CN108568216B - Polylactic acid microporous membrane and manufacturing method thereof - Google Patents
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Abstract
The invention relates to a polylactic acid microporous membrane which is formed by compounding L-type polylactic acid and D-type polylactic acid, wherein the surface of the polylactic acid microporous membrane comprises a plurality of openings. The invention also relates to a preparation method of the polylactic acid microporous membrane, which comprises the following steps: (1) dissolving D-type polylactic acid by an organic solvent to obtain a D-type polylactic acid solution; (2) adding L-type polylactic acid into a D-type polylactic acid solution, and uniformly stirring to obtain a polylactic acid membrane casting solution; (3) defoaming the polylactic acid casting solution, and preparing a polylactic acid nascent membrane; (4) and (3) placing the polylactic acid primary membrane into a coagulating bath at the temperature of 0-60 ℃ for solidification, and drying to obtain the polylactic acid microporous membrane.
Description
Technical Field
The invention relates to the field of polymer microporous membranes, in particular to a polylactic acid microporous membrane and a preparation method thereof.
Background
Membrane separation materials have become the mainstream core materials in the fields of water purification, hemodialysis and the like. Wherein the material of the membrane separation material is various. Compared with the traditional petrochemical-based polymer materials such as polyvinylidene fluoride, polysulfone, polyether sulfone, polytetrafluoroethylene and the like, the polylactic acid is a bio-based polymer, has good biocompatibility and is biodegradable, and is an environment-friendly material. Based on this, polylactic acid is gradually becoming the material of choice for polymer-based membrane separation materials.
Currently, many studies have been made on polylactic acid separation membranes. The polylactic acid membrane prepared by regulating the structure of polylactic acid membrane by polyoxyethylene (please refer to the L.Chen, et al. journal of nanoparticel Research, 2010, 9: 777-785) has a retention rate of 90% to bovine serum albumin, but the polylactic acid membrane has a retention rate of Bovine Serum Albumin (BSA)The water flux of the separation membrane is small (only 225L/m)2H) high flux polylactic acid membranes have also been prepared by β cyclodextrin regulation (see al. gao, et. journal of Materials chemistry a, 2016, 4: 12058-12064), but the retention of bovine serum albumin by the polylactic acid separation membrane is only 65%.
Disclosure of Invention
In view of this, the present invention provides a polylactic acid microporous membrane with high flux and high rejection rate and a preparation method thereof.
The invention provides a polylactic acid microporous membrane which is formed by compounding L-type polylactic acid and D-type polylactic acid, wherein the surface of the polylactic acid microporous membrane comprises a plurality of openings.
Preferably, the pore size of the open pores is 10 nanometers to 3 micrometers.
Preferably, the mass ratio of the L-type polylactic acid to the D-type polylactic acid in the polylactic acid microporous membrane is (50-99.9): (0.1-50).
The invention also provides a preparation method of the polylactic acid microporous membrane, which comprises the following steps:
(1) dissolving D-type polylactic acid by an organic solvent to obtain a D-type polylactic acid solution;
(2) adding L-type polylactic acid into a D-type polylactic acid solution, and uniformly stirring to obtain a polylactic acid membrane casting solution;
(3) defoaming the polylactic acid casting solution, and preparing a polylactic acid nascent membrane;
(4) and (3) placing the polylactic acid primary membrane into a coagulating bath at the temperature of 0-60 ℃ for solidification, and drying to obtain the polylactic acid microporous membrane.
Preferably, when the D-type polylactic acid is dissolved in the step (1), the dissolving temperature is 80 to 110 ℃, the dissolving time is 1 to 4 hours, and the organic solvent is at least one of N-methylpyrrolidone, N-dimethylacetamide, dimethylsulfoxide, dimethylformamide, and triethyl phosphate.
Preferably, the polylactic acid casting solution in the step (2) contains 75-88% by mass of an organic solvent, and the total mass ratio of the D-type polylactic acid to the L-type polylactic acid is 12-25%.
Preferably, the stirring temperature in the step (2) is 60 ℃ to 100 ℃, and the stirring time is 3 hours to 24 hours.
Preferably, the solvent used in the coagulation bath in step (4) is water or a mixture of water and at least one of the organic solvents in step (1).
Preferably, the curing time in the step (4) is 1 minute to 30 minutes.
Preferably, after the step (4) of curing and before the step of drying, a step of removing residual organic solvent is further included, specifically: and soaking the cured polylactic acid nascent membrane in water at the temperature of 10-60 ℃ for more than 12 hours.
Compared with the prior art, the preparation method of the polylactic acid microporous membrane has the following advantages:
the D-type polylactic acid and the L-type polylactic acid are compounded to form a special three-dimensional structure, and the surface layer of the special three-dimensional structure comprises a plurality of open pores. In other words, the microstructure of the L-type polylactic acid microporous membrane is regulated and controlled by introducing the D-type polylactic acid with chiral characteristics, and other types of pore opening agents are not required to be added, so that the polylactic acid microporous membrane with high flux, high interception and pollution resistance can be obtained. In addition, the size of the plurality of open pores can be regulated and controlled through the mass ratio between the D-type polylactic acid and the L-type polylactic acid, the organic solvent and the coagulation bath process, so that the microporous membrane with controllable pore diameter is obtained.
The traditional non-solvent induced phase separation method (NIPS) is adopted, the preparation method is simple, the process adjustment is mild, and the method is suitable for industrial production.
The polylactic acid microporous membrane has the following advantages: firstly, the polylactic acid microporous membrane has the characteristics of high flux, good interception and pollution resistance; secondly, the prepared polylactic acid microporous membrane is made of pure polylactic acid, has good biocompatibility and is biodegradable, and is an environment-friendly separation membrane; thirdly, the obtained polylactic acid microporous membrane can be used in the fields of water body purification, hemodialysis, microorganism culture and the like, and has very important scientific and application prospects.
Drawings
FIG. 1 is a photograph of the surface microtopography of the polylactic acid microporous membrane prepared in example 2;
FIG. 2 is a cross-sectional micro-topography photograph of the polylactic acid microporous membrane prepared in example 2;
FIG. 3 is a graph showing pure water flux, protein aqueous solution flux and flux recovery of the polylactic acid microporous membrane prepared in example 3.
Fig. 4 is a laser confocal microscope photograph of the polylactic acid microporous membrane prepared in example 3.
Detailed Description
The polylactic acid microporous membrane and the preparation method thereof provided by the present invention will be further described below.
The invention provides a preparation method of a polylactic acid microporous membrane, which comprises the following steps:
s1, dissolving D-type polylactic acid by an organic solvent to obtain a D-type polylactic acid solution;
s2, adding the L-type polylactic acid into the D-type polylactic acid solution, and uniformly stirring to obtain a polylactic acid membrane casting solution;
s3, defoaming the polylactic acid casting solution, and preparing a polylactic acid nascent membrane; and
s4, placing the polylactic acid primary membrane into a coagulating bath at 0-60 ℃ for solidification, and drying to obtain the polylactic acid microporous membrane.
In step S1, the organic solvent is used to dissolve the D-form polylactic acid. The organic solvent is at least one of N-methyl pyrrolidone, N-dimethylacetamide, dimethyl sulfoxide, dimethylformamide and triethyl phosphate. The temperature and time for dissolving the D-type polylactic acid are not limited as long as it is dissolved. Preferably, the dissolution temperature is 80 to 110 ℃ and the dissolution time is 1 to 4 hours when the D-type polylactic acid is dissolved.
In step S2, the D-type polylactic acid plays a role in regulation, and is uniformly mixed with the L-type polylactic acid, and is solidified in the subsequent coagulation bath, and the D-type polylactic acid and the L-type polylactic acid are effectively compounded to form a special three-dimensional structure. The mass ratio of the L-type polylactic acid to the D-type polylactic acid is (50-99.9) to (0.1-50). The polylactic acid casting solution comprises 75-88% of organic solvent and 12-25% of D-type polylactic acid and L-type polylactic acid in total mass ratio. Considering the influence of the viscosity of the polylactic acid casting solution on the forming and curing process of the polylactic acid primary film, preferably, the mass ratio of the organic solvent in the polylactic acid casting solution is 78-85%, and the total mass ratio of the D-type polylactic acid and the L-type polylactic acid is 15-22%.
The stirring temperature is 60-100 ℃, and the stirring time is 3-24 hours.
It should be further emphasized that the order of dissolving the D-form polylactic acid in step S1 and adding the L-form polylactic acid to the D-form polylactic acid solution in step S2 cannot be reversed. This is because the dissolution temperature of the D-type polylactic acid is higher than that of the L-type polylactic acid, and if the L-type polylactic acid is dissolved first and then the D-type polylactic acid is dissolved, the temperature of the solution needs to be increased when the D-type polylactic acid is dissolved, which causes degradation of the L-type polylactic acid; however, if the temperature of the solution is not increased, the D-type polylactic acid is difficult to be dissolved sufficiently, which causes the bad phenomenon that the casting solution is flocculent gel.
In step S3, the degassing of the polylactic acid casting solution may be performed by vacuum pumping and standing. The form of the polylactic acid primary membrane is not limited, and the polylactic acid primary membrane can be a flat membrane, a hollow fiber composite membrane, a homogeneous membrane, an asymmetric membrane and the like. The method for preparing the polylactic acid nascent membrane is not limited, and spinning, membrane scraping and the like can be adopted. The method to be used varies depending on the specific form of the polylactic acid microporous membrane.
In step S4, the solvent used in the coagulation bath is water or a mixture of water and at least one of the organic solvents in step S1. When a mixture of water and an organic solvent is used as a solvent of the coagulating bath, the volume ratio of the water to the organic solvent is 10: 90-99: 1. Preferably, water is used as the solvent for the coagulation bath.
The curing time is 1 to 30 minutes. Preferably, the curing time is 5-20 minutes, and the curing temperature is 20-45 ℃.
Further, before drying after curing, the method also comprises a step of removing residual organic solvent, specifically: and soaking the cured polylactic acid nascent membrane in water at the temperature of 10-60 ℃ for more than 12 hours.
Referring to fig. 1 and 2, the present invention further provides a polylactic acid microporous membrane, which is formed by compounding L-type polylactic acid and D-type polylactic acid, and the surface of the polylactic acid microporous membrane includes a plurality of openings. The pore size of the open pore is not limited, and is preferably 10 nanometers to 3 micrometers. The mass ratio of the L-type polylactic acid to the D-type polylactic acid in the polylactic acid microporous membrane is (50-99.9): (0.1-50).
It can be appreciated that referring to fig. 2, a plurality of smaller sized openings are provided near the upper surface of the polylactic acid microporous membrane for filtration. The open pore is formed in the curing and compounding process between the L-type polylactic acid and the D-type polylactic acid. The pore diameter of the open pores with smaller size can be determined by the addition ratio of the D-type polylactic acid, the organic solvent and the process of the coagulation bath. And a plurality of channels with larger sizes are arranged near the lower surface and the middle part of the polylactic acid microporous membrane and can drain substances obtained after the substances are filtered by the upper surface of the polylactic acid microporous membrane.
Compared with the prior art, the preparation method of the polylactic acid microporous membrane has the following advantages:
the D-type polylactic acid and the L-type polylactic acid are compounded to form a special three-dimensional structure, and the surface layer of the special three-dimensional structure comprises a plurality of open pores. In other words, the microstructure of the L-type polylactic acid microporous membrane is regulated and controlled by introducing the D-type polylactic acid with chiral characteristics, and other types of pore opening agents are not required to be added, so that the polylactic acid microporous membrane with high flux, high interception and pollution resistance can be obtained. In addition, the size of the plurality of open pores can be regulated and controlled through the mass ratio between the D-type polylactic acid and the L-type polylactic acid, the organic solvent and the coagulation bath process, so that the microporous membrane with controllable pore diameter is obtained.
The traditional non-solvent induced phase separation method is adopted, the preparation method is simple, the process adjustment is mild, and the method is suitable for industrial production.
The polylactic acid microporous membrane has the following advantages: firstly, the polylactic acid microporous membrane has the characteristics of high flux, good interception and pollution resistance; secondly, the prepared polylactic acid microporous membrane is made of pure polylactic acid, has good biocompatibility and is biodegradable, and is an environment-friendly separation membrane; thirdly, the obtained polylactic acid microporous membrane can be used in the fields of water body purification, hemodialysis, microorganism culture and the like, and has very important scientific and application prospects.
Hereinafter, the polylactic acid microporous membrane and the method for preparing the same according to the present invention will be further described with reference to specific examples.
Example 1
Step (1), adding 0.2g D type polylactic acid and 85g triethyl phosphate into a container, and stirring and dissolving for 3 hours at 90 ℃;
reducing the temperature to 70 ℃, adding 14.8g L type polylactic acid, stirring and dissolving for 16 hours;
step (3) carrying out vacuum defoaming on the polylactic acid casting solution obtained by full dissolution for 20 minutes, standing and defoaming at 70 ℃ for 12 hours, and preparing a hollow fiber nascent membrane by a hollow fiber membrane spinning system;
and (4) solidifying the prepared polylactic acid hollow fiber membrane by using deionized water at 20 ℃, then soaking the polylactic acid hollow fiber membrane in deionized water at 25 ℃ for 16 hours, fully removing the organic solvent, and drying to obtain the polylactic acid hollow fiber microporous membrane.
Example 2
Adding 2g D polylactic acid and 82g N, N-dimethyl acetamide into a container, and stirring and dissolving for 2 hours at 100 ℃;
reducing the temperature to 80 ℃, adding 16g L type polylactic acid, stirring and dissolving for 20 hours;
step (3) carrying out vacuum defoaming on the polylactic acid casting solution obtained by full dissolution for 30 minutes, standing and defoaming at 80 ℃ for 12 hours, and preparing a flat primary membrane by using a flat membrane scraping system;
and (4) the prepared polylactic acid flat primary membrane is subjected to deionization curing at 30 ℃, then is soaked in deionized water at 30 ℃ for 24 hours, organic solvents are fully removed, and the polylactic acid flat microporous membrane is obtained after drying.
And carrying out performance test on the polylactic acid flat microporous membrane. The results were: the water flux is 2300L/m2H, the retention rate of BSA reaches 94%, and the protein adsorption capacity is 4%.
Further, the morphology of the polylactic acid flat plate microporous membrane is characterized, and the results are shown in fig. 1 and fig. 2.
As can be seen from FIG. 1, the microporous structure is uniformly distributed on the surface of the polylactic acid flat microporous membrane.
As can be seen from fig. 2, a stereocomplex structure exists in the polylactic acid flat microporous membrane, and the polylactic acid flat microporous membrane is formed with a multi-scale microporous structure, wherein the size of micropores near the upper surface of the polylactic acid flat microporous membrane is smaller, so as to perform a filtering function; while the pores near the lower layer are larger in size and serve as channels.
Example 3
Adding 3g D type polylactic acid and 80g N-methyl pyrrolidone into a container, and stirring and dissolving for 1 hour at 110 ℃;
reducing the temperature to 85 ℃, adding 17g L type polylactic acid, stirring and dissolving for 24 hours;
step (3) carrying out vacuum defoaming on the polylactic acid casting solution obtained by full dissolution for 30 minutes, standing and defoaming at 80 ℃ for 20 hours, and preparing a flat primary membrane by using a flat membrane scraping system;
and (4) the prepared polylactic acid flat primary membrane is subjected to deionization curing at 25 ℃, then is soaked in deionized water at 25 ℃ for 20 hours, organic solvents are fully removed, and the polylactic acid flat microporous membrane is obtained after drying.
And carrying out performance test on the polylactic acid flat microporous membrane. The results were: the contact angle of the membrane surface is 84 degrees, and the water flux is 3500L/m2H, the retention rate of BSA reaches 90%, and the protein adsorption capacity is 7%.
As can be seen in fig. 3, the flux of the polylactic acid flat microporous membrane can be returned to the initial level, which indicates that the polylactic acid flat microporous membrane has excellent protein contamination resistance.
Further, the polylactic acid flat microporous membrane is subjected to surface morphology characterization, and the result is shown in fig. 4.
As can be seen from fig. 4, the surface roughness of the polylactic acid microporous membrane reached 0.80 μm.
Example 4
Adding 4g D type polylactic acid and 83g dimethyl sulfoxide into a container, and stirring and dissolving for 2 hours at 95 ℃;
reducing the temperature to 80 ℃, adding 13g L type polylactic acid, stirring and dissolving for 24 hours;
step (3) carrying out vacuum defoaming on the polylactic acid casting solution obtained by full dissolution for 30 minutes, standing and defoaming at 80 ℃ for 20 hours, and preparing a flat primary membrane by using a flat membrane scraping system;
and (4) the prepared polylactic acid flat primary membrane is subjected to deionization curing at 25 ℃, then is soaked in deionized water at 25 ℃ for 20 hours, organic solvents are fully removed, and the polylactic acid flat microporous membrane is obtained after drying.
And carrying out performance test on the polylactic acid flat microporous membrane. The results were: the water flux is 4200L/m2H, BSA retention of 85%.
Example 5
Adding 1g D type polylactic acid and 86g dimethyl sulfoxide into a container, stirring and dissolving for 4 hours at 85 ℃;
reducing the temperature to 70 ℃, adding 13gL type polylactic acid, stirring and dissolving for 12 hours;
step (3) carrying out vacuum defoaming on the polylactic acid casting solution obtained by full dissolution for 15 minutes, standing and defoaming at 70 ℃ for 16 hours, and preparing a flat composite nascent membrane on non-woven fabric by a flat membrane scraping system;
and (4) the prepared polylactic acid flat plate composite primary membrane is subjected to deionization curing at 25 ℃, then is soaked in deionized water at 25 ℃ for 15 hours, organic solvents are fully removed, and the polylactic acid flat plate composite microporous membrane is obtained after drying.
And carrying out performance test on the polylactic acid flat plate composite microporous membrane. The results were: the filtration flux of the nano titanium dioxide solution is 1000L/m2H, retention 95%.
Example 6
Adding 7g D type polylactic acid and 82g dimethylformamide into a container, stirring and dissolving for 3 hours at 90 ℃;
reducing the temperature to 80 ℃, adding 9g L type polylactic acid, stirring and dissolving for 16 hours;
step (3), the polylactic acid casting solution obtained by full dissolution is defoamed in vacuum for 20 minutes, then is kept stand and defoamed for 18 hours at 80 ℃, and a flat composite nascent membrane is prepared on a screen mesh by a flat membrane scraping system;
and (4) the prepared polylactic acid flat plate composite nascent membrane is subjected to deionization curing at 40 ℃, then is soaked in deionized water at 50 ℃ for 12 hours, organic solvent is fully removed, and the polylactic acid flat plate composite microporous membrane is obtained after drying.
And carrying out performance test on the polylactic acid flat plate composite microporous membrane. The results were: the filtering flux of the ink water solution is 4800L/m2H, retention 96%.
Example 7
Adding 1.5g D polylactic acid and 82g N, N-dimethyl acetamide into a container, and stirring and dissolving for 2 hours at 95 ℃;
reducing the temperature to 75 ℃, adding 16.5g L type polylactic acid, stirring and dissolving for 10 hours;
step (3) carrying out vacuum defoaming on the polylactic acid casting solution obtained by full dissolution for 10 minutes, standing and defoaming at 75 ℃ for 18 hours, and preparing a hollow fiber composite nascent membrane by using a hollow fiber membrane spinning system and a braided tube as a substrate;
and (4) the prepared polylactic acid hollow fiber composite primary membrane is subjected to deionization curing at 50 ℃, then is soaked in deionized water at 25 ℃ for 16 hours, organic solvents are fully removed, and the polylactic acid hollow fiber composite microporous membrane is obtained after drying.
And carrying out performance test on the polylactic acid hollow fiber composite microporous membrane. The results were: the contact angle of the membrane surface is 76 degrees, and the water flux is 1100L/m2H, the retention rate of BSA reaches 93%, and the protein adsorption capacity is 5%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A preparation method of a polylactic acid microporous membrane is characterized by comprising the following steps:
(1) dissolving D-type polylactic acid by an organic solvent to obtain a D-type polylactic acid solution;
(2) adding L-type polylactic acid into a D-type polylactic acid solution, and uniformly stirring to obtain a polylactic acid membrane casting solution;
(3) defoaming the polylactic acid casting solution, and preparing a polylactic acid nascent membrane;
(4) and (2) placing the polylactic acid primary membrane into a coagulating bath at the temperature of 0-60 ℃ for solidification, and drying to obtain a polylactic acid microporous membrane, wherein the polylactic acid microporous membrane is formed by compounding L-type polylactic acid and D-type polylactic acid, and the surface of the polylactic acid microporous membrane comprises a plurality of openings.
2. The method of preparing a polylactic acid microporous membrane according to claim 1, wherein the dissolving of the D-type polylactic acid in the step (1) is carried out at a temperature of 80 ℃ to 110 ℃ for 1 hour to 4 hours, and the organic solvent is at least one of N-methylpyrrolidone, N-dimethylacetamide, dimethylsulfoxide, dimethylformamide, and triethyl phosphate.
3. The method for preparing a polylactic acid microporous membrane according to claim 1, wherein the polylactic acid membrane casting solution in the step (2) contains 75 to 88 mass% of an organic solvent, and the total mass ratio of the D-type polylactic acid to the L-type polylactic acid is 12 to 25%.
4. The method of claim 1, wherein the stirring temperature in step (2) is 60 ℃ to 100 ℃ and the stirring time is 3 hours to 24 hours.
5. The method for preparing a polylactic acid microporous membrane according to claim 1, wherein the solvent used in the coagulation bath in step (4) is water or a mixture of water and at least one of the organic solvents in step (1).
6. The method for preparing a polylactic acid microporous membrane according to claim 1, wherein the curing time in the step (4) is 1 to 30 minutes.
7. The method for preparing a polylactic acid microporous membrane according to claim 1, further comprising a step of removing residual organic solvent after the step (4) of curing and before the step of drying, specifically: and soaking the cured polylactic acid nascent membrane in water at the temperature of 10-60 ℃ for more than 12 hours.
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| Title |
|---|
| 《Facile preparation of patterned petal-like PLA surfaces with tunable water micro-droplet adhesion properties based on stereo-complex co-crystallization from non-solvent induced phase separation processes》;Ailin Gao et al;《Journal of Materials Chemistry A》;20160525;第4卷(第31期);12058–12064 * |
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| CN108568216A (en) | 2018-09-25 |
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