CN111004485A - Polylactic acid composite material containing Kevlar nanofiber and preparation method thereof - Google Patents
Polylactic acid composite material containing Kevlar nanofiber and preparation method thereof Download PDFInfo
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- CN111004485A CN111004485A CN201911379936.9A CN201911379936A CN111004485A CN 111004485 A CN111004485 A CN 111004485A CN 201911379936 A CN201911379936 A CN 201911379936A CN 111004485 A CN111004485 A CN 111004485A
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- 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
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- 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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- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
Abstract
The invention relates to a polylactic acid composite material containing Kevlar nano fiber and a preparation method thereof. Mixing the Kevlar nanofiber solution and the polylactic acid solution according to a certain proportion, uniformly stirring, adding a small amount of deionized water, forming gel in the mixed solution, performing vacuum filtration by adopting a nylon membrane, and performing vacuum drying to obtain a composite material of Kevlar nanofiber and polylactic acid, wherein the composite material has good biocompatibility and degradability, is green and environment-friendly, and simultaneously has high-strength mechanical properties, the ultimate tensile strength can reach 16.8-34.9 MPa, and the elongation at break can reach 4.2-6.3%; the maximum thermal decomposition temperature can reach 357.9-371.2 ℃, and the composite membrane prepared by the invention can be used in the fields of flexible electronics, bionic materials and the like.
Description
Technical Field
The invention relates to a polylactic acid composite material containing Kevlar nanofibers and a preparation method thereof, belonging to the technical field of polylactic acid material preparation.
Background
In recent years, with the development of society, people pursue the concept of ecological harmony and green cycle more and more, and biodegradable materials begin to get attention of people. Among them, polylactic acid (PLA) is favored by researchers because of its excellent degradable property. Polylactic acid adopts starch extracted from plants as a raw material, the starch is converted into glucose through certain reaction, lactic acid is formed through fermentation, and finally, a polylactic acid polymer with certain molecular weight is synthesized through chemical reaction. The polylactic acid material can be decomposed in the environment through the microbial decomposition after being discarded, and the process hardly generates harmful substances. Therefore, the polylactic acid material is an environment-friendly material and can promote the harmony and coexistence of nature and people.
However, due to the defects of high brittleness, poor thermal stability, non-ideal barrier property and the like of the polylactic acid, the further use of the polylactic acid in the field of engineering materials is limited, and the defect of the polylactic acid material can be greatly improved by adding an additive into the polylactic acid to prepare a composite material.
Kevlar (Kevlar) fiber is widely used in the fields of aerospace, military and the like as a high-performance synthetic fiber, and with the development of nano materials, nano-scale Kevlar fiber is also developed to enhance various performances of nano composite materials. The solution blending method used to pack Kevlar nanofibers into polyvinyl alcohol is reported in Composites Science and Technology, 2017, 144: 193-one 201, resulting in a polymeric material with both high strength and high thermal stability.
Disclosure of Invention
The invention aims to provide a polylactic acid composite material containing Kevlar nano-fiber and having high mechanical strength and high thermal stability and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
the composite material comprises 1-9% of Kevlar nanofibers by mass and the balance of polylactic acid.
Preferably, the Kevlar nanofiber has the strength of 3.6 GPa, the elongation modulus of 131 GPa and the elongation at break of 2.8 percent, and has the length of 5-10 mu m and the diameter of 3-30 nm.
Preferably, the molecular weight of the polylactic acid is 5 to 20 ten thousand.
A preparation method of a polylactic acid composite material containing Kevlar nano-fibers comprises the following steps: (1) cutting Kevlar fiber into thin sections of 1-2 cm, immersing the Kevlar fiber in a dimethyl sulfoxide solvent containing potassium hydroxide, and continuously magnetically stirring for 7 days to obtain a Kevlar nanofiber solution; (2) mixing the Kevlar nanofiber solution and the dimethyl sulfoxide solution of polylactic acid according to a certain proportion, uniformly stirring, adding a small amount of deionized water to form gel, performing vacuum filtration by adopting a nylon membrane, and drying in a vacuum drying oven to obtain the composite material of the Kevlar nanofiber and the polylactic acid.
Preferably, in the step (1), the mass-to-volume ratio of the Kevlar nanofibers to the dimethyl sulfoxide solvent is 0.4-1: 200 g/mL.
Preferably, in the dimethyl sulfoxide solution of polylactic acid, the mass-volume ratio of polylactic acid to dimethyl sulfoxide is 0.2-0.5: 10 g/mL.
Preferably, the Kevlar nanofiber solution and the dimethyl sulfoxide solution of polylactic acid are mixed according to the mass ratio of 1-9: 100.
Preferably, the aperture size of the nylon membrane is 0.1 to 0.5 μm.
Preferably, the temperature of the vacuum drying oven is 40-50 ℃, and the drying is continuously carried out for 8-12 h.
Compared with the prior art, the invention has the following remarkable advantages: the prepared Kevlar nanofiber and polylactic acid composite film material is non-toxic and harmless, has good biocompatibility and degradability, is green and environment-friendly, and has high-strength mechanical properties, the ultimate tensile strength can reach 16.8-34.9 MPa, and the elongation at break can reach 4.2-6.3%; the maximum thermal decomposition temperature can reach 357.9-371.2 ℃. Meanwhile, the polylactic acid composite film material can not deteriorate after being placed for a long time, is convenient to transport and store, and has a certain application prospect in the fields of flexible electronics, bionic materials and the like.
Detailed Description
The inventor notices that compared with other fibers, Kevlar nanofiber has higher strength, stability and length-diameter ratio and should have better reinforcing effect on polylactic acid, however, the research on Kevlar nanofiber reinforced polylactic acid composite materials is rarely reported.
The preparation method of the Kevlar nanofiber and polylactic acid composite film can be further illustrated by the following examples:
example 1:
weighing 2g of Kevlar fiber fine wire and 3 g of potassium hydroxide, putting into a reactor, adding 400 mL of dimethyl sulfoxide solution, and magnetically stirring at 25 ℃ for 7 days to obtain a Kevlar nanofiber solution.
Weighing 10 g of polylactic acid particles with the molecular weight of 5 ten thousand, putting the polylactic acid particles into a beaker, adding 5000 mL of dimethyl sulfoxide, placing the beaker in a water bath, and heating the beaker at 80 ℃ until the polylactic acid is completely dissolved in the dimethyl sulfoxide solvent.
Measuring corresponding Kevlar nanofiber solution and polylactic acid solution according to the proportion of the Kevlar nanofiber and the polylactic acid being 1:100, and stirring for 30 min on a magnetic stirrer.
And 4 mL of deionized water is added into the mixed solution, at the moment, gel appears in the solution, and the magnetic stirring is continued for 2 hours, so that the Kevlar nanofiber solution and the polylactic acid solution are uniform and stable. Then, a nylon membrane with the aperture of 0.1 mu m is adopted for vacuum filtration to obtain a composite material of Kevlar nano-fiber and polylactic acid, the composite material is washed by deionized water and dried in a vacuum drying oven to form a film. The polylactic acid composite film has the tensile strength of 16.8 MPa, the elongation at break of 4.2 percent and the maximum thermal decomposition temperature of 357.9 ℃.
Example 2:
weighing 2g of Kevlar fiber fine wire and 3 g of potassium hydroxide, putting into a reactor, adding 400 mL of dimethyl sulfoxide solution, and magnetically stirring at 25 ℃ for 7 days to obtain a Kevlar nanofiber solution.
Weighing 10 g of polylactic acid particles with the molecular weight of 10 ten thousand, putting the polylactic acid particles into a beaker, adding 600 mL of dimethyl sulfoxide, placing the beaker in a water bath, and heating the beaker at 80 ℃ until the polylactic acid is completely dissolved in the dimethyl sulfoxide solvent.
Measuring corresponding Kevlar nanofiber solution and polylactic acid solution according to the ratio of the Kevlar nanofiber to the polylactic acid of 3:100, and stirring for 30 min on a magnetic stirrer.
And 4 mL of deionized water is added into the mixed solution, at the moment, gel appears in the solution, and the magnetic stirring is continued for 2 hours, so that the Kevlar nanofiber solution and the polylactic acid solution are uniform and stable. Then, a nylon membrane with the aperture of 0.1 mu m is adopted for vacuum filtration to obtain a composite material of Kevlar nano-fiber and polylactic acid, the composite material is washed by deionized water and dried in a vacuum drying oven to form a film. The polylactic acid composite film has the tensile strength of 23.4 MPa, the elongation at break of 4.7 percent and the maximum thermal decomposition temperature of 362.3 ℃.
Example 3:
weighing 2g of Kevlar fiber fine wire and 3 g of potassium hydroxide, putting into a reactor, adding 400 mL of dimethyl sulfoxide solution, and magnetically stirring at 25 ℃ for 7 days to obtain a Kevlar nanofiber solution.
Weighing 10 g of polylactic acid particles with the molecular weight of 12 ten thousand, putting the polylactic acid particles into a beaker, adding 800 mL of dimethyl sulfoxide, placing the beaker in a water bath, and heating the beaker at 80 ℃ until the polylactic acid is completely dissolved in the dimethyl sulfoxide solvent.
Measuring corresponding Kevlar nanofiber solution and polylactic acid solution according to the ratio of the Kevlar nanofiber to the polylactic acid of 5:100, and stirring for 30 min on a magnetic stirrer.
And 4 mL of deionized water is added into the mixed solution, at the moment, gel appears in the solution, and the magnetic stirring is continued for 2 hours, so that the Kevlar nanofiber solution and the polylactic acid solution are uniform and stable. Then, a nylon membrane with the aperture of 0.1 mu m is adopted for vacuum filtration to obtain a composite material of Kevlar nano-fiber and polylactic acid, the composite material is washed by deionized water and dried in a vacuum drying oven to form a film. The polylactic acid composite film has the tensile strength of 27.3 MPa, the elongation at break of 5.1 percent and the maximum thermal decomposition temperature of 365.8 ℃.
Example 4:
weighing 2g of Kevlar fiber fine wire and 3 g of potassium hydroxide, putting into a reactor, adding 400 mL of dimethyl sulfoxide solution, and magnetically stirring at 25 ℃ for 7 days to obtain a Kevlar nanofiber solution.
Weighing 10 g of polylactic acid particles with the molecular weight of 16 ten thousand, putting the polylactic acid particles into a beaker, adding 1000 mL of dimethyl sulfoxide, placing the beaker in a water bath, and heating the beaker at 80 ℃ until the polylactic acid is completely dissolved in the dimethyl sulfoxide solvent.
Measuring corresponding Kevlar nanofiber solution and polylactic acid solution according to the proportion of the Kevlar nanofiber and the polylactic acid being 7:100, and stirring for 30 min on a magnetic stirrer.
And 4 mL of deionized water is added into the mixed solution, at the moment, gel appears in the solution, and the magnetic stirring is continued for 2 hours, so that the Kevlar nanofiber solution and the polylactic acid solution are uniform and stable. Then, a nylon membrane with the aperture of 0.1 mu m is adopted for vacuum filtration to obtain a composite material of Kevlar nano-fiber and polylactic acid, the composite material is washed by deionized water and dried in a vacuum drying oven to form a film. The polylactic acid composite film has the tensile strength of 32.0 MPa, the elongation at break of 5.9 percent and the maximum thermal decomposition temperature of 369.1 ℃.
Example 5:
weighing 2g of Kevlar fiber fine wire and 3 g of potassium hydroxide, putting into a reactor, adding 400 mL of dimethyl sulfoxide solution, and magnetically stirring at 25 ℃ for 7 days to obtain a Kevlar nanofiber solution.
Weighing 10 g of polylactic acid particles with the molecular weight of 20 ten thousand, putting the polylactic acid particles into a beaker, adding 1200 mL of dimethyl sulfoxide, placing the beaker in a water bath, and heating the beaker at 80 ℃ until the polylactic acid is completely dissolved in the dimethyl sulfoxide solvent.
Measuring corresponding Kevlar nanofiber solution and polylactic acid solution according to the ratio of the Kevlar nanofiber to the polylactic acid of 9:100, and stirring for 30 min on a magnetic stirrer.
And 4 mL of deionized water is added into the mixed solution, at the moment, gel appears in the solution, and the magnetic stirring is continued for 2 hours, so that the mixed solution of the Kevlar nanofiber solution and the polylactic acid solution is uniform and stable. Then, a nylon membrane with the aperture of 0.1 mu m is adopted for vacuum filtration to obtain a composite material of Kevlar nano-fiber and polylactic acid, the composite material is washed by deionized water and dried in a vacuum drying oven to form a film. The polylactic acid composite film has the tensile strength of 34.9 MPa, the elongation at break of 6.3 percent and the maximum thermal decomposition temperature of 371.2 ℃.
Comparative example:
weighing 10 g of polylactic acid particles with the molecular weight of 5 ten thousand, putting the polylactic acid particles into a beaker, adding 5000 mL of dimethyl sulfoxide, placing the beaker in a water bath, and heating the beaker at 80 ℃ until the polylactic acid is completely dissolved in the dimethyl sulfoxide solvent.
And pouring the uniformly dissolved polylactic acid solution into a polytetrafluoroethylene surface dish, and drying in a vacuum drying oven to form a film. The polylactic acid film is tested to have the tensile strength of 14.2 MPa, the elongation at break of 3.9 percent and the maximum thermal decomposition temperature of 353.8 ℃.
Table 1 shows the data of the performance tests of examples 1 to 5 and comparative examples.
Claims (9)
1. The polylactic acid composite material containing Kevlar nano-fibers is characterized in that the weight content of the Kevlar nano-fibers in the composite material is 1-9%, and the balance is polylactic acid.
2. The composite material of claim 1, wherein the Kevlar nanofibers have a strength of 3.6 GPa, an elongation modulus of 131 GPa, an elongation at break of 2.8%, a length of 5 to 10 μm and a diameter of 3 to 30 nm.
3. The composite material of claim 1, wherein the polylactic acid has a molecular weight of 5 to 20 ten thousand.
4. A method for preparing a composite material according to any one of claims 1 to 3, comprising the steps of: (1) cutting Kevlar fiber into 1-2 cm thin sections, immersing the Kevlar fiber in a dimethyl sulfoxide solvent containing potassium hydroxide, and continuously stirring for 7 days to obtain a Kevlar nanofiber solution; (2) mixing the Kevlar nanofiber solution and the dimethyl sulfoxide solution of polylactic acid according to a certain proportion, uniformly stirring, adding a small amount of water to form gel, carrying out vacuum filtration, and carrying out vacuum drying to obtain the composite material.
5. The method according to claim 4, wherein in the step (1), the mass-to-volume ratio of the Kevlar nanofibers to the dimethyl sulfoxide solvent is 0.4-1: 200 g/mL.
6. The method according to claim 4, wherein the mass-to-volume ratio of polylactic acid to dimethyl sulfoxide in the dimethyl sulfoxide solution of polylactic acid is 0.2-0.5: 10 g/mL.
7. The method according to claim 4, wherein the Kevlar nanofiber solution and the dimethyl sulfoxide solution of polylactic acid are mixed in a mass ratio of 1-9: 100.
8. The method of claim 4, wherein the vacuum filtration is performed by using a nylon membrane, and the pore size of the nylon membrane is 0.1-0.5 μm.
9. The method of claim 4, wherein the vacuum drying temperature is 40 to 50 ℃ and the drying time is 8 to 12 hours.
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- 2019-12-27 CN CN201911379936.9A patent/CN111004485A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008160360A (en) * | 2006-12-22 | 2008-07-10 | Matsushita Electric Ind Co Ltd | Frame for speaker and speaker using same |
| CN102660097A (en) * | 2012-04-11 | 2012-09-12 | 上海交通大学 | Preparation method of reinforced polyvinyl alcohol compound |
| CN108699259A (en) * | 2015-12-30 | 2018-10-23 | 密执安州立大学董事会 | Gel containing ANF and nanocomposite |
| CN106863772A (en) * | 2017-02-27 | 2017-06-20 | 上海大学 | Double shower nozzle 3D printing system and method for thermoplastic resin base continuous fibers prepreg |
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