CN102408578B - Preparation method for super hydrophobic biodegradable compound film and product thereof - Google Patents
Preparation method for super hydrophobic biodegradable compound film and product thereof Download PDFInfo
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Abstract
The invention discloses a preparation method for super hydrophobic biodegradable compound film and a product thereof. Under a certain temperature, hydrophobic inorganic nano particles are added into transparent aliphatic biodegradable polyester liquid and stirred to form a mixed liquid dispersed uniformly. A dip-coating method is used for coating the mixed liquid on a certain substrate material and the volatizing speed of a solvent is adjusted by controlling the temperature rising speed to a certain temperature and then the temperature is kept constant for a certain period of time; then the mixed liquid is dried to obtain the super hydrophobic biodegradable compound film with a special micro-nano structure. The compound film is a compound film with a structure-controllable microporous network micro-nano secondary microscopic surface. The static contact angle between film and water is 155-164 degrees; moreover, the contact angle hysteresis of drops on the surface of the film is less than 5 degrees. A super hydrophobic coating formed by coating the super hydrophobic biodegradable compound film on the surface of a starch base biodegradable material can greatly reduce the hygroscopy of the starch base biodegradable material.
Description
Technical field
The present invention relates to preparation method of a kind of super hydrophobic biodegradable compound film and products thereof.
Background technology
Super hydrophobic surface refers generally to and the contact angle of the water surface greater than 150 °, and this class material has boundless application prospect in industrial and agricultural production and daily life.A large amount of studies show that, two kinds of methods of the general employing of the preparation of super hydrophobic surface, and a kind of is to modify the low surface energy material at uneven surface, another kind is at water repellent surface structure coarse structure.The preparation method of super hydrophobic surface mainly contains template, sol-gel method, phase separation method, Electrospinning Method, etching, self-assembly and additive method.
In recent years, after in the solution such as polymkeric substance such as polystyrene, polyvinyl chloride, adding the hydrophobic nano particle, form the film with super-hydrophobicity at substrate surface and seen that patent and bibliographical information are arranged.Chinese patent CN 104156016 A disclose a kind of preparation method of super-hydrophobic coat, after this method is evenly mixed polymers soln and hydrophobic silica dispersion liquid, adopt spray gun that mixture evenly is sprayed on the basal plane that cleans up, obtain super hydrophobic surface finally by thermal treatment.(the Yonggang Guo such as Guo, Qihua Wang et al. Facile approach in fabricating superhydrophobic coatings from silica-base nanocomposite. Applied Surface Science [J], 2010 (257): 33 – 36) be reported in and add water drain silica in the solution of general-purpose plastics such as polymethylmethacrylate, polystyrene, polyvinyl chloride etc. and fully mix, this mixed solution is applied and realized super-hydrophobicity in fact on surfaces such as glass, copper sheet, aluminium flake, filter paper.This method obtains super-hydrophobicity and has benefited from solvent evaporates post polymerization thing and the random micro-nano secondary coarse structure of similar island that is gathered into of inorganic nano-particle.If above method and coatings applications thereof are then had its limitation in Biodegradable material, because used superpolymer does not have biodegradability.Further how forming micro-nano secondary coarse structure on the surface of Biodegradable material also is a challenge, if base material is hydrophilic such as starch, fiber or chitosan etc., organic coating is difficult to sprawl; If base material is aliphatic polyester, then erosion action occurs in organic solvent easily.
On the other hand, the surface-coated super-hydrophobic coat at complete Biodegradable material is highly significant.Except can reaching antifouling and automatic cleaning action, Biodegradable material such as poly(lactic acid) or thermoplastic starch material may be degraded, be out of shape because of suction or be changed performance.Usual method such as chemical modification (CN 101205315A) or blending and modifying (CA 101481506A) can not make Biodegradable material realize super-hydrophobicity.Therefore, seek a kind of new method and realize that the Biodegradable material surface super-hydrophobic is necessary.
Summary of the invention
The objective of the invention is difficulty and limitation for the prior art existence, preparation method of a kind of biodegradable compound film with super-hydrophobicity and products thereof is provided, and this biodegradable compound film with super-hydrophobicity can be used for the surface-coated Biodegradable material to reach the effect of water proof anti-soil.
For realizing that the technical scheme that the object of the invention adopts is: at a certain temperature, a certain amount of aliphatics biodegradable polyesters is added in the volatile organic solvent, be stirred to and dissolve fully and form transparent solution, then add a certain amount of hydrophobicity inorganic nano-particle, continue to stir, form finely dispersed mixed solution.The method that adopts dipping to lift is coated to above-mentioned mixed solution on certain base material, regulate the evaporation rate of solvent to certain temperature by the control temperature rise rate, constant temperature regular hour again, obtain being combined with the product of the base material of the super hydrophobic biodegradable compound film with special micro and nano structure after the drying.
In the product of the base material that is combined with the super hydrophobic biodegradable compound film with special micro and nano structure, the static contact angle of super hydrophobic biodegradable compound film and water at 150 ° ~ 164 ° and water droplet at the contact angle hysteresis on the surface of film less than 5 °, and the super hydrophobic biodegradable compound film of the micro-nano secondary microcosmic surface of porous network shape and metal, glass, plastics, thermoplastic starch, polyvinyl alcohol, chitosan, Mierocrystalline cellulose, aliphatic polyester or starch/aliphatic poly ester blend mortise.
The product water-intake rate that described easy suction biodegradable base material is coated with behind the super hydrophobic biodegradable compound film is 0 ~ 0.9%.Easily suction biodegradable base material is in particular a kind of in starch/aliphatic poly ester blend, thermoplastic starch, polyvinyl alcohol, chitosan, Mierocrystalline cellulose, the aliphatic polyester.Best easy suction biodegradable base material is the base material that polylactic acid/starch (50:50) blend makes.
The principle that the laminated film that the present invention forms at base material has super-hydrophobicity is to form the film that one deck has three-dimensional network-like structure, shown in Fig. 2 a and Fig. 2 b, network bore hole size size is micron order, inorganic nano-particle then is evenly distributed on the thin film netowrk skeleton, particle size is that process through hydrophobicity on nano level and surface, thereby has formed the micro nano structure that is similar to lotus leaf.The formation of this micro nano structure at first is decided by the composition of material, and the biodegradable polyesters of high molecular consists of network skeleton and the hydrophobicity inorganic nano-particle is bonded together.If the amount of hydrophobicity inorganic nano-particle is less, then do not have the effect that increases surfaceness, if the amount of hydrophobicity inorganic nano-particle is higher, play the effect that increases surfaceness although can play to increase, can cause adhesion of thin film to descend.The mass ratio of hydrophobicity inorganic nano-particle of the present invention and biodegradable polyesters effect of hydrophobicity and sticking power in 0.3 ~ 0.9:1 scope is better.The second, depend on medium and the concentration of mixed solution.The volatility of organic solvent is lower, and polyester then can not form micrometer level porous structure.The concentration of polyester is lower, then can not form the film of continuous vesicular structure; The concentration of polyester is higher, add more nanoparticle and could increase surface microroughness, is unfavorable for forming micro-nano secondary porous network structure, also is not easy to obtain simultaneously uniform film.The medium of preferred mixed solution of the present invention is a kind of or its combination in boiling point 35 ~ 75 ℃ of organic solvents, particularly acetone, chloroform, methylene dichloride, the tetrahydrofuran (THF); Biodegradable polyesters and solvent preferred proportion are 0.5 ~ 2.5% (w/v).The 3rd, dipping time, pull rate and drying means.Reduce dipping time and can reduce the solvent solvent to aliphatics biodegradable polyesters surface erosion effect, suitable pull rate is conducive to form uniform thin film at matrix surface, drying means also forms above-mentioned special construction to film and plays important, the present invention adopts the control temperature rise rate, obtains the more orderly micro-nano secondary microtexture of structure.For example, the time that the present invention controls in the mixed solution that the polylactic acid/starch blend is immersed in poly(lactic acid) and nano silicon was 3 seconds, adopt the pull rate pulling film forming of 5cm/s, with 1 ℃/min temperature rise rate to 60 ℃, constant temperature 15min drying obtains the even laminated film of super-hydrophobicity in lactic acid/starch blend surface-coated again.This technique is applicable to glass, metal, plastics etc. simultaneously, and especially the materials such as Biodegradable material such as thermoplastic starch, polyvinyl alcohol, chitosan, Mierocrystalline cellulose, aliphatic polyester, starch/aliphatic polyester being reduced water-absorbent more has Practical significance.
The concrete preparation method of the present invention is:
Under 50 ℃ ~ 80 ℃, a certain amount of biodegradable polyesters is dissolved in a kind of volatilization organic solvent, stirring and dissolving forms clear solution, described biodegradable polyesters and organic solvent weightmeasurement ratio are controlled at 0.5 ~ 2.5% (w/v), solvent temperature is controlled at 50 ℃ ~ 80 ℃, add a certain amount of 10nm ~ 100nm hydrophobicity inorganic nanoparticles, the inorganic nano-particle protonatomic mass of wherein adding and the mass ratio of biodegradable polyester are 0.3 ~ 0.9:1 again; Continue to stir 1 ~ 2 hour, be cooled to room temperature, obtain finely dispersed mixed solution.Matrix is immersed in the above-mentioned mixed solution, the control dipping time is 3 ~ 8s, then controlling pull rate 3 ~ 5cm/s lifts out with matrix, be the evaporation rate that solvent ℃ is regulated in 0.5 ~ 2 ℃/min to 50 ~ 80 by regulating temperature rise rate, constant temperature 10 ~ 20min again obtains having the product of the starch/polylactic acid matrix material that is combined with the super hydrophobic biodegradable compound film with special micro and nano structure of the super hydrophobic biodegradable compound film (seeing Fig. 1, Fig. 2 a and Fig. 2 b) of special micro and nano structure after the drying.
Characteristics of the present invention are:
1, adopt biodegradable polyesters to prepare based superhydrophobic thin films, so based superhydrophobic thin films have biodegradability;
2, adopt the appropriate combination of biodegradable polyesters and hydrophobicity inorganic nano-particle, use lower boiling easy volatile organic solvent and control film preparation condition, make network-like micro-nano membrane structure, realize super-hydrophobicity;
3, to have a nanoparticle consumption few for this superhydrophobic film, and the film physical strength is high, the advantage of good permeability; Preparation process is simple, quick, cost is low, need not special equipment, universality is wide, be easy to realize industrialization.The method of dipping also can be eliminated organic solvent to the erosion action of substrate on the Biodegradable material surface;
4, super-hydrophobic Biodegradable film is coated on the Biodegradable material of easy suction, can effectively reduces the water-intake rate of material and the hydrolysis rate of the material that slows down, but do not affect the biodegradable characteristics of material.
Description of drawings
Fig. 1 is the contact angle test pattern of the poly(lactic acid) that obtains of the present invention/silicon-dioxide laminated film and water.
Fig. 2 a is the scanning electron microscope (SEM) photograph of the poly(lactic acid) that obtains of the present invention/silicon-dioxide laminated film.
Fig. 2 b is the partial enlarged drawing of Fig. 2 a.
Fig. 3 is the present invention (a) and rear (b) before polylactic acid/starch (50:50) composite matrix applies super-hydrophobic laminated film, the water-intake rate test pattern of matrix.
Fig. 4 is pellet injection molding (temperature of injection moulding machine is 150 ~ 175 ℃), the surface topography map of batten.
Embodiment
Can further be expressly understood the present invention by specific embodiments of the invention given below, but the following example is not limitation of the invention.
Embodiment 1: under 60 ℃, poly(lactic acid) (U.S. NatureWork LLC with 1.5g, 3051D) be dissolved in the chloroform of 60g, the magnetic agitation dissolving forms transparent solution, adding the 0.8g median size is that the 18nm hydrophobic silica (is won the wound Degussa again, R972) continue to stir 2 hours, be cooled to room temperature, obtain finely dispersed mixed solution.
Embodiment 2: under 60 ℃, poly(lactic acid) (U.S. NatureWork LLC with 1.5g, 3051D) be dissolved in the chloroform of 60g, the magnetic agitation dissolving forms transparent solution, adding the 0.5g median size is that the 18nm hydrophobic silica (is won the wound Degussa again, R972) continue to stir 2 hours, be cooled to room temperature, obtain finely dispersed mixed solution.
Embodiment 3: under 60 ℃, poly(lactic acid) (U.S. NatureWork LLC with 1.5g, 3051D) be dissolved in the chloroform of 50g, the magnetic agitation dissolving forms transparent solution, adding the 0.8g median size is that the 18nm hydrophobic silica (is won the wound Degussa again, R972) continue to stir 2 hours, be cooled to room temperature, obtain finely dispersed mixed solution.
Embodiment 4: under 60 ℃, poly(lactic acid) (U.S. NatureWork LLC with 1.5g, 3051D) be dissolved in the acetone of 60g, the magnetic agitation dissolving forms transparent solution, adding the 0.8g median size is that the 18nm hydrophobic silica (is won the wound Degussa again, R972) continue to stir 2 hours, be cooled to room temperature, obtain finely dispersed mixed solution.
Embodiment 5: under 60 ℃, poly(lactic acid) (U.S. NatureWork LLC with 1.5g, 3051D) be dissolved in the tetrahydrofuran (THF) of 60g, the magnetic agitation dissolving forms transparent solution, (the Guangzhou Son is received trade Co., Ltd to add the 0.8g median size again and be 20nm hydrophobicity titanium dioxide, JT-F1) continue to stir 2 hours, obtain finely dispersed mixed solution.
Embodiment 6: under 60 ℃, polycaprolactone (Shenzhen City Guanghua Weiye Industry Co.,Ltd with 1.5g, 1000C) be dissolved in the chloroform of 60g, the magnetic agitation dissolving forms transparent solution, adding the 0.8g median size is that the 18nm hydrophobic silica (is won the wound Degussa again, R972) continue to stir 2 hours, be cooled to room temperature, obtain finely dispersed mixed solution.
Embodiment 7: the sheet glass of cleaning is immersed in the mixed solution that embodiment 1 obtains, the control dipping time is 3 seconds, then with the pull rate sheet glass of 3cm/s out, with 1 ℃/min temperature rise rate to 60 ℃, constant temperature 15min drying obtains the even laminated film of super-hydrophobicity that applies at glass surface again.Referring to Fig. 1 and Fig. 2 a and Fig. 2 b, with the wettability of this film of Shanghai Solon SL200S contact angle instrument test test, the result shows that the contact angle of this film surface and water is 162 ± 1.4 °.Film morphology JSM-7500F scanning electron microscopic observation finds that this film has the micro-nano secondary structure of porous network shape.
Embodiment 8: the sheet glass of cleaning is immersed in the mixed solution that embodiment 2 obtains, the control dipping time is 3 seconds, then with the pull rate sheet glass of 3cm/s out, with 2 ℃/min temperature rise rate to 60 ℃, constant temperature 15min drying obtains the even laminated film of super-hydrophobicity that applies at glass surface again.With the wettability of this film of Shanghai Solon SL200S contact angle instrument test test, the result shows that the contact angle of this film surface and water is 153 ± 1.6 °.Film morphology JSM-7500F scanning electron microscopic observation finds that this film has the micro-nano secondary structure of porous network shape.
Embodiment 9: the sheet glass of cleaning is immersed in the mixed solution that embodiment 3 obtains, the control dipping time is 6 seconds, then with the pull rate sheet glass of 5cm/s out, with 2 ℃/min temperature rise rate to 60 ℃, constant temperature 15min drying obtains the even laminated film of super-hydrophobicity that applies at glass surface again.With the wettability of this film of Shanghai Solon SL200S contact angle instrument test test, the result shows that the contact angle of this film surface and water is 148 ± 1.7 °.Film morphology JSM-7500F scanning electron microscopic observation finds that this film has the micro-nano secondary structure of porous network shape.
Embodiment 10: the sheet glass of cleaning is immersed in the mixed solution that embodiment 4 obtains, the control dipping time is 3 seconds, then with the pull rate sheet glass of 3cm/s out, with 2 ℃/min temperature rise rate to 70 ℃, constant temperature 15min drying obtains the even laminated film of super-hydrophobicity that applies at glass surface again.With the wettability of this film of Shanghai Solon SL200S contact angle instrument test test, the result shows that the contact angle of this film surface and water is 151 ± 1.3 °.Film morphology JSM-7500F scanning electron microscopic observation finds that this film has the micro-nano secondary structure of porous network shape.
Embodiment 11: the sheet glass of cleaning is immersed in the mixed solution that embodiment 5 obtains, the control dipping time is 3 seconds, then with the pull rate sheet glass of 3cm/s out, with 2 ℃/min temperature rise rate to 75 ℃, constant temperature 15min drying obtains the even laminated film of super-hydrophobicity that applies at glass surface again.With the wettability of this film of Shanghai Solon SL200S contact angle instrument test test, the result shows that the contact angle of this film surface and water is 155 ± 1.3 °.Film morphology JSM-7500F scanning electron microscopic observation finds that this film has the micro-nano secondary structure of porous network shape.
Embodiment 12: the sheet glass of cleaning is immersed in the mixed solution that embodiment 6 obtains, the control dipping time is 3 seconds, then with the pull rate sheet glass of 3cm/s out, with 2 ℃/min temperature rise rate to 65 ℃, constant temperature 15min drying obtains the even laminated film of super-hydrophobicity that applies at glass surface again.With the wettability of this film of Shanghai Solon SL200S contact angle instrument test test, the result shows that the contact angle of this film surface and water is 158 ± 1.5 °.Film morphology JSM-7500F scanning electron microscopic observation finds that this film has the micro-nano secondary structure of porous network shape.
Embodiment 13: the mixed solution that embodiment 1 is obtained, press the film of embodiment 7, in (the self-control of polylactic acid/starch (50:50) blends surface, the preparation method sees remarks *) apply and to obtain super hydrophobic film, to have the super-hydrophobicity film coating the starch/polylactic acid matrix material product of the present invention and be immersed in the tap water without super-hydrophobic coat starch/polylactic acid matrix material, investigate every three days the water-absorbent of bi-material.As shown in Figure 3, found afterwards in 40 days, polylactic acid/starch (50:50) blend (self-control without super-hydrophobic coating, the preparation method sees remarks *) the water-intake rate of matrix material be 14%, and has the product water-intake rate 0.2% of the present invention of the starch/polylactic acid matrix material of super-hydrophobicity film coating, show good water tolerance, and super-hydrophobicity film coating and starch/polylactic acid matrix material be without coming off, show in conjunction with firmly.
Remarks * (polylactic acid/starch (50:50) blend preparation method):
Starch (Fujian Pepsida Biology Materials Co., Ltd) and poly(lactic acid) (U.S. NatureWork LLC with drying, 3051D) (mass ratio is 50:50) is in high-speed mixer (SHR-5 type, Zhangjagang City Rui Da engineering works) mix in, then use twin screw extruder (PheoDrive 4 Haake Polylab OS type torque rheometers, Germany Haake company) (temperature of forcing machine is 150 ~ 170 ℃ to melt extrude granulation, screw speed is 60r/min), use at last injection moulding machine (JN55-E type, shake male machine company limited) pellet injection molding (temperature of injection moulding machine is 150 ~ 175 ℃), the surface topography of batten is as shown in Figure 4.
Claims (7)
1. the preparation method of a super hydrophobic biodegradable compound film is characterized in that:
At a certain temperature, a certain amount of biodegradable polyesters is added in the volatile organic solvent, be stirred to and dissolve fully and form transparent solution; Add a certain amount of hydrophobicity inorganic nano-particle to above-mentioned solution, continue to stir, form finely dispersed mixed solution, cool to room temperature obtains mixed solution for subsequent use; Adopt dip-coating method, base material is immersed in the above-mentioned mixed solution, the control dipping time, then controlling pull rate lifts out with base material, regulate the evaporation rate of solvent by control temperature rise rate to constant temp, constant temperature regular hour again, obtain being combined with the product of the base material of the super hydrophobic biodegradable compound film with special micro and nano structure after the drying; Described biodegradable polyesters and organic solvent weightmeasurement ratio are controlled at 0.5 ~ 2.5% (w/v), and solvent temperature is controlled at 50 ℃ ~ 80 ℃; Hydrophobicity inorganic nano-particle and biodegradable polyesters mass ratio are controlled at 0.3 ~ 0.9:1; The dipping time of described dip-coating method is 3 ~ 8s; Pull rate is 3 ~ 5cm/s; Heat-up rate is 0.5 ~ 2 ℃/min, and steady temperature is controlled at 50 ℃ ~ 80 ℃, and constant temperature time is 10 ~ 20min.
2. preparation method as claimed in claim 1, it is characterized in that, described biodegradable polyesters is that weight-average molecular weight is 60,000 ~ 120,000 aliphatic polyester, is selected from a kind of or its combination in poly(lactic acid), poly(hydrobutyl ester), poly-succinic fourth diester or the pla-pcl.
3. preparation method as claimed in claim 1 is characterized in that, described volatile organic solvent boiling point is 35 ℃-75 ℃, is selected from a kind of or its combination in acetone, chloroform, methylene dichloride, the tetrahydrofuran (THF).
4. preparation method as claimed in claim 1 is characterized in that, described hydrophobicity inorganic nano-particle is that primary particle diameter is the inorganic particulate of 10nm ~ 100nm, is selected from a kind of or its combination of silicon-dioxide, titanium dioxide, aluminium sesquioxide, calcium carbonate.
5. preparation method as claimed in claim 1 or 2 is characterized in that, described base material is metal, glass, plastics or the Biodegradable material that easily absorbs water.
6. preparation method as claimed in claim 5 is characterized in that, described easy suction Biodegradable material is a kind of in starch/aliphatic poly ester blend, thermoplastic starch, polyvinyl alcohol, chitosan, Mierocrystalline cellulose, the aliphatic polyester.
7. the product that makes of the arbitrary described preparation method of claim 1 ~ 6, it is characterized in that, make the product of the base material that is combined with the super hydrophobic biodegradable compound film with special micro and nano structure, the static contact angle of described super hydrophobic biodegradable compound film and water at 150 ° ~ 164 ° and water droplet at the contact angle hysteresis on the surface of film less than 5 °, and super hydrophobic biodegradable compound film and the metal of the micro-nano secondary microcosmic surface of porous network shape, glass, plastics, thermoplastic starch, polyvinyl alcohol, chitosan, Mierocrystalline cellulose or starch/aliphatic poly ester blend mortise.
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| CN103409028B (en) * | 2013-07-29 | 2017-11-17 | 复旦大学 | A kind of photocatalytic type self-repairing super-hydrophobic coating and preparation method thereof |
| CN105085953B (en) * | 2015-08-25 | 2018-03-16 | 郑州大学 | The method that PLA based superhydrophobic thin films are prepared using phase separation method |
| CN105348725B (en) * | 2015-11-20 | 2018-10-30 | 江苏怡丽科姆新材料股份有限公司 | A kind of degradable based superhydrophobic thin films and preparation method thereof |
| CN105646920B (en) * | 2016-03-16 | 2018-09-25 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method based on the super-hydrophobic interface of Stereocomplex crystalline substance structure polylactic acid membrane |
| CN106977948A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that PLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance |
| CN107353740B (en) * | 2017-08-23 | 2020-02-21 | 重庆索利特装饰有限公司 | Energy-saving self-cleaning exterior wall latex paint, preparation method thereof and building exterior wall |
| CN109954171A (en) * | 2017-12-26 | 2019-07-02 | 先健科技(深圳)有限公司 | Absorbable implantable device |
| CN108559084B (en) * | 2018-04-13 | 2020-12-04 | 华东理工大学 | Preparation method of polylactic acid-based hydrophobic film |
| CN111100310A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Full-biodegradable high-water-resistance film and preparation method and application thereof |
| CN110201244B (en) * | 2019-07-17 | 2022-09-20 | 山东百多安医疗器械股份有限公司 | Lyophobic low functional catheter that glues |
| CN114874592B (en) * | 2022-03-30 | 2023-11-03 | 中原工学院 | Flexible porous super-hydrophobic film and preparation method thereof |
| CN114773649B (en) * | 2022-05-11 | 2024-01-05 | 向蕾 | Waterproof degradable PLA plastic packaging film and preparation method thereof |
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| KR100551742B1 (en) * | 2003-12-09 | 2006-02-13 | 도레이새한 주식회사 | Transparent and Bioresolvable Polyester Film Having Improved Elongation Rate and Separation Charater and the Manufacturing Method Thereof |
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| CN1200750A (en) * | 1995-09-12 | 1998-12-02 | Fvp股份有限公司 | Process for producing mouldings with a barrier layer made of biodegradable material, and mouldings produced according to this process |
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