1) is dimethylformamide, dimethylacetylamide, methyl pyrrolidone, dimethyl sulfoxide (DMSO)
With 1,4- dioxane is one such or arbitrary two kinds of mixture.
5. a kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane as described in claim 1,
It is characterized in that step (2) coagulation bath temperature is 15~35 DEG C, hardening time is 15~40min.
6. a kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane as described in claim 1,
It is characterized in that the thickness of the primary membrane described in step (2) is 100~500 μm.
7. a kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane as described in claim 1,
It is characterized in that the coagulating bath described in step (2) is the mixture of deionized water and organic solvent methyl pyrrolidone, methylpyrrole
The volume ratio that alkanone accounts for total coagulating bath is 0~30 ﹪.
8. a kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane as described in claim 1,
It is characterized in that the polylactic acid membrane interface with super-hydrophobicity described in step (3) is the face contacted with frosted glass.
9. a kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane as described in claim 1,
It is characterized in that the polylactic acid membrane interface distributions with super-hydrophobicity described in step (3) to have size being 1~8 μm of microballoon, each
It is the groove of 50~200nm to have gap on microballoon.
10. a kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane as described in claim 1,
It is characterized in that the polylactic acid membrane interface with super-hydrophobicity described in step (3) can be used for micro drop free of losses and transport, be anti-fake
Design, information transmit field.
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| CN108559084B (en) * | 2018-04-13 | 2020-12-04 | 华东理工大学 | Preparation method of polylactic acid-based hydrophobic film |
| CN109912825A (en) * | 2019-02-26 | 2019-06-21 | 华东理工大学 | A kind of preparation method of polylactic acid durable hydrophobic surfaces |
| CN110158316B (en) * | 2019-05-29 | 2021-02-26 | 南京大学 | Modified polylactic acid non-woven fabric for oil-water separation and preparation method and application thereof |
| CN111471204B (en) * | 2020-04-14 | 2021-06-08 | 北京航空航天大学 | Hydrophobic anisotropic surface and preparation method and application thereof |
| CN112076022B (en) * | 2020-09-29 | 2022-02-22 | 苏州永沁泉智能设备有限公司 | Wound dressing paste and preparation method thereof |
| CN114656682A (en) * | 2020-12-23 | 2022-06-24 | 中国科学院宁波材料技术与工程研究所 | Preparation method of super-hydrophobic polylactic acid porous material |
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| CN102408578A (en) * | 2011-09-22 | 2012-04-11 | 福建师范大学 | Preparation method for super hydrophobic biodegradable compound film and product thereof |
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| CN105085953A (en) * | 2015-08-25 | 2015-11-25 | 郑州大学 | Method for preparing polylactic acid super-hydrophobic membranes by aid of phase separation process |
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| CN102408578A (en) * | 2011-09-22 | 2012-04-11 | 福建师范大学 | Preparation method for super hydrophobic biodegradable compound film and product thereof |
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| CN105085953A (en) * | 2015-08-25 | 2015-11-25 | 郑州大学 | Method for preparing polylactic acid super-hydrophobic membranes by aid of phase separation process |
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