CN113956529B - Method for preparing porous and super-hydrophobic PLA film with adjustable aperture by using solvent freezing phase separation method - Google Patents
Method for preparing porous and super-hydrophobic PLA film with adjustable aperture by using solvent freezing phase separation method Download PDFInfo
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Abstract
The invention discloses a method for preparing a porous super-hydrophobic PLA film with adjustable aperture by using a solvent freezing phase separation method, which comprises the following steps: 1) Mixing PLA and a solvent, stirring for dissolving, and then pouring into a mould, wherein the solvent contains 10-95% of 1, 4-dioxane by volume; 2) And (3) putting the mould with the PLA solution in the step 1) into low temperature for freezing, taking out after freezing, and standing at room temperature to obtain the porous super-hydrophobic PLA film with adjustable aperture. The invention utilizes the freezing point of the solvent to fix the distance between PLA chains through freezing to prepare the porous super-hydrophobic material which is not easy to collapse. The method is simple to prepare and easy to realize large-scale production, and meanwhile, the porous super-hydrophobic PLA film with the adjustable pore diameter has degradability and biocompatibility and can be used in the fields of energy storage, adsorption materials, oil-water separation, microfluid transportation, self-cleaning, sound absorption, heat insulation and the like.
Description
Technical Field
The invention relates to a method for preparing a porous and super-hydrophobic PLA film with adjustable aperture by using a solvent freezing phase separation method, belonging to the technical field of high polymer materials.
Background
At present, the preparation methods of the polymer film include a spin coating method, a dip coating method, a screen printing method, a sintering method, a nuclear track method and the like, however, when the methods are used for preparing the functional PLA film, modification or mixing with other materials of the PLA material are often needed to achieve the purpose, so that the defects of complex preparation process, time consumption, high cost and the like exist, and the industrial production development is not facilitated.
In order to improve the hydrophobicity and porosity of the PLA film, cellulose, fluorine-containing materials and other modification modifications need to be added in the prior art, and the problems of high cost, complex operation and the like exist.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing a porous and super-hydrophobic PLA film with adjustable aperture by using a solvent freezing phase separation method, which realizes simple preparation process, can produce a porous and super-hydrophobic PLA film and has controllable aperture.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing a porous and super-hydrophobic PLA film with adjustable aperture by using a solvent freezing phase separation method comprises the following steps:
1) Mixing PLA and a solvent, stirring for dissolving, and then pouring the mixture into a mould, wherein the solvent contains 10-95% by volume of 1, 4-dioxane;
2) And (2) putting the mould with the PLA solution in the step 1) into low temperature for freezing, taking out after freezing is finished, and standing at room temperature to obtain the porous super-hydrophobic PLA film with adjustable aperture.
In the solvent, 1, 4-dioxane with the volume content of 10-95% is needed, the freezing point of the 1, 4-dioxane solvent is utilized for crystallization, the distance between PLA chains is frozen and fixed, meanwhile, PLA is crystallized at low temperature to form a three-dimensional polymer framework, and when the 1, 4-dioxane solvent is unfrozen, phase separation is carried out, so that the porous super-hydrophobic material with adjustable aperture, porosity, uniformity, super-hydrophobicity and difficult collapse is prepared.
In the prior art, in order to improve hydrophobicity, porosity and the like, modification such as addition of cellulose and fluorine-containing materials is required, so that the problems of high cost, complex operation and the like exist; according to the solvent freezing phase separation method, no plant fiber or fluorine-containing material is required to be added, and the raw material composition is simple, the operation steps are simple, the cost is low, and the method is environment-friendly; and has the characteristics of adjustable pore diameter, porosity and super-hydrophobicity.
The phase separation is a phenomenon caused by thermodynamic instability in a high molecular solution system, the PLA film is prepared by using the phase separation method, and the used organic reagent can be recycled and reused, so that the method has the advantages of simplicity, greenness and the like; meanwhile, with the use of a large amount of petroleum-based products, the problem of serious environmental pollution is caused, so the invention of the method for simply preparing the porous super-hydrophobic PLA functional film with adjustable aperture has important significance.
The method is simple to prepare and easy to realize large-scale production, and the porous super-hydrophobic PLA film with adjustable pore diameter has degradability and biocompatibility and can be used in the fields of energy storage, adsorption materials, oil-water separation, microfluid transportation, self-cleaning, sound absorption, heat insulation and the like.
In order to further improve the porous and super-hydrophobic characteristics of the film, in the step 1), the volume ratio of the solvent 1, 4-dioxane to the cosolvent is (1.0-9.0): (0.01-7.0), and the cosolvent is at least one of dichloromethane, tetrahydrofuran, N-dimethylformamide and dimethyl sulfoxide.
In order to take account of the comprehensive performance of the film, the addition amount of PLA in the step 1) is 1.0 to 5 weight percent of the 1, 4-dioxane solvent.
In order to improve the mixing sufficiency, in the step 1), the temperature for stirring and dissolving is 25-40 ℃, and the stirring time is 3-4 h.
The mould can be made of glass or stainless steel and the like, and films with different sizes and thicknesses can be prepared according to requirements.
In order to further improve the porous and super-hydrophobic characteristics of the film, in the step 2), the low-temperature freezing temperature is 11 to-20 ℃, the freezing time is 0.1 to 4 hours, and the freezing cycle time is 1 to 3 times.
In the step 2), the frozen food is taken out and kept standing for 3 to 6 hours.
The invention utilizes the solvent freezing technology to realize the phase separation of PLA and the solvent, can prepare a porous PLA film, has micro-nano-scale pore diameter and high porosity, can reasonably regulate and control the pore diameter size through different dosage ratios of the 1, 4-dioxane solvent and other solvents, has important influence on the surface appearance of the film through different dosage ratios, and can prepare the porous and super-hydrophobic PLA film with adjustable pore diameter. The inventor finds that the 1, 4-dioxane solvent is frozen and solidified, so that the distance between chains is fixed according to a specific size, PLA is crystallized at low temperature to form a three-dimensional high polymer framework, the porous PLA film which is not easy to collapse can be obtained after the 1, 4-dioxane solvent is unfrozen, and the porous, uniform and super-hydrophobic PLA film with adjustable pore diameter can be obtained when the volume content of the 1, 4-dioxane is 10-95%.
Abbreviations for each solvent are as follows: 1, 4-dioxane: DIOX; dichloromethane: DCM; tetrahydrofuran (tetrahydrofuran): THF; n, N-dimethylformamide: DMF; dimethyl sulfoxide: and (4) DMSO.
The technology not mentioned in the present invention is referred to the prior art.
Compared with the prior art, the invention has the following advantages:
(1) The invention adopts the PLA material with biodegradability as the raw material, and the solvent used in the process preparation is easy to recycle, has environmental friendliness and meets the social development requirement.
(2) The method utilizes a solvent freezing technology to realize the phase separation of PLA and a solvent, can prepare a porous PLA film, has multistage pore diameters and high porosity, and can prepare the porous super-hydrophobic PLA film with adjustable pore diameters by reasonably regulating and controlling the size of the pore diameters and the surface appearance of the film through different dosage ratios. Wherein the aperture regulation and control range of the PLA film is 0.16-10.60 μm, the porosity regulation and control range is 50-95%, and the contact angle of the film to water is 154-160 degrees.
(3) The method has the advantages of obviously simplifying the preparation process, easily realizing large-scale production, easily operating and low cost, and can be used in the fields of energy storage, adsorption materials, oil-water separation, microfluid transportation, self-cleaning, sound absorption, heat insulation and the like.
Drawings
FIG. 1 is a scanning electron micrograph of PLA without freezing (left) and with freezing (right) in example 1;
FIG. 2 is a scanning electron micrograph of PLA (DIOX: DCM 90;
FIG. 3 is a scanning electron micrograph of PLA (DIOX: THF 50);
FIG. 4 is a scanning electron micrograph of PLA (DIOX: DMF 90;
FIG. 5 is a scanning electron micrograph of PLA (DIOX: DCM: DMF: DMSO 50;
FIG. 6 is a scanning electron micrograph of the cross section of PLA (DIOX: DCM 90.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The room temperature in each case was 20-30 ℃.
Example 1
A method for preparing a porous and super-hydrophobic PLA film with adjustable aperture by using a solvent freezing phase separation method comprises the following specific steps:
the solvent is 1, 4-dioxane: 0.5g of PLA and 10ml of 1, 4-dioxane are weighed, added and stirred for 3h at the temperature of 30 ℃ to obtain a dissolving solution with the uniform concentration of 50mg/ml, the dissolving solution is poured into a glass culture dish with the thickness of 90mm, the glass culture dish is frozen for 3h at the temperature of minus 20 ℃, and the glass culture dish is taken out and kept stand for 6h at the room temperature. The same amounts of substances were taken as comparative references without cryogenic freezing, and other preparation conditions were the same.
Example 2
A method for preparing a porous super-hydrophobic PLA film with adjustable aperture by using a solvent freezing phase separation method comprises the following specific steps:
the solvent is 1, 4-dioxane and dichloromethane: referring to example 1, 0.5g of PLA was weighed, and the volume ratio (%) of 1, 4-dioxane to methylene chloride solvent was respectively weighed as: 90, 70, 30, 50, stirring at 30 ℃ for 3h to obtain a solution with a uniform concentration of 50mg/ml, pouring the solution into a 90mm glass culture dish, freezing at-20 ℃ for 3h, and taking out and standing at room temperature for 6h.
Example 3
A method for preparing a porous and super-hydrophobic PLA film with adjustable aperture by using a solvent freezing phase separation method comprises the following specific steps:
the solvent is 1, 4-dioxane and tetrahydrofuran: referring to example 1, 0.5g of PLA was weighed, and the volume ratios (%) of 1, 4-dioxane and tetrahydrofuran solvents were respectively weighed as: 90, 70, 30, 50, stirring at 30 ℃ for 3h to obtain a solution with a uniform concentration of 50mg/ml, pouring the solution into a 90mm glass culture dish, freezing at-20 ℃ for 3h, and taking out and standing at room temperature for 6h.
Example 4
A method for preparing a porous and super-hydrophobic PLA film with adjustable aperture by using a solvent freezing phase separation method comprises the following specific steps:
the solvent is 1, 4-dioxane and N, N-dimethylformamide: referring to example 1, 0.5g of PLA was weighed, and the volume ratios (%) of N, N-dimethylformamide agents were respectively weighed as follows: 90, 95, 5, 99, adding and stirring at 30 ℃ for 3 hours to obtain a solution with a uniform concentration of 50mg/ml, pouring the solution into a 90mm glass culture dish, freezing at-20 ℃ for 3 hours, and taking out and standing at room temperature for 6 hours.
Example 5
A method for preparing a porous super-hydrophobic PLA film with adjustable aperture by using a solvent freezing phase separation method comprises the following specific steps:
the solvent is 1, 4-dioxane, dichloromethane, N-dimethylformamide and dimethyl sulfoxide: referring to example 1, 0.5g of PLA was weighed, and the volume ratios (%) of 1, 4-dioxane, dichloromethane, N-dimethylformamide and dimethylsulfoxide solvent were respectively: 50.
And (3) performance testing:
(1) And (3) pore diameter testing: the PLA film prepared by the invention is taken, the pore size and the pore size distribution of the PLA film are measured by a capillary flow pore diameter instrument POROMETER, a sample is cut into a specification of 25mm, and a dry sample and a wet sample are respectively measured under the pressure of 2-6 bar.
(2) Contact angle testing: taking the PLA film prepared by the invention, adopting an OCA15EC optical contact angle tester to test the hydrophobic property of the surface of the PLA film, respectively measuring and measuring 5 different positions with the amount of water drops of 1 mu L at room temperature, and calculating and averaging;
(3) Porosity test of the membrane: the weight of the liquid contained in the pores of the membrane was measured by gravimetric method and the porosity of the membrane was calculated. The membrane samples were immersed in isobutanol for 12h. The porosity of the membrane is calculated as follows:
ε＝(W w -W d /(A×d×ρ))×100％
wherein, W w Is the weight of the wet film (g), W d Is the weight (g) of the dry film, A is the area (cm) of the film 2 ) D is the film thickness (cm) and ρ is the density of isobutanol (0.8 g/cm) 3 )。
The data obtained are shown in tables 1, 2 and 3.
Table 1:
as can be seen from the test results of table 1 and fig. 1: the pore size, the contact angle and the porosity of a frozen sample and an unfrozen sample of PLA in a1, 4-dioxane solvent are greatly different, and the inventor finds that the freezing and solidification of the 1, 4-dioxane solvent can fix the distance between chains according to a specific size, and simultaneously, the PLA is crystallized at low temperature to form a three-dimensional high molecular framework, and when the 1, 4-dioxane solvent is unfrozen, the phase separation is carried out, so that a porous PLA film which is not easy to collapse can be obtained. And then, the super-hydrophobic PLA film with the regulated pore size can be realized through the dosage ratio of the solvent. As the average pore diameter of the PLA film is reduced, the hydrophobic angle is increased, and the porosity is increased along with the introduction of the dichloromethane solvent, the introduction of the dichloromethane solvent has more important significance for regulating the smaller pore diameter of the PLA (as shown in figure 2).
Table 2:
as can be seen from the test results of table 2 and fig. 3: the introduction of tetrahydrofuran solvent can show that the average pore diameter of the PLA film can be regulated and controlled at 4.06-1.27 mu m, the hydrophobic angle can reach 157 degrees, and the porosity can reach 74 percent. The introduction of N, N-dimethylformamide solvent can regulate and control the pore diameter of the PLA film to be 10.60-7.16 mu m, the hydrophobic angle can reach 156 degrees, and the porosity can reach 82 percent, so that the introduction of N, N-dimethylformamide solvent can obtain higher porosity and has important effect on preparing porous PLA (as shown in figure 4).
Table 3:
as can be seen from the test results of table 3 and fig. 5: the introduction of N, N-dimethylformamide and dimethyl sulfoxide solvent can show that the average pore diameter of the PLA film can be regulated and controlled within 2.36-6.21 mu m, the hydrophobic angle can reach 158 degrees, the porosity can reach 95 percent, and the PLA films with different pore diameters, super hydrophobicity and high porosity can be obtained through the combined action of the N, N-dimethylformamide and the dimethyl sulfoxide solvent; as can be seen in fig. 6, the cross-sectional pores are uniform and complete, indicating that a porous PLA film that does not collapse easily is produced.
To sum up, the above embodiment utilizes a solvent freezing technology to realize phase separation of PLA and 1, 4-dioxane solvent, and can prepare a porous PLA film with a micro-nano pore size and high porosity, and the preparation of a porous superhydrophobic PLA film with an adjustable pore size is realized by reasonably adjusting the pore size of the 1, 4-dioxane solvent and other solvents (dichloromethane, tetrahydrofuran, N-dimethylformamide, and dimethyl sulfoxide) according to different dosage ratios, wherein the different dosage ratios have important influence on the surface morphology of the film.
Application examples
The oil leakage and the oil wastewater always cause serious harm to the ecological environment, and the solution of the oil-water separation problem is concerned. The membrane separation is one of the methods for effectively treating oil-water separation, and if the membrane separation technology has the advantages of high separation efficiency, low operation cost, capability of treating oil-water emulsion and the like, the membrane separation technology has great competitive advantages in the future. The key influencing the membrane separation technology in the oil-water separation process is the interface wettability and the membrane flux of a separation membrane, the excellent oil-water separation effect needs to have good interface wettability, and the high membrane flux needs to be appropriate in membrane aperture size, so that the control of the membrane aperture size has important significance. The invention discloses a method for preparing a porous super-hydrophobic PLA film with adjustable aperture by using a solvent freezing phase separation method, which is applied to oil-water separation. The invented PLA (DIOX: DCM 70) film has an average pore diameter of 0.50 μm, a contact angle of 158 degrees and a porosity of 82 percent, and can separate heavy oil and adsorb light oil through different oil types. The membrane shows high filterability to heavy oil and has a membrane flux of 8513L m -2 h -1 bar -1 The separation efficiency is 99 percent,the film thickness is only 0.4mm, the adsorption capacity of the film to light oil is 8g/g, the super-hydrophobicity is still maintained after 20 cycles, various oil-water separation scenes are met, and the film has universality.
Claims (6)
1. A method for preparing a porous and super-hydrophobic PLA film with adjustable aperture by using a solvent freezing phase separation method is characterized by comprising the following steps: the preparation method comprises the following steps:
1) Mixing PLA and a solvent, stirring for dissolving, and then pouring the mixture into a mould, wherein the solvent contains 10-95% by volume of 1, 4-dioxane, and the stirring and dissolving temperature is 25-40 ℃;
2) And (3) putting the mould with the PLA solution in the step 1) into low temperature for freezing, taking out after freezing, and standing at room temperature to obtain the porous super-hydrophobic PLA film with adjustable aperture.
2. The method for preparing a porous and super-hydrophobic PLA film with adjustable pore size by using the solvent freezing phase separation method as claimed in claim 1, which is characterized in that: in the step 1), the volume ratio of the solvent 1, 4-dioxane to the cosolvent is (1.0-9.0): (0.01-7.0), and the cosolvent is at least one of dichloromethane, tetrahydrofuran, N-dimethylformamide and dimethyl sulfoxide.
3. The method for preparing a porous superhydrophobic PLA film using the solvent freezing phase separation method as claimed in claim 1 or 2, wherein: in the step 1), the addition amount of PLA is 1.0-5 wt% of the 1, 4-dioxane solvent.
4. The method for preparing a porous super-hydrophobic PLA film with adjustable pore size by using the solvent freezing phase separation method as claimed in claim 1 or 2, which is characterized in that: in the step 1), the stirring time is 3-4 h.
5. The method for preparing a porous superhydrophobic PLA film using the solvent freezing phase separation method as claimed in claim 1 or 2, wherein: in the step 2), the low-temperature freezing temperature is 11 to-20 ℃, the freezing time is 0.1 to 4 hours, and the freezing cycle times are 1 to 3.
6. The method for preparing a porous superhydrophobic PLA film using the solvent freezing phase separation method as claimed in claim 1 or 2, wherein: in the step 2), the frozen food is taken out and kept stand for 3 to 6 hours.
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| CN1394654A (en) * | 2002-07-10 | 2003-02-05 | 浙江大学 | Polylactic acid porous scaffold for tissue engineering and its preparation method |
| CN1792379A (en) * | 2005-11-03 | 2006-06-28 | 同济大学 | Method for preparing organic and inorganic nanometer composite organization engineering stent material by using thermal phase separation |
| CN110655766A (en) * | 2019-10-14 | 2020-01-07 | 成都大学 | Preparation method of polylactic acid porous membrane for food preservation |
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| JPH0678460B2 (en) * | 1985-05-01 | 1994-10-05 | 株式会社バイオマテリアル・ユニバース | Porous transparent polyvinyl alcohol gel |
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| CN1394654A (en) * | 2002-07-10 | 2003-02-05 | 浙江大学 | Polylactic acid porous scaffold for tissue engineering and its preparation method |
| CN1792379A (en) * | 2005-11-03 | 2006-06-28 | 同济大学 | Method for preparing organic and inorganic nanometer composite organization engineering stent material by using thermal phase separation |
| CN110655766A (en) * | 2019-10-14 | 2020-01-07 | 成都大学 | Preparation method of polylactic acid porous membrane for food preservation |
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| "Formation of poly(l-lactic acid) microfiltration membranes via thermally induced phase separation";Takaaki Tanaka et al.;《Journal of Membrane Science》;20040511;第238卷;摘要，实验部分第2.3节 * |
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