CN113980308A - Method for preparing high-crystallinity polylactic acid film - Google Patents
Method for preparing high-crystallinity polylactic acid film Download PDFInfo
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- CN113980308A CN113980308A CN202111287272.0A CN202111287272A CN113980308A CN 113980308 A CN113980308 A CN 113980308A CN 202111287272 A CN202111287272 A CN 202111287272A CN 113980308 A CN113980308 A CN 113980308A
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- polylactic acid
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- 229920006381 polylactic acid film Polymers 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 123
- 239000004626 polylactic acid Substances 0.000 claims abstract description 123
- 239000002904 solvent Substances 0.000 claims abstract description 54
- 238000001035 drying Methods 0.000 claims abstract description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229960001701 chloroform Drugs 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011521 glass Substances 0.000 description 15
- 239000002667 nucleating agent Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000118 poly(D-lactic acid) Polymers 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a method for preparing a high-crystallinity porous polylactic acid film, and belongs to the field of preparation methods of high-crystallinity polylactic acid. The low crystallinity of polylactic acid causes the low heat distortion temperature and heat resistance, which restricts the daily scale application of polylactic acid, and the effective improvement of the crystallinity is one of the problems to be solved in important points for improving the heat resistance. The invention provides a method for preparing polylactic acid with high crystallinity, which comprises the steps of firstly dissolving polylactic acid in a single or mixed good solvent to obtain a uniform and transparent solution, then adding the polylactic acid solution and poor solvent of the polylactic acid into a flat-bottom container respectively or after mixing, standing for 4-24 hours at room temperature to enable the polylactic acid to be completely filmed, and completely removing the solvent in the polylactic acid film through a drying process to obtain the polylactic acid film with high crystallinity. The method can regulate and control the crystallinity and the structure of the polylactic acid through the preparation conditions, and has the outstanding advantages of simple and convenient operation, mild conditions, low cost, obvious effect and the like.
Description
Technical Field
The invention relates to the field of preparation of high-crystallinity polylactic acid films.
Background
Polylactic acid is a biomass degradable plastic, has higher thermoplasticity and strength, biocompatibility and bioabsorbability, and is a green polymer which is most promising to replace petroleum-based non-degradable plastics. The products with different configurations, such as levorotatory polylactic acid, dextrorotatory polylactic acid, meso-polylactic acid and the like, can be obtained by using monomers with different hand shapes, wherein the levorotatory polylactic acid and the dextrorotatory polylactic acid are semi-crystalline polymers. However, polylactic acid has problems, for example, low crystallinity of L-polylactic acid, which results in low heat distortion temperature and heat resistance, and restricts its scale use in daily life. The improvement of the crystallinity of polylactic acid is one of the problems that needs to be solved in an important way to improve the heat resistance.
At present, the filling method and the heat treatment method are commonly used for improving the crystallinity of the polylactic acid, wherein the filling method is to promote the ordered arrangement of the molecular chains of the polylactic acid by adding an organic or inorganic nucleating agent and the like into the polylactic acid, although the method can improve the crystallinity of the polylactic acid to a certain extent, the addition of the nucleating agent can also influence the degradability and biocompatibility of the polylactic acid, and in order to improve the dispersibility of the nucleating agent, the dosage and the surface interface physical property of the nucleating agent also need to be controlled, and the nucleating agent can be agglomerated when the dosage is high, so that the toughness, the elongation and other properties of the polylactic acid are reduced; the heat treatment method improves the crystallinity of the polylactic acid by regulating and controlling the cooling rate, the heat preservation temperature and the time length in the polylactic acid molding process, or can also improve the crystallinity of the molded polylactic acid by annealing or isothermal treatment, and the improvement of the crystallinity of the polylactic acid by the heat treatment can reduce the molding efficiency and also relates to the use of heating equipment and the consumption of electric energy.
In view of the problems of the filling method and the heat treatment method for improving the crystallization of polylactic acid, it is necessary to find a simple method for improving the crystallinity of polylactic acid without using a nucleating agent and without heating.
Disclosure of Invention
Based on the method, the invention provides a preparation method of the high-crystallinity polylactic acid film.
The technical scheme of the invention is as follows:
the invention provides a preparation method of a high-crystallinity polylactic acid film, which is characterized by comprising the following steps:
(1) firstly, dissolving polylactic acid in a single or mixed good solvent to obtain a uniform and transparent polylactic acid solution;
(2) respectively adding a poor solvent of polylactic acid and a polylactic acid solution into a flat-bottom container, standing the mixed system at room temperature for 4-24 hours to enable the polylactic acid to be completely filmed, and completely removing the solvent in the mixed system through a drying process to obtain the high-crystallinity polylactic acid.
The polylactic acid is levorotatory polylactic acid, dextrorotatory polylactic acid or the mixture of the levorotatory polylactic acid and the dextrorotatory polylactic acid;
preferably, the good solvent is dichloromethane or trichloromethane;
the polylactic acid solution is a levorotatory polylactic acid solution, a dextrorotatory polylactic acid solution or a mixed solution of the levorotatory polylactic acid solution and the dextrorotatory polylactic acid solution.
Preferably, the poor solvent is one or more of water, absolute ethyl alcohol, methanol, isopropanol, propanol, tetrahydrofuran, acetone, ethyl acetate, cyclohexane and n-hexane.
Preferably, the mass-to-volume ratio of the polylactic acid to the good solvent in the step (1) is 5-120 mg:1 mL.
Preferably, the volume ratio of the poor solvent to the good solvent in the step (2) is (0.1-10): 1.
In the step (2), the poor solvent and the polylactic acid solution can be added into the flat-bottom container in sequence, or the polylactic acid solution and the poor solvent can be added into the flat-bottom container in sequence.
The drying process comprises the following steps: completely removing the solvent component in the polylactic acid by vacuum drying for 2-24 hours at the temperature of 196-40 ℃.
Advantageous effects
Compared with the prior art, the method for preparing the high-crystallinity polylactic acid film does not need to use an organic or inorganic nucleating agent, does not need to perform annealing or isothermal treatment on the polylactic acid, can change the crystal structure and the crystallinity of the polylactic acid film by regulating and controlling the preparation conditions such as the type of poor solvent, the ratio of good solvent to poor solvent, the concentration of the polylactic acid and the like, and has the outstanding advantages and progresses of simple and convenient operation, mild conditions, low cost, obvious effect and the like.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1:
(1) dissolving 20mg of L-polylactic acid in 4ml of dichloromethane solvent to obtain uniform and transparent solution;
(2) respectively adding the polylactic acid solution and 0.4ml of absolute ethyl alcohol into a glass culture dish with the diameter of 6cm, standing the mixed system at room temperature for 4-24 hours to completely form a film by polylactic acid, and drying in a vacuum oven at 40 ℃ for 8 hours to completely remove the solvent to obtain the levorotatory polylactic acid film with the crystallinity of 28.1%.
Example 2:
(1) 480mg of L-polylactic acid is dissolved in 4ml of dichloromethane solvent to obtain uniform and transparent solution;
(2) respectively adding 2ml of isopropanol and polylactic acid solution into a glass culture dish with the diameter of 6cm, standing the mixed system at room temperature for 4-24 hours to completely form polylactic acid films, and drying in a vacuum oven at 40 ℃ for 8 hours to completely remove the solvent in the mixed system to obtain the levorotatory polylactic acid film with the crystallinity of 38.2%.
Example 3:
(1) dissolving 320mg of L-polylactic acid and 80mg of D-polylactic acid in 4ml of dichloromethane solvent to obtain uniform and transparent solution;
(2) adding polylactic acid solution and 2ml anhydrous ethanol into glass culture dish with diameter of 6cm, respectively, and standing the mixed system at room temperature to 4 ∞
And (3) forming a film of all polylactic acid within 24 hours, and drying in a vacuum oven at 40 ℃ for 8 hours to completely remove the solvent to obtain the stereocomplex polylactic acid film with the crystallinity of 43.4 percent.
Example 4:
(1) dissolving 400mg of L-polylactic acid in 4ml of chloroform solvent to obtain a uniform and transparent solution;
(2) mixing the polylactic acid solution with 2ml of absolute ethyl alcohol, adding the mixture into a glass culture dish with the diameter of 6cm, standing the mixed system at room temperature for 4-24 hours to enable all polylactic acid to form a film, and drying in a vacuum oven at 40 ℃ for 8 hours to completely remove the solvent to obtain the levorotatory polylactic acid film with the crystallinity of 37.3%.
Example 5:
(1) dissolving 400mg of L-polylactic acid in 4ml of dichloromethane solvent to obtain uniform and transparent solution;
(2) respectively adding 2ml of methanol and polylactic acid solution into a glass culture dish with the diameter of 6cm, standing the mixed system at room temperature for 4-24 hours to completely form a film by polylactic acid, and drying in a vacuum oven at 40 ℃ for 8 hours to completely remove the solvent in the film to obtain the levorotatory polylactic acid film with the crystallinity of 32.3%.
Example 6:
(1) 300mg of poly (D-lactic acid) is dissolved in 4ml of dichloromethane solvent to obtain a uniform and transparent solution;
(2) adding polylactic acid solution and 2ml anhydrous ethanol into glass culture dish with diameter of 6cm, respectively, and standing the mixed system at room temperature to 4 ∞
And (3) forming a film of all polylactic acid within 24 hours, and drying in a vacuum oven at 40 ℃ for 8 hours to completely remove the solvent to obtain the dextro-polylactic acid film with the crystallinity of 36.1 percent.
Example 7:
(1) dissolving 400mg of L-polylactic acid in 4ml of dichloromethane solvent to obtain uniform and transparent solution;
(2) adding polylactic acid solution and 8ml anhydrous ethanol into 6cm diameter glass culture dish, respectively, and standing the mixed system at room temperature to 4E [ E ] E
And (3) forming a film of all polylactic acid within 24 hours, and drying in a vacuum oven at 40 ℃ for 10 hours to completely remove the solvent to obtain the levorotatory polylactic acid film with the crystallinity of 28.1 percent.
Example 8:
(1) dissolving 400mg of L-polylactic acid in 4ml of dichloromethane solvent to obtain uniform and transparent solution;
(2) adding polylactic acid solution and 6ml of anhydrous ethanol into a glass culture dish with the diameter of 6cm respectively, and standing the mixed system at room temperature for 4 to
And (3) forming a film of all polylactic acid within 24 hours, and drying in a vacuum oven at 40 ℃ for 8 hours to completely remove the solvent to obtain the levorotatory polylactic acid film with the crystallinity of 30.7 percent.
Example 9:
(1) dissolving 400mg of L-polylactic acid in 4ml of dichloromethane solvent to obtain uniform and transparent solution;
(2) adding 4ml of anhydrous ethanol and polylactic acid solution into a glass culture dish with the diameter of 6cm respectively, and allowing the mixed system to stand at room temperature for 4E to E
And (3) forming a film of all polylactic acid within 24 hours, and drying in a vacuum oven at 40 ℃ for 8 hours to completely remove the solvent to obtain the levorotatory polylactic acid film with the crystallinity of 39.5 percent.
Example 10:
(1) respectively dissolving 360mg of L-polylactic acid and 40mg of D-polylactic acid in 4ml of dichloromethane and 1ml of dichloromethane, and mixing to obtain uniform and transparent solution;
(2) 5ml of the mixed solution of the absolute ethyl alcohol and the polylactic acid is respectively added into a glass culture dish with the diameter of 8cm, the mixed system is allowed to stand at room temperature for 12 hours to enable the polylactic acid to be completely formed into a film, and then the film is dried in a vacuum oven at the temperature of 196 ℃ below zero for 8 hours to completely remove the solvent in the film, so that the stereo composite polylactic acid film with the crystallinity of 40.3 percent can be obtained.
Example 11:
(1) respectively dissolving 240mg of L-polylactic acid and 160mg of D-polylactic acid in 5ml of dichloromethane and 3ml of dichloromethane, and mixing to obtain uniform and transparent solutions;
(2) 80ml of absolute ethyl alcohol and polylactic acid mixed solution are respectively added into a flat-bottom glass culture dish, the mixed system is allowed to stand at room temperature for 12 hours to enable all polylactic acid to form a film, and then the film is dried in a vacuum oven at the temperature of 25 ℃ for 12 hours to completely remove the solvent in the film, so that the stereo composite polylactic acid film with the crystallinity of 45.2 percent can be obtained.
Example 12:
(1) respectively dissolving 200mg of L-polylactic acid and 200mg of D-polylactic acid in 5ml and 3ml of dichloromethane, and mixing to obtain uniform and transparent solutions;
(2) adding 24ml of mixed solution of absolute ethyl alcohol and polylactic acid into a glass culture dish with the diameter of 8cm, standing the mixed system at room temperature for 12 hours to enable all polylactic acid to form a film, and drying in a vacuum oven at 25 ℃ for 12 hours to completely remove the solvent in the film so as to obtain the stereocomplex polylactic acid film with the crystallinity of 50.2%.
Example 13:
(1) dissolving 500mg of L-polylactic acid in 10ml of dichloromethane to obtain a uniform and transparent solution;
(2) respectively adding 10ml of acetone and polylactic acid solution into a glass culture dish with the diameter of 8cm, standing the mixed system at room temperature for 12 hours to enable all polylactic acid to form a film, and drying in a vacuum oven at the temperature of 20 ℃ for 16 hours to completely remove the solvent to obtain the levorotatory polylactic acid film with the crystallinity of 39.2%.
Example 14:
(1) dissolving 400mg of L-polylactic acid in a mixed solvent of 2ml of dichloromethane and 2ml of trichloromethane to obtain a uniform and transparent solution;
(2) respectively adding 4ml of isopropanol and polylactic acid mixed solution into a glass culture dish with the diameter of 5cm, standing the mixed system at room temperature for 10 hours to completely form a film of polylactic acid, and drying in a vacuum oven at 25 ℃ for 12 hours to completely remove the solvent in the film to obtain the levorotatory polylactic acid film with the crystallinity of 48.5 percent.
Example 15:
(1) dissolving 400mg of L-polylactic acid in a mixed solvent of 2ml of dichloromethane and 2ml of trichloromethane to obtain a uniform and transparent solution;
(2) respectively adding 4ml of water and polylactic acid mixed solution into a glass culture dish with the diameter of 5cm, standing the mixed system at room temperature for 10 hours to enable all polylactic acid to form a film, and drying in a vacuum oven at 25 ℃ for 24 hours to completely remove the solvent to obtain the levorotatory polylactic acid film with the crystallinity of 25.2%.
Example 16:
(1) dissolving 400mg of L-polylactic acid in 6ml of chloroform to obtain a uniform and transparent solution;
(2) adding 1ml of cyclohexane, 3ml of isopropanol and polylactic acid mixed solution into a metal flat-bottom container respectively, standing the mixed system at room temperature for 10 hours to enable all polylactic acid to form a film, and drying in a vacuum oven at 40 ℃ for 24 hours to completely remove the solvent to obtain the levorotatory polylactic acid film with the crystallinity of 48.1%.
Example 17:
(1) dissolving 400mg of dextrorotatory polylactic acid in 6ml of mixed solvent of trichloromethane to obtain uniform and transparent solution;
(2) respectively adding 6ml of isopropanol and polylactic acid mixed solution into a polytetrafluoroethylene flat-bottom container, standing the mixed system at room temperature for 10 hours to completely form a polylactic acid film, and drying in a vacuum oven at 25 ℃ for 24 hours to completely remove the solvent to obtain the dextro-polylactic acid film with the crystallinity of 48.3%.
Claims (2)
1. A method for preparing a high-crystallinity polylactic acid film is characterized by comprising the following steps:
(1) firstly, dissolving polylactic acid in a single or mixed good solvent to obtain a uniform and transparent polylactic acid solution;
(2) respectively adding a poor solvent of polylactic acid and a polylactic acid solution into a flat-bottom container, standing the mixed system at room temperature for 4-24 hours to completely form a film of the polylactic acid, and completely removing the solvent in the mixed system through a drying process to obtain a high-crystallinity polylactic acid film;
the polylactic acid is levorotatory polylactic acid, dextrorotatory polylactic acid or the mixture of the levorotatory polylactic acid and the dextrorotatory polylactic acid;
the good solvent is dichloromethane or trichloromethane;
the polylactic acid solution is a levorotatory polylactic acid solution, a dextrorotatory polylactic acid solution or a mixed solution of the levorotatory polylactic acid solution and the dextrorotatory polylactic acid solution;
the poor solvent is one or more of water, absolute ethyl alcohol, methanol, isopropanol, propanol, tetrahydrofuran, acetone, ethyl acetate, cyclohexane and normal hexane;
in the step (1), the mass-to-volume ratio of the polylactic acid to the good solvent is 5-120 mg:1 mL;
the volume ratio of the poor solvent to the good solvent in the step (2) is (0.1-10): 1;
the drying process comprises the following steps: completely removing the solvent component in the polylactic acid by vacuum drying for 2-24 hours at-196-40 ℃.
2. The method of claim 1, wherein the poor solvent and the polylactic acid solution are added to the flat-bottom container sequentially, or the polylactic acid solution and the poor solvent are added to the flat-bottom container sequentially.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111287272.0A CN113980308A (en) | 2021-11-02 | 2021-11-02 | Method for preparing high-crystallinity polylactic acid film |
| PCT/CN2021/128332 WO2023077289A1 (en) | 2021-11-02 | 2021-11-03 | Method for preparing high-crystallinity polylactic acid film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111287272.0A CN113980308A (en) | 2021-11-02 | 2021-11-02 | Method for preparing high-crystallinity polylactic acid film |
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| CN113980308A true CN113980308A (en) | 2022-01-28 |
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| CN202111287272.0A Pending CN113980308A (en) | 2021-11-02 | 2021-11-02 | Method for preparing high-crystallinity polylactic acid film |
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| Country | Link |
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| CN (1) | CN113980308A (en) |
| WO (1) | WO2023077289A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114874592A (en) * | 2022-03-30 | 2022-08-09 | 中原工学院 | Flexible porous super-hydrophobic film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125931A (en) * | 2007-07-24 | 2008-02-20 | 陕西科技大学 | Polylactic acid with different crystallinity and preparation technique for copolymer film thereof |
| JP2008208172A (en) * | 2007-02-23 | 2008-09-11 | Tokyo Univ Of Science | Solid polylactic acid and method for producing the same |
| CN111909417A (en) * | 2020-08-13 | 2020-11-10 | 贵州省材料产业技术研究院 | Preparation method of polylactic acid film with uniform pore on surface |
| CN113461995A (en) * | 2021-07-22 | 2021-10-01 | 郑州大学 | Preparation method of polylactic acid material with anti-adhesion and sterilization functions |
-
2021
- 2021-11-02 CN CN202111287272.0A patent/CN113980308A/en active Pending
- 2021-11-03 WO PCT/CN2021/128332 patent/WO2023077289A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008208172A (en) * | 2007-02-23 | 2008-09-11 | Tokyo Univ Of Science | Solid polylactic acid and method for producing the same |
| CN101125931A (en) * | 2007-07-24 | 2008-02-20 | 陕西科技大学 | Polylactic acid with different crystallinity and preparation technique for copolymer film thereof |
| CN111909417A (en) * | 2020-08-13 | 2020-11-10 | 贵州省材料产业技术研究院 | Preparation method of polylactic acid film with uniform pore on surface |
| CN113461995A (en) * | 2021-07-22 | 2021-10-01 | 郑州大学 | Preparation method of polylactic acid material with anti-adhesion and sterilization functions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114874592A (en) * | 2022-03-30 | 2022-08-09 | 中原工学院 | Flexible porous super-hydrophobic film and preparation method thereof |
| CN114874592B (en) * | 2022-03-30 | 2023-11-03 | 中原工学院 | Flexible porous super-hydrophobic film and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| WO2023077289A1 (en) | 2023-05-11 |
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Application publication date: 20220128 |