CN102408578A - 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
- Publication number
- CN102408578A CN102408578A CN2011102823758A CN201110282375A CN102408578A CN 102408578 A CN102408578 A CN 102408578A CN 2011102823758 A CN2011102823758 A CN 2011102823758A CN 201110282375 A CN201110282375 A CN 201110282375A CN 102408578 A CN102408578 A CN 102408578A
- Authority
- CN
- China
- Prior art keywords
- biodegradable
- super
- film
- preparation
- base material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
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 laminated 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 type material all has boundless application prospect in industrial and agricultural production and daily life.A large amount of researchs show, 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, and phase separation method, electricity spins method, etching, self-assembly and other methods.
In recent years, after in solution such as polymkeric substance such as PS, SE, adding the hydrophobic nano particle, form film at substrate surface and seen that patent and bibliographical information are arranged with super-hydrophobicity.Chinese patent CN 104156016 A disclose a kind of preparation method of super-hydrophobic coat; This method with polymers soln and hydrophobic silica dispersion liquid uniform mixing after; Adopt spray gun that mixture evenly is sprayed on the basal plane that cleans up, after thermal treatment obtains super hydrophobic surface.(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 and thorough mixing in the solution of general-purpose plastics such as polymethylmethacrylate, PS, SE etc., reality applies and has realized super-hydrophobicity on surfaces such as glass, copper sheet, aluminium flake, filter paper with this mixed solution.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 like starch, fiber or chitosan etc., organic coating is difficult to sprawl; If base material is an aliphatic polyester, then erosion action takes place 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 POLYACTIC ACID or thermoplastic starch material possibly degraded, be out of shape or changed performance because of suction.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 to the prior art existence; Preparing method of a kind of biodegradable laminated film with super-hydrophobicity and products thereof is provided, and this biodegradable laminated film with super-hydrophobicity can be used for the surface-coated Biodegradable material to reach the antifouling effect of waterproof.
For realizing that the technical scheme that the object of the invention adopted 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; Add a certain amount of hydrophobicity inorganic nano-particle then, 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 through the control temperature rise rate; Constant temperature regular hour again, obtain being combined with the product of the base material of super-hydrophobic biodegradable laminated film after the drying with special micro and nano structure.
In the product of the base material that is combined with super-hydrophobic biodegradable laminated film with special micro and nano structure; The static contact angle of super-hydrophobic biodegradable laminated 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 laminated film of the micro-nano secondary microcosmic surface of porous network shape and metal, glass, plastics, thermoplastic starch, Z 150PH, chitosan, Mierocrystalline cellulose, aliphatic polyester or starch/aliphatic poly ester blend mortise.
The product water-intake rate that said easy suction biodegradable base material is coated with behind the super-hydrophobic biodegradable laminated film is 0 ~ 0.9%.Be prone to suction biodegradable base material and be in particular a kind of in starch/aliphatic poly ester blend, thermoplastic starch, Z 150PH, 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 on 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 a micron order; Inorganic nano-particle then is evenly distributed on the thin film netowrk skeleton, and particle size is that handle 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 high-molecular weight biodegradable polyesters constitutes 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 though 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 the 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 successive 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 THF; Biodegradable polyesters and solvent preferred proportion are 0.5 ~ 2.5% (w/v).The 3rd, time of immersion, pull rate and drying means.Reduce time of immersion and can reduce solvent aliphatics biodegradable polyesters surface erosion effect; Suitable pull rate helps forming 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 texture ratio.For example; The time that the present invention controls in the mixed solution that the polylactic acid/starch blend is immersed in POLYACTIC 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 technology is applicable to glass, metal, plastics etc. simultaneously, and especially materials such as Biodegradable material such as thermoplastic starch, Z 150PH, 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, and said biodegradable polyesters and organic solvent weightmeasurement ratio are controlled at 0.5 ~ 2.5% (w/v), and solvent temperature is controlled at 50 ℃ ~ 80 ℃; Add a certain amount of 10nm ~ 100nm hydrophobicity inorganic nanoparticles again, the inorganic nano-particle protonatomic mass of wherein being added and the mass ratio of biodegradable polyester are 0.3 ~ 0.9:1; 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 time of immersion is 3 ~ 8s; Controlling pull rate 3 ~ 5cm/s then lifts out with matrix; Through regulating temperature rise rate is the evaporation rate that solvent ℃ is regulated in 0.5 ~ 2 ℃/min to 50 ~ 80; Constant temperature 10 ~ 20min again obtains having the product of the starch/lactic acid composite material that is combined with the super-hydrophobic biodegradable laminated film with special micro and nano structure of the super-hydrophobic biodegradable laminated 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 super-hydrophobicity film, and the film physical strength is high, the advantage of good permeability; The preparation process is simple, quick, cost is low, need not special devices, universality is wide, be easy to realize industriallization.The method of dipping also can be eliminated the erosion action of organic solvent to substrate on the Biodegradable material surface;
4, super-hydrophobic Biodegradable film is coated on the Biodegradable material that is prone to suction, can effectively reduces the water-intake rate of material and the hydrolysis rate of the material that slows down, but do not influence the biodegradable characteristics of material.
Description of drawings
Fig. 1 is the POLYACTIC ACID/silicon-dioxide laminated film that obtains of the present invention and the contact angle test pattern of water.
Fig. 2 a is the sem photograph of POLYACTIC ACID/silicon-dioxide laminated film of obtaining of the present invention.
Fig. 2 b is the partial enlarged drawing of Fig. 2 a.
Fig. 3 is the present invention (a) and back (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 through specific embodiment of the present invention given below, but the following example is not to qualification of the present invention.
Embodiment 1: under 60 ℃; (U.S. NatureWork LLC 3051D) is dissolved in the chloroform of 60g, and the magnetic agitation dissolving forms transparent solution with the POLYACTIC ACID of 1.5g; Adding the 0.8g median size again is that the 18nm hydrophobic silica (is won the wound Degussa; R972) continue to stir 2 hours, be cooled to room temperature, obtain finely dispersed mixed solution.
Embodiment 2: under 60 ℃; (U.S. NatureWork LLC 3051D) is dissolved in the chloroform of 60g, and the magnetic agitation dissolving forms transparent solution with the POLYACTIC ACID of 1.5g; Adding the 0.5g median size again is that the 18nm hydrophobic silica (is won the wound Degussa; R972) continue to stir 2 hours, be cooled to room temperature, obtain finely dispersed mixed solution.
Embodiment 3: under 60 ℃; (U.S. NatureWork LLC 3051D) is dissolved in the chloroform of 50g, and the magnetic agitation dissolving forms transparent solution with the POLYACTIC ACID of 1.5g; Adding the 0.8g median size again is that the 18nm hydrophobic silica (is won the wound Degussa; R972) continue to stir 2 hours, be cooled to room temperature, obtain finely dispersed mixed solution.
Embodiment 4: under 60 ℃; (U.S. NatureWork LLC 3051D) is dissolved in the acetone of 60g, and the magnetic agitation dissolving forms transparent solution with the POLYACTIC ACID of 1.5g; Adding the 0.8g median size again is that the 18nm hydrophobic silica (is won the wound Degussa; R972) continue to stir 2 hours, be cooled to room temperature, obtain finely dispersed mixed solution.
Embodiment 5: under 60 ℃; POLYACTIC ACID (U.S. NatureWork LLC with 1.5g; 3051D) be dissolved in the THF of 60g, magnetic agitation dissolving forms transparent solution, and (the Guangzhou Son is received trade Co., Ltd to add the 0.8g median size again and be 20nm hydrophobicity titanium oxide; JT-F1) continue to stir 2 hours, obtain finely dispersed mixed solution.
Embodiment 6: under 60 ℃; (Shenzhen City Guanghua Weiye Industry Co.,Ltd 1000C) is dissolved in the chloroform of 60g, and the magnetic agitation dissolving forms transparent solution with the polycaprolactone of 1.5g; Adding the 0.8g median size again is that the 18nm hydrophobic silica (is won the wound Degussa; 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 time of immersion is 3 seconds; Pull rate sheet glass with 3cm/s comes out then; 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 appearance test test, the result shows that the contact angle of this film surface and water is 162 ± 1.4 °.Film morphology is used the 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 time of immersion is 3 seconds; Pull rate sheet glass with 3cm/s comes out then; 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 appearance test test, the result shows that the contact angle of this film surface and water is 153 ± 1.6 °.Film morphology is used the 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 time of immersion is 6 seconds; Pull rate sheet glass with 5cm/s comes out then; 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 appearance test test, the result shows that the contact angle of this film surface and water is 148 ± 1.7 °.Film morphology is used the 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 time of immersion is 3 seconds; Pull rate sheet glass with 3cm/s comes out then; 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 appearance test test, the result shows that the contact angle of this film surface and water is 151 ± 1.3 °.Film morphology is used the 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 time of immersion is 3 seconds; Pull rate sheet glass with 3cm/s comes out then; 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 appearance test test, the result shows that the contact angle of this film surface and water is 155 ± 1.3 °.Film morphology is used the 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 time of immersion is 3 seconds; Pull rate sheet glass with 3cm/s comes out then; 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 appearance test test, the result shows that the contact angle of this film surface and water is 158 ± 1.5 °.Film morphology is used the 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, the product of the present invention that will have the starch/lactic acid composite material of super-hydrophobicity film coating is immersed in the tap water with no super-hydrophobic coat starch/lactic acid composite material, investigates the water-absorbent of two kinds of materials every three days.As shown in Figure 3; Find after 40 days that the water-intake rate of the matrix material of the polylactic acid/starch of no super-hydrophobic coating (50:50) blend (self-control, the preparation method sees remarks *) is 14%; And has the product water-intake rate 0.2% of the present invention of the starch/lactic acid composite material of super-hydrophobicity film coating; Show excellent water tolerance, and the super-hydrophobicity film coating do not have with starch/lactic acid composite material and comes off, show combine firm.
Remarks * (polylactic acid/starch (50:50) blend preparation method):
With exsiccant starch (Fujian Pepsida Biology Materials Co., Ltd) and POLYACTIC ACID (U.S. NatureWork LLC; 3051D) (mass ratio is 50:50) is in high-speed mixer (SHR-5 type; Zhangjagang City Rui Da engineering works) mix in, (temperature of forcing machine is 150 ~ 170 ℃ to melt extrude granulation to use twin screw extruder (PheoDrive 4 Haake Polylab OS type torque rheometers, German Haake company) then; Screw speed is 60r/min); Pellet injection molding (temperature of injection moulding machine is 150 ~ 175 ℃), the surface topography of batten is as shown in Figure 4 to use injection moulding machine (the JN55-E type shakes male machine ltd) at last.
Claims (10)
1. the preparation method of a super-hydrophobic biodegradable laminated 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 in a certain amount of hydrophobicity inorganic nano-particle to the above-mentioned solution, continue to stir, form finely dispersed mixed solution, cool to room temperature obtains subsequent use mixed solution; Adopt dip-coating method; Base material is immersed in the above-mentioned mixed solution; The control time of immersion is controlled pull rate then base material is lifted out, regulates the evaporation rate of solvent through control temperature rise rate to constant temp; Constant temperature regular hour again, obtain being combined with the product of the base material of super-hydrophobic biodegradable laminated film after the drying with special micro and nano structure.
2. preparation method as claimed in claim 1 is characterized in that, said 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 time of immersion of said 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.
3. according to claim 1 or claim 2 preparation method; It is characterized in that; Described biodegradable polyesters is that weight-average molecular weight is 60,000 ~ 120,000 aliphatic polyester, and special is a kind of or its combination in POLYACTIC ACID, poly(hydrobutyl ester), poly-succinic fourth diester or the pla-pcl.
4. according to claim 1 or claim 2 preparation method is characterized in that described volatile organic solvent boiling point is 35 ℃-75 ℃, and special is a kind of or its combination in acetone, chloroform, methylene dichloride, the THF.
5. according to claim 1 or claim 2 preparation method; It is characterized in that; Described hydrophobicity inorganic nano-particle is that primary particle diameter is the inorganic particulate of 10nm ~ 100nm, and special is a kind of or its combination of silicon-dioxide, titanium oxide, aluminium sesquioxide, lime carbonate.
6. according to claim 1 or claim 2 preparation method is characterized in that described base material is metal, glass, plastics, and special in being prone to the suction Biodegradable material, the shape of base material is not limit.
7. preparation method as claimed in claim 6 is characterized in that, described easy suction Biodegradable material is a kind of in starch/aliphatic poly ester blend, thermoplastic starch, Z 150PH, chitosan, Mierocrystalline cellulose, the aliphatic polyester.
8. the product that makes of the arbitrary described preparation method of claim 1 ~ 7; It is characterized in that; Make the product of the base material that is combined with super-hydrophobic biodegradable laminated film with special micro and nano structure; The static contact angle of said super-hydrophobic biodegradable laminated 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 laminated film of the micro-nano secondary microcosmic surface of porous network shape and metal, glass, plastics, thermoplastic starch, Z 150PH, chitosan, Mierocrystalline cellulose, aliphatic polyester or starch/aliphatic poly ester blend mortise.
9. product as claimed in claim 8 is characterized in that, the product water-intake rate that easy suction biodegradable base material is coated with behind the super-hydrophobic biodegradable laminated film is 0 ~ 0.9%.
10. product as claimed in claim 8 is characterized in that, being prone to suction biodegradable base material is the base material that polylactic acid/starch (50:50) blend makes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110282375 CN102408578B (en) | 2011-09-22 | 2011-09-22 | Preparation method for super hydrophobic biodegradable compound film and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110282375 CN102408578B (en) | 2011-09-22 | 2011-09-22 | Preparation method for super hydrophobic biodegradable compound film and product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102408578A true CN102408578A (en) | 2012-04-11 |
| CN102408578B CN102408578B (en) | 2013-04-03 |
Family
ID=45910953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110282375 Expired - Fee Related CN102408578B (en) | 2011-09-22 | 2011-09-22 | Preparation method for super hydrophobic biodegradable compound film and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102408578B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409028A (en) * | 2013-07-29 | 2013-11-27 | 复旦大学 | Photocatalytic type self-repairing super-hydrophobic coating and preparation method thereof |
| CN103852401A (en) * | 2012-11-29 | 2014-06-11 | 金发科技股份有限公司 | Measuring method of the intrinsic viscosity of biodegradable polymer |
| 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 |
| CN105348725A (en) * | 2015-11-20 | 2016-02-24 | 福州顺升科技有限公司 | Degradable super-hydrophobic film and preparation method thereof |
| CN105646920A (en) * | 2016-03-16 | 2016-06-08 | 中国科学院宁波材料技术与工程研究所 | Preparation method for constructing polylactic acid film super-hydrophobic interface based on stereocomplex crystals |
| 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 |
| CN107353740A (en) * | 2017-08-23 | 2017-11-17 | 重庆索利特涂料有限公司 | One kind energy-conservation automatically cleaning exterior wall latex paint, its preparation method and external wall |
| CN108559084A (en) * | 2018-04-13 | 2018-09-21 | 华东理工大学 | A kind of preparation method of polylactic acid base hydrophobic film |
| CN109954171A (en) * | 2017-12-26 | 2019-07-02 | 先健科技(深圳)有限公司 | Absorbable implantable device |
| CN110201244A (en) * | 2019-07-17 | 2019-09-06 | 山东百多安医疗器械有限公司 | A kind of low viscous functional catheter of lyophoby |
| 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 |
| CN114773649A (en) * | 2022-05-11 | 2022-07-22 | 向蕾 | Waterproof degradable PLA plastic packaging film and preparation method thereof |
| CN114874592A (en) * | 2022-03-30 | 2022-08-09 | 中原工学院 | Flexible porous super-hydrophobic film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| KR20050056020A (en) * | 2003-12-09 | 2005-06-14 | 도레이새한 주식회사 | Transparent and bioresolvable polyester film having improved elongation rate and separation charater and the manufacturing method thereof |
-
2011
- 2011-09-22 CN CN 201110282375 patent/CN102408578B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| KR20050056020A (en) * | 2003-12-09 | 2005-06-14 | 도레이새한 주식회사 | Transparent and bioresolvable polyester film having improved elongation rate and separation charater and the manufacturing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YONGGANG GUO ET AL.: "Facile approach in fabricating superhydrophobic coatings from silica-based nanocomposite", 《APPLIED SURFACE SCIENCE》 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103852401A (en) * | 2012-11-29 | 2014-06-11 | 金发科技股份有限公司 | Measuring method of the intrinsic viscosity of biodegradable polymer |
| CN103409028A (en) * | 2013-07-29 | 2013-11-27 | 复旦大学 | Photocatalytic type self-repairing super-hydrophobic coating and preparation method thereof |
| 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 |
| 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 |
| 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 |
| CN105348725A (en) * | 2015-11-20 | 2016-02-24 | 福州顺升科技有限公司 | Degradable super-hydrophobic film and preparation method thereof |
| 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 |
| CN105646920A (en) * | 2016-03-16 | 2016-06-08 | 中国科学院宁波材料技术与工程研究所 | Preparation method for constructing polylactic acid film super-hydrophobic interface based on stereocomplex crystals |
| 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 |
| CN107353740A (en) * | 2017-08-23 | 2017-11-17 | 重庆索利特涂料有限公司 | One kind energy-conservation automatically cleaning exterior wall latex paint, its preparation method and external wall |
| 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 |
| CN108559084A (en) * | 2018-04-13 | 2018-09-21 | 华东理工大学 | A kind of preparation method of polylactic acid base hydrophobic film |
| 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 |
| CN110201244A (en) * | 2019-07-17 | 2019-09-06 | 山东百多安医疗器械有限公司 | A kind of low viscous functional catheter of lyophoby |
| CN114874592A (en) * | 2022-03-30 | 2022-08-09 | 中原工学院 | Flexible porous super-hydrophobic film and preparation method thereof |
| CN114874592B (en) * | 2022-03-30 | 2023-11-03 | 中原工学院 | Flexible porous super-hydrophobic film and preparation method thereof |
| CN114773649A (en) * | 2022-05-11 | 2022-07-22 | 向蕾 | Waterproof degradable PLA plastic packaging 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102408578B (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102408578B (en) | Preparation method for super hydrophobic biodegradable compound film and product thereof | |
| Moghadam et al. | Multifunctional superhydrophobic surfaces | |
| CN109370418A (en) | A kind of super hydrophobic coating, coating and its preparation method and application | |
| CN101307210B (en) | Ultra-discharging water-soluble fluor-silicon-acrylic coatings with nano particles | |
| CN108301202A (en) | A kind of Self-cleaning fabric and preparation method thereof that two dimension titanium dioxide/graphene sheet is modified | |
| CN107090087B (en) | Method for preparing adhesion-controllable PLA (polylactic acid) super-hydrophobic film by using solvent-non-solvent assisted microphase separation method | |
| Guan et al. | Design and fabrication of vapor-induced superhydrophobic surfaces obtained from polyethylene wax and silica nanoparticles in hierarchical structures | |
| CN108641419B (en) | Super-hydrophilic coating sol and preparation and use methods thereof | |
| CN109880470B (en) | Preparation method of water-based acrylate time-delay antibacterial coating | |
| CN104587924B (en) | Oligomer precoating prepares low-density without permeability porous or the method for hollow microsphere | |
| CN114752275A (en) | Preparation method of bionic super-hydrophobic coating capable of being sprayed on various substrates | |
| CN101745352A (en) | Superhydrophobic surface material and special nano-particles thereof with core-shell structures | |
| CN109833836B (en) | Method for preparing zein-based titanium dioxide hybrid microcapsules by interfacial polymerization method | |
| WO2006099791A1 (en) | A method for preparing multi-substance dispersion-effect thin membrane with nano-structure and the use thereof | |
| CN108912754A (en) | A kind of super-hydrophobic SiO2The preparation method and application of nano functional liquid | |
| CN112206353B (en) | Chitin whisker liquid crystal elastomer modified polylactic acid composite material and preparation method and application thereof | |
| Li et al. | Self-healing system of superhydrophobic surfaces inspired from and beyond nature | |
| CN102099100A (en) | Method for dry dispersion of nanoparticles and production of hierarchical structures and coatings | |
| TWI640565B (en) | Polymer latex particle composition containing nano silver particles | |
| CN101148550B (en) | Multi-substance straggling effect nano structure liquid membrane and its preparation method and application | |
| CN102115543B (en) | Method for preparing high-hydrophobic polyester | |
| CN114656682A (en) | Preparation method of super-hydrophobic polylactic acid porous material | |
| CN103060773B (en) | A kind of preparation method of superhydrophobic surface material | |
| CN101302361B (en) | Preparation of zircite cladding iron oxide powder | |
| CN107445627B (en) | A kind of preparation method of phenolic resin and manganese dioxide bilayer film coated ceramic powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130403 Termination date: 20150922 |
|
| EXPY | Termination of patent right or utility model |