CN113996188A - Degradable Janus membrane material and preparation method and application thereof - Google Patents
Degradable Janus membrane material and preparation method and application thereof Download PDFInfo
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- CN113996188A CN113996188A CN202111280198.XA CN202111280198A CN113996188A CN 113996188 A CN113996188 A CN 113996188A CN 202111280198 A CN202111280198 A CN 202111280198A CN 113996188 A CN113996188 A CN 113996188A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/02—Layered materials
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/10—Impermeable to liquids, e.g. waterproof; Liquid-repellent
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/12—Hygroscopic; Water retaining
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses a degradable Janus film material and a preparation method and application thereof. The preparation method comprises the following steps: carrying out super-hydrophilic modification treatment on the membrane substrate to obtain a super-hydrophilic membrane substrate; and attaching the two super-hydrophilic membrane substrates to each other, then carrying out water wetting treatment, and then placing the super-hydrophilic membrane substrates in a hydrophobic degradable high molecular solution for phase inversion, thereby obtaining the degradable Janus membrane material. The preparation process of the degradable Janus film material provided by the invention is simplified, the raw materials are cheap and easy to obtain, and the equipment investment is less; meanwhile, the degradable Janus film material prepared by the invention has excellent performance, obvious one-way transport characteristic and high oil-water separation efficiency and rate, can be applied to the fields of masks, oil-water separation and the like, and is degradable and harmless to the environment.
Description
Technical Field
The invention belongs to the technical field of functional membrane materials, and particularly relates to a degradable Janus membrane material and a preparation method and application thereof.
Background
The concept of Janus membrane was originally proposed in 2010 or so, its two faces have asymmetric characteristics, showing new functions not possessed by traditional membranes, being able to achieve excellent performance in traditional membrane processes, exhibiting unique functions in all the aspects involved in interfaces (liquid directional transport, electrocatalysis, alkaline ion batteries, biological skin protection, solar evaporation process, etc.). Especially the internal driving force generated by the asymmetric configuration of the two sides of the Janus film can effectively change the separation and transportation process. Therefore, the Janus membrane is widely concerned and rapidly developed, and the preparation method thereof becomes the foundation of the field, researchers propose various preparation methods, and two paths, namely asymmetric preparation and asymmetric modification, are formed in a summary way. Asymmetric fabrication is the simplest method of fabricating a Janus membrane, and the basic process is to separately fabricate two sides of a Janus membrane and then combine them to form a Janus membrane. Researchers adopt a continuous electrostatic spinning method to prepare a hydrophobic PU nanofiber membrane, and then continue to perform electrospinning on the surface of the hydrophobic PU nanofiber membrane to form a hydrophilic cross-linked PVA nanofiber membrane, so that the PU/PVAJanus membrane is prepared. Also, researchers have used continuous filtration to sequentially filter hydrophobic and hydrophilic nanotubes or nanowires onto a porous substrate and then remove the substrate to form a Janus membrane. Zhang et al reported that a solution of the blend, after casting into a film, formed a Janus film by molecular migration or phase separation of incompatible systems. The other route is asymmetric modification, namely modification with different properties is carried out on one side of the formed film. Lin and the like adopt POSS to modify a ZnO-coated fiber membrane, and then carry out photodegradation treatment on a single surface to obtain super-hydrophilic performance in a recovery period, thereby preparing a Janus membrane. Wang et al, however, uses a single-sided cross-linking method, by first soaking cotton cloth in a PDMS solution, then cross-linking one side of the PDMS solution using ultraviolet light, and washing off the PDMS from the other side using a solvent, a Janus membrane is produced. Tian et al used a single-sided CVD process to vapor deposit perfluorodecyl trichlorosilane on one side of a cotton cloth to form a hydrophobic side, while leaving the other side untreated to maintain its own hydrophobicity, thereby forming a Janus film. Due to the capillary action of the membrane material, the modified material solution is easy to dip into the pore structure, so that both sides are modified, and the difficulty in preparing the Janus membrane by a wet method is high. To solve the difficulty, Liu et al hydrophobically modify one side of the membrane material with high viscosity fluoropolymer foam, which overcomes capillary force and prevents both sides of the membrane from being modified, thereby producing Janus membranes. Xu et al developed a floating deposition method, i.e., using an ethanol-soaked PP membrane to prevent the modifying solution from soaking into the pore structure of the membrane, thereby floating on the surface of a solution of dopamine, low molecular weight polyethyleneimine PEI, and depositing hydrophilic PEI on the side in contact with the modifying solution, thereby preparing a Janus membrane. For the asymmetric preparation path, the preparation method is simple, the thicknesses of the two surfaces and the like are easy to control, but the compatibility of the interface between the two surface films is weak, the stability of the film material is easy to influence, and the compatibility requirement between the materials is high. The phase separation method or the molecular migration method has high material selection requirements, a suitable mixing system is limited, and the phase separation or the molecular migration is difficult to control to realize complete separation. And the asymmetric modification path directly utilizes the formed membrane material to modify a single surface, and the method is simple. However, the materials adopted by the existing modification method are generally expensive, toxic and volatile, and generally need corresponding equipment to assist the modification process, so that the large-scale preparation is difficult. For example, a single-sided photodegradation method requires POSS modification, single-sided photodegradation, and expensive POSS and photodegradation equipment. Therefore, the problem to be solved is to provide a simple preparation method capable of preparing the degradable Janus membrane material in a large scale.
Disclosure of Invention
The invention mainly aims to provide a degradable Janus film material and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a degradable Janus film material, which comprises the following steps:
carrying out super-hydrophilic modification treatment on the membrane substrate to obtain a super-hydrophilic membrane substrate;
and attaching the two super-hydrophilic membrane substrates to each other, then carrying out water wetting treatment, and then placing the super-hydrophilic membrane substrates in a hydrophobic degradable high molecular solution for phase inversion, thereby obtaining the degradable Janus membrane material.
The embodiment of the invention also provides the degradable Janus film material prepared by the method, the degradable Janus film material has a porous structure, the pore diameter of pores contained in the degradable Janus film material is 0.2-30 mu m, and the porosity is 70-95%.
The embodiment of the invention also provides application of the degradable Janus film material in the field of mask preparation or oil-water separation.
The embodiment of the invention also provides a mask which comprises the degradable Janus film material.
The embodiment of the invention also provides an oil-water separation method, which comprises the following steps: passing the mixture of oil and water through the degradable Janus membrane material of claim 7, and collecting the liquid passing through the membrane material, thereby realizing oil-water separation.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation process of the degradable Janus film material provided by the invention is simplified, the raw materials are cheap and easy to obtain, the equipment investment is less, and the used raw materials are all commercially available and are cheap and easy to obtain; the Janus membrane performance is optimized and prepared conveniently by optimizing parameters such as membrane substrate thickness, adjusting water protection amount, time for invading modification solution and the like without complex equipment by adopting an asymmetric modification path and combining a phase inversion method, and the Janus membrane can be prepared in a large scale;
(2) the degradable Janus film material prepared by the invention has excellent performance, obvious one-way transport property and high oil-water separation efficiency and rate, can be applied to the fields of masks, oil-water separation and the like, and the whole Janus film is degradable and cannot cause harm to the environment.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made long-term research and extensive practice to provide a technical scheme of the present invention, which mainly uses cheap and easily available natural material fabrics such as cotton, hemp, silk, etc. as membrane substrates, carries out super-hydrophilic and super-oleophobic treatment on the membrane substrates, then adopts an asymmetric modification method, specifically adopts a water protection method, namely two membrane substrates are attached together, then is wetted by water and then is immersed in a solution of hydrophobic degradable polymers such as polylactic acid, etc. so that the polylactic acid, etc. is reversely rotated near the surface of the membrane substrates to form a porous membrane structure, and the two membrane substrates are taken out, dried and separated, thereby simultaneously preparing two degradable Janus membranes. The method is simple to operate, the raw materials are cheap and easy to obtain, additional equipment is not needed, and the degradable Janus membrane with a stable structure can be prepared in batches.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Specifically, as one aspect of the technical scheme of the invention, the preparation method of the degradable Janus film material comprises the following steps:
carrying out super-hydrophilic modification treatment on the membrane substrate to obtain a super-hydrophilic membrane substrate;
and attaching the two super-hydrophilic membrane substrates to each other, carrying out water wetting treatment, and then placing the super-hydrophilic membrane substrates in a hydrophobic degradable high molecular solution for phase inversion to obtain the degradable Janus membrane material.
In the invention, the super-hydrophilic membrane is quickly wetted after contacting water and absorbs the water into the pores of the membrane material through capillary action, and because the water is a poor solvent of the hydrophobic degradable macromolecules, when the solution contacts the water, the solvent is diffused, the degradable macromolecules are separated out and cannot be separated out in the pores of the membrane, and thus the solution is only attached to the surface of the membrane material.
In some preferred embodiments, the superhydrophilic modification treatment specifically includes: and (3) placing the membrane substrate in an alkaline solution, and heating and treating at 60-100 ℃ for 1-4 h to obtain the super-hydrophilic membrane substrate.
Further, the concentration of the alkaline solution is 1-10 wt%.
Further, the alkaline substance contained in the alkaline solution includes NaOH, KOH, Ca (OH)2And is not limited thereto.
In some preferred embodiments, the film substrate comprises a natural fiber fabric, and is not limited thereto.
Further, the material of the film substrate includes any one or a combination of two or more of cotton, hemp, and silk, but is not limited thereto.
Further, the thickness of the film substrate is 30 to 400 μm.
In some preferred embodiments, the preparation method specifically comprises:
mutually attaching one surface of the super-hydrophilic membrane substrate and one surface of the other super-hydrophilic membrane substrate to form the mutually attached super-hydrophilic membrane substrates;
and carrying out water wetting treatment on the super-hydrophilic membrane substrates which are attached to each other to form a wetted super-hydrophilic membrane substrate, wherein the water content of a saturated wetted super-hydrophilic membrane substrate formed by carrying out the water wetting treatment on the super-hydrophilic membrane substrates which are attached to each other is recorded as m0The water content of the wet super-hydrophilic membrane substrate is (1/3-2/3) m0And the wetting treatment at least enables the mutually attached super-hydrophilic membrane base materials to form water protection.
In some preferred embodiments, the preparation method specifically comprises: and (3) soaking the wetted super-hydrophilic membrane substrate in a hydrophobic degradable high molecular solution for 5-20 min to enable the surface of the wetted super-hydrophilic membrane substrate to generate phase inversion to form a super-hydrophobic porous membrane structure, and drying and splitting to obtain the degradable Janus membrane material.
In some preferred embodiments, the hydrophobic degradable polymer solution includes a hydrophobic degradable polymer and a solvent.
Further, the hydrophobic degradable polymer includes any one or a combination of two or more of polylactic acid, polyglycolic acid, polyhydroxyalkanoate, polybutylene succinate, polybutylene adipate/terephthalate, polycaprolactone, and degradable polycarbonate, but is not limited thereto.
Further, the solvent includes any one or a combination of two or more of chloroform, formamide, acetamide, and acetone, and is not limited thereto.
Further, the concentration of the hydrophobic degradable polymer solution is 2-20 wt%.
In some more preferred embodiments, the preparation method of the degradable Janus membrane material comprises the following steps: the method is characterized in that natural fiber fabrics such as cotton, hemp, silk and the like are used as membrane substrates, the thickness of the membrane substrates is 30-400 mu m, and the membrane substrates are subjected to super-hydrophilic and super-oleophobic modification, namely, 2 wt% of NaOH aqueous solution is adopted for heating treatment for 2 hours at 80 ℃. Then, an asymmetric modification method is adopted, namely two film substrates are attached together, then the film substrates are wetted by water, the water amount is 1/3-2/3 of saturated wetting, water protection is formed, the immersion thickness of the modification layer is regulated and controlled by controlling the wetted water amount, and the stability of the Janus film and the thickness of two surfaces are further regulated and controlled; and then soaking the membrane into a solution of polylactic acid (PLA) (polyglycolic acid (PGA), Polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), poly (adipic acid)/polybutylene terephthalate (PBAT), Polycaprolactone (PCL), degradable Polycarbonate (PC)) and other hydrophobic degradable macromolecules for 5-20 min, so that the polylactic acid and the like are subjected to phase inversion near the surface of the membrane substrate to form a super-hydrophobic porous membrane structure, regulating the thickness of the hydrophobic layer by soaking time, taking out and airing the membrane substrate, and separating the two membrane substrates to simultaneously prepare the two degradable Janus membranes.
The embodiment of the invention also provides the degradable Janus film material prepared by the method, the degradable Janus film material has a porous structure, the pore diameter of pores contained in the degradable Janus film material is 0.2-30 mu m, and the porosity is 70-95%.
Further, the contact angle between the hydrophilic surface of the degradable Janus film material and water is 0 degree, and the contact angle between the hydrophobic surface of the degradable Janus film material and water is 145-160 degrees.
Further, the oil-water separation rate of the degradable Janus membrane material is 86-132L/m2·h。
The embodiment of the invention also provides application of the degradable Janus film material in the field of mask preparation or oil-water separation.
Another aspect of the embodiment of the present invention further provides a mask, which includes the degradable Janus membrane material.
In some preferred embodiments, the mask comprises a moisture absorption layer, a filtration layer and a water-resistant layer from inside to outside, wherein the moisture absorption layer and the water-resistant layer are both the degradable Janus film material, the hydrophobic surface of the degradable Janus film material as the moisture absorption layer faces outwards, and the hydrophilic surface of the degradable Janus film material as the water-resistant layer faces outwards.
Another aspect of the embodiments of the present invention also provides an oil-water separation method, including: passing the mixture of oil and water through the degradable Janus membrane material of claim 7, and collecting the liquid passing through the membrane material, thereby realizing oil-water separation.
The technical solution of the present invention is further described in detail with reference to several preferred embodiments, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
Cotton cloth with a thickness of 30 μm is heated at 80 ℃ for 2h by using 2 wt% NaOH aqueous solution. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the mixture is uniformly adsorbed by one third m0And water, sticking two pieces of water-protected cotton cloth together, then soaking the cotton cloth into 20 wt% of PLA chloroform solution for 5min, taking out and drying the cotton cloth, and separating the two pieces of cotton cloth to obtain the two degradable Janus films.
Example 2
Adding 200 μm thick cotton cloth with 2 wt% NaOH aqueous solution at 80 deg.CAnd (5) carrying out heat treatment for 2 h. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the mixture is uniformly adsorbed by a half m0And water, sticking two pieces of water-protected cotton cloth together, then soaking the cotton cloth into 20 wt% of PLA chloroform solution for 10min, taking out and drying the cotton cloth, and separating the two pieces of cotton cloth to obtain the two degradable Janus films.
Example 3
Cotton cloth with a thickness of 400 μm is heated at 80 ℃ for 2h by using 2 wt% NaOH aqueous solution. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the mixture is made to uniformly adsorb two thirds of m0And water, sticking two pieces of water-protected cotton cloth together, then soaking the cotton cloth into 20 wt% of PLA chloroform solution for 20min, taking out and drying the cotton cloth, and separating the two pieces of cotton cloth to obtain the two degradable Janus films.
Example 4
Linen with the thickness of 100 mu m is heated and treated for 2h by 2 wt% NaOH aqueous solution at 80 ℃. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the mixture is uniformly adsorbed by a half m0And water, sticking the two pieces of water-protected linen together, then soaking the linen in 20 wt% of PBS (phosphate buffer solution) in chloroform solution for 10min, taking out the linen and drying the linen, and separating the two pieces of linen to obtain the two degradable Janus films.
Example 5
The silk with the thickness of 100 μm is heated and treated for 2 hours at 80 ℃ by adopting 2 wt% of NaOH aqueous solution. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the mixture is uniformly adsorbed by a half m0Water, sticking two pieces of silk protected by water together, soaking in 20 wt% PBAT chloroform solution for 15min, taking out, oven drying, and separating two pieces of silk to obtain two pieces of degradable Janus film.
Example 6
The linen with the thickness of 200 mu m is heated and treated for 4 hours at 60 ℃ by using 1 wt% KOH aqueous solution. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the mixture is uniformly adsorbed by a half m0And water, sticking the two pieces of water-protected linen together, then soaking the linen in 20 wt% of PLA formamide solution for 10min, taking out the linen and drying the linen, and separating the two pieces of linen to obtain the two degradable Janus films.
Example 7
Silk with a thickness of 200 μm, using 10 wt% Ca (OH)2The aqueous solution is heated for 1h at 100 ℃. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the mixture is made to uniformly adsorb two thirds of m0And water, sticking the two pieces of water-protected silk together, then soaking the silk into 20 wt% of PLA acetone solution, taking out the silk after soaking for 10min, drying the silk, and separating the two pieces of silk to obtain the two pieces of degradable Janus films.
Comparative example 1
The mass m was measured on a 100 μm thick cotton cloth without treatment with NaOH solution1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the mixture is uniformly adsorbed by a half m0And water, sticking two pieces of water-protected cotton cloth together, then soaking the cotton cloth into 20 wt% of PLA chloroform solution for 10min, taking out and drying the cotton cloth, and separating the two pieces of cotton cloth to obtain the two degradable Janus films.
Comparative example 2
Cotton cloth with a thickness of 20 μm is heated with 2 wt% NaOH aqueous solution at 80 deg.C for 2 h. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the mixture is uniformly adsorbed by a half m0Water, two pieces of water-protected cotton cloth are stuck togetherAnd then soaking the film in 20 wt% of PLA chloroform solution for 10min, taking out and drying the film, and separating two cotton cloths to obtain two degradable Janus films.
Comparative example 3
Cotton cloth with a thickness of 500 μm is heated with 2 wt% NaOH aqueous solution at 80 ℃ for 2 h. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the mixture is uniformly adsorbed by a half m0And water, sticking two pieces of water-protected cotton cloth together, then soaking the cotton cloth into 20 wt% of PLA chloroform solution for 10min, taking out and drying the cotton cloth, and separating the two pieces of cotton cloth to obtain the two degradable Janus films.
Comparative example 4
Cotton cloth with a thickness of 100 μm is heated at 80 ℃ for 2h by using 2 wt% NaOH aqueous solution. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the uniform adsorption is one fourth of m0And water, sticking two pieces of water-protected cotton cloth together, then soaking the cotton cloth into 20 wt% of PLA chloroform solution for 10min, taking out and drying the cotton cloth, and separating the two pieces of cotton cloth to obtain the two degradable Janus films.
Comparative example 5
Cotton cloth with a thickness of 100 μm is heated at 80 ℃ for 2h by using 2 wt% NaOH aqueous solution. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the adsorbent is allowed to uniformly adsorb four fifths of a meter0And water, sticking two pieces of water-protected cotton cloth together, then soaking the cotton cloth into 20 wt% of PLA chloroform solution for 10min, taking out and drying the cotton cloth, and separating the two pieces of cotton cloth to obtain the two degradable Janus films.
Comparative example 6
Cotton cloth with a thickness of 100 μm is heated at 80 ℃ for 2h by using 2 wt% NaOH aqueous solution. After drying, the mass m was measured1And mass m after saturated water absorption2Saturated water absorption capacity thereofIs m0＝m2-m1(ii) a After drying, the mixture is uniformly adsorbed by a half m0And water, sticking two pieces of water-protected cotton cloth together, then soaking the cotton cloth into 20 wt% of PLA chloroform solution for 3min, taking out and drying the cotton cloth, and separating the two pieces of cotton cloth to obtain the two degradable Janus films.
Comparative example 7
Cotton cloth with a thickness of 100 μm is heated at 80 ℃ for 2h by using 2 wt% NaOH aqueous solution. After drying, the mass m was measured1And mass m after saturated water absorption2The saturated water absorption capacity of the water-absorbent polymer is m0＝m2-m1(ii) a After drying, the mixture is uniformly adsorbed by a half m0And water, sticking two pieces of water-protected cotton cloth together, then soaking the cotton cloth into 20 wt% of PLA chloroform solution for 30min, taking out and drying the cotton cloth, and separating the two pieces of cotton cloth to obtain the two degradable Janus films.
And (3) performance characterization: the degradable Janus membranes prepared in examples 1 to 7 and comparative examples 1 to 7 were tested, and the results are shown in table 1 and table 2, respectively;
table 1 test results for degradable Janus membranes prepared in examples 1-7
Note: the oil-water separation efficiency is the proportion of the collected oil in the oil-water mixture after the oil-water mixture is filtered to the oil mass in the oil-water mixture; the unidirectional transportation performance is that water drops can pass from a hydrophobic surface to a hydrophilic surface, and conversely, the water drops can not pass; the structural stability of the film means whether the hydrophobic modification layer formed on the film-forming substrate is easy to fall off or not, and the structure is stable if the hydrophobic modification layer is not easy to fall off.
Table 2 test results for degradable Janus membranes prepared in comparative examples 1-7
Note: the oil-water separation efficiency is the proportion of the collected oil in the oil-water mixture after the oil-water mixture is filtered to the oil mass in the oil-water mixture; the unidirectional transportation performance is that water drops can pass from a hydrophobic surface to a hydrophilic surface, and conversely, the water drops can not pass; the structural stability of the film means whether the hydrophobic modification layer formed on the film-forming substrate is easy to fall off or not, and the structure is stable if the hydrophobic modification layer is not easy to fall off.
Example 8
The degradable Janus membrane of embodiment 1 is used for preparing the mask, the inner layer of the mask is a moisture absorption layer, the middle layer is a filter layer, the outer layer is a water-resistant layer, the moisture absorption layer and the water-resistant layer are the degradable Janus membrane of embodiment 1, the hydrophobic surface of the degradable Janus membrane of the inner layer faces outwards, the moisture absorption layer is formed due to the directional transportation effect, the hydrophilic surface of the degradable Janus membrane of the outer layer faces outwards, and the water-resistant layer is formed due to the directional transportation effect. The water contact angle of the inner layer and the outer layer of the common mask is 102 degrees, and exhaled water vapor is difficult to pass through the inner layer, so that the breathing is difficult; and the water drops on the inner layer of the mask prepared in the embodiment 1 are rapidly spread and absorbed to form a hydrophilic layer, the water contact angle of the outer layer is 150 degrees, and a high-efficiency water-blocking layer is formed, so that the reduction of the air permeability of the mask caused by the water vapor exhaled can be effectively avoided.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.
Claims (10)
1. A preparation method of a degradable Janus film material is characterized by comprising the following steps:
carrying out super-hydrophilic modification treatment on the membrane substrate to obtain a super-hydrophilic membrane substrate;
and attaching the two super-hydrophilic membrane substrates to each other, then carrying out water wetting treatment, and then placing the super-hydrophilic membrane substrates in a hydrophobic degradable high molecular solution for phase inversion, thereby obtaining the degradable Janus membrane material.
2. The preparation method according to claim 1, wherein the superhydrophilic modification treatment specifically comprises: placing a membrane substrate in an alkaline solution, and heating and treating at 60-100 ℃ for 1-4 h to obtain the super-hydrophilic membrane substrate;
preferably, the concentration of the alkaline solution is 1-10 wt%; preferably, the alkaline substance contained in the alkaline solution includes NaOH, KOH, Ca (OH)2Any one or a combination of two or more of them.
3. The method of claim 1, wherein: the film substrate comprises a natural fiber fabric; preferably, the material of the film substrate comprises any one or a combination of more than two of cotton, hemp and silk;
and/or the thickness of the film substrate is 30-400 μm.
4. The method according to claim 1, comprising:
mutually attaching one surface of the super-hydrophilic membrane substrate and one surface of the other super-hydrophilic membrane substrate to form the mutually attached super-hydrophilic membrane substrates;
and carrying out water wetting treatment on the super-hydrophilic membrane substrates which are attached to each other to form a wetted super-hydrophilic membrane substrate, wherein the water content of a saturated wetted super-hydrophilic membrane substrate formed by carrying out the water wetting treatment on the super-hydrophilic membrane substrates which are attached to each other is recorded as m0The water content of the wet super-hydrophilic membrane substrate is (1/3-2/3) m0And the wetting treatment at least enables the mutually attached super-hydrophilic membrane base materials to form water protection.
5. The preparation method according to claim 4, characterized by specifically comprising: and (3) soaking the wetted super-hydrophilic membrane substrate in a hydrophobic degradable high molecular solution for 5-20 min to enable the surface of the wetted super-hydrophilic membrane substrate to generate phase inversion to form a super-hydrophobic porous membrane structure, and drying and splitting to obtain the degradable Janus membrane material.
6. The method of claim 1, wherein: the hydrophobic degradable polymer solution comprises hydrophobic degradable polymers and a solvent; preferably, the hydrophobic degradable polymer comprises any one or a combination of more than two of polylactic acid, polyglycolic acid, polyhydroxyalkanoate, polybutylene succinate, polybutylene adipate/terephthalate, polycaprolactone and degradable polycarbonate; preferably, the solvent comprises any one or the combination of more than two of chloroform, formamide, acetamide and acetone; preferably, the concentration of the hydrophobic degradable polymer solution is 2-20 wt%.
7. The degradable Janus film material prepared by the method of any one of claims 1-6, wherein the degradable Janus film material has a porous structure, the pore diameter of pores contained in the degradable Janus film material is 0.2-30 μm, and the porosity is 70-95%;
preferably, the contact angle between the hydrophilic surface of the degradable Janus film material and water is 0 degree, and the contact angle between the hydrophobic surface of the degradable Janus film material and water is 145-160 degrees;
preferably, the oil-water separation rate of the degradable Janus membrane material is 86-132L/m2·h。
8. The use of the degradable Janus film material of claim 7 in the field of mask preparation or oil-water separation.
9. A mask comprising the degradable Janus membrane material of claim 7;
preferably, the mask comprises a moisture absorption layer, a filter layer and a water-blocking layer from inside to outside, wherein the moisture absorption layer and the water-blocking layer are both the degradable Janus membrane material, the hydrophobic surface of the degradable Janus membrane material serving as the moisture absorption layer faces outwards, and the hydrophilic surface of the degradable Janus membrane material serving as the water-blocking layer faces outwards.
10. An oil-water separation method is characterized by comprising the following steps: passing the mixture of oil and water through the degradable Janus membrane material of claim 7, and collecting the liquid passing through the membrane material, thereby realizing oil-water separation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115467084A (en) * | 2022-09-05 | 2022-12-13 | 南通大学 | Hydrophilic PLA oil-water separation membrane and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110575794A (en) * | 2018-06-08 | 2019-12-17 | 北方民族大学 | super-hydrophobic cotton cellulose aerogel and preparation method and application thereof |
| US20200131693A1 (en) * | 2018-10-24 | 2020-04-30 | Cornell University | Hydrophobic/oleophobic fabrics with directional liquid transport property |
| CN111330462A (en) * | 2020-02-28 | 2020-06-26 | 浙江工业大学 | Super-hydrophobic demulsification oil-water separation membrane material and preparation method and application thereof |
| CN111871001A (en) * | 2020-07-07 | 2020-11-03 | 中山大学 | Janus type material with one-way water transmission property and preparation method and application thereof |
| CN111926570A (en) * | 2020-06-18 | 2020-11-13 | 北京服装学院 | Janus fabric film based on polylactic acid and preparation method and application thereof |
-
2021
- 2021-10-28 CN CN202111280198.XA patent/CN113996188B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110575794A (en) * | 2018-06-08 | 2019-12-17 | 北方民族大学 | super-hydrophobic cotton cellulose aerogel and preparation method and application thereof |
| US20200131693A1 (en) * | 2018-10-24 | 2020-04-30 | Cornell University | Hydrophobic/oleophobic fabrics with directional liquid transport property |
| CN111330462A (en) * | 2020-02-28 | 2020-06-26 | 浙江工业大学 | Super-hydrophobic demulsification oil-water separation membrane material and preparation method and application thereof |
| CN111926570A (en) * | 2020-06-18 | 2020-11-13 | 北京服装学院 | Janus fabric film based on polylactic acid and preparation method and application thereof |
| CN111871001A (en) * | 2020-07-07 | 2020-11-03 | 中山大学 | Janus type material with one-way water transmission property and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| PRAKASH M. GORE AND BALASUBRAMANIAN KANDASUBRAMANIAN: "《Heterogeneous wettable cotton based superhydrophobic Janus biofabric engineered with PLA/functionalized-organoclay microfibers for efficient oil–water separation》", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 谢婉婷等: "《超吸水改性棉纤维膜的制备及其性能》", 《纺织学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115467084A (en) * | 2022-09-05 | 2022-12-13 | 南通大学 | Hydrophilic PLA oil-water separation membrane and preparation method thereof |
| CN115467084B (en) * | 2022-09-05 | 2023-08-08 | 南通大学 | Hydrophilic PLA oil-water separation film and preparation method thereof |
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