CN106609400B - A kind of preparation method of multi-functional acid fiber by polylactic - Google Patents

Abstract

The invention discloses a preparation method of multifunctional polylactic acid fiber, which belongs to the technical field of preparation of functional materials and functional fibers. The method includes the following steps: Step 1: Incorporate functional metal ions into α-ZrP through ion exchange to form functional α-ZrP, and then use KH550 to modify the functional α-ZrP to acidify the carbon material to obtain acidified Carbon material, using E51 epoxy modifier to modify the acidified carbon material to obtain a modified carbon material, adding functional α-ZrP modified by KH550 to the modified carbon material to form polycarbonate Functional nano-clusters; the second step: the multi-functional nano-clusters and polylactic acid matrix are blended and granulated at 180-230°C, dried, and finally spun into multi-functional polylactic acid fibers by melt spinning. The antibacterial guest component in the multifunctional polylactic acid fiber has less added amount, uniform dispersion, long-lasting function and easy operation.

Description

A kind of preparation method of multifunctional polylactic acid fiber

technical field

The invention belongs to the technical field of preparation of functional materials and functional fibers, and in particular relates to a preparation method of multifunctional polylactic acid fibers.

Background technique

At present, there are more and more varieties of polylactic acid fiber functionalization, and the realization methods are different according to different functions. For example, in order to realize the functionalization of polylactic acid fiber, the common methods are surface modification technology and blending modification technology. However, with the development of society, it becomes more and more difficult for a single function to meet the multi-field and multi-functional requirements.

Patent CN101942759A is to add fibers to a solution containing silver nitrate to absorb silver nitrate in the solution, and then reduce the fibers after absorbing silver nitrate to obtain antibacterial fibers or fabrics with silver attached to the surface. This method cannot form a uniform and stable antibacterial coating, and the antibacterial time is limited, so it cannot achieve durable antibacterial. The whole process is too complicated and easily pollutes the environment. The latter is to add the antibacterial component directly or after modification to the polymer, prepare antibacterial masterbatch through screw extrusion, and then prepare antibacterial fiber through melt spinning technology. Patent CN103038403A prepares polyester fiber with wear resistance function by performing relaxation heat treatment within a specific range after stretching treatment. Patent CN103710963A provides multi-functionality for the polyester matrix by adding a variety of inorganic nanopowders with high content. This method is difficult to disperse due to high addition amount, and the effect is poor.

Contents of the invention

The object of the present invention is to provide a preparation method of multifunctional polylactic acid fiber, the addition of antibacterial guest components in the multifunctional polylactic acid fiber is small, evenly dispersed, durable in function, and easy to operate.

In order to achieve the above object, the invention provides a kind of preparation method of multifunctional polylactic acid fiber, comprises the following steps:

Step 1: Put functional metal ions into α-ZrP through ion exchange to form functional α-ZrP, then use KH550 to modify functional α-ZrP, acidify the carbon material to obtain acidified carbon material, use E51 epoxy modifier modifies the acidified carbon material to obtain a modified carbon material, and the functional α-ZrP modified by KH550 is added to the modified carbon material to form a multifunctional nano-cluster ;

The second step: blending and granulating the multifunctional nano-clusters and the polylactic acid matrix at 180-230° C., drying, and finally spinning into multifunctional polylactic acid fibers by melt spinning.

Preferably, the functional metal ion is at least one of copper chloride, copper sulfate, copper nitrate, silver nitrate and germanium chloride.

Preferably, the carbon material is at least one of carbon nanotubes, nano-carbon black and nano-graphite.

Preferably, the mass ratio of the KH550 modified functional α-ZrP to the modified carbon material is 1:1-10.

Preferably, the size of the multifunctional nanoclusters is 300-700 nm.

Preferably, the mass ratio of the multifunctional nano-clusters to the polylactic acid matrix is 0.5-3:99.5-97.

Compared with the prior art, the beneficial effects of the present invention are as follows:

(1) The functional metal ions were introduced into α-ZrP by ion exchange, realizing the loading of α-ZrP on functional metal ions; and the compatibility of α-ZrP with the polymer matrix was increased by KH550 modification, and at the same time, it was A large number of amino groups were introduced into the surface of α-ZrP;

(2) E51 is used to modify the acidified nano-carbon material, which increases the compatibility between the carbon material and the matrix, and provides a large number of epoxy groups for the surface of the carbon material;

(3) The obtained multifunctional nanoclusters can add multiple functions at one time with a small amount of added, long-lasting functions, and does not affect the forming of polymer nanomaterials;

(4) The method is simple, efficient, low-cost, durable in effect and broad in application prospects;

(5) The prepared multifunctional polylactic acid fiber can be effectively used in home textiles, clothing, large aircraft, high-speed rail and other interiors, astronaut clothing, military combat clothing, etc. Through the industrialization of the multifunctional polylactic acid fiber of the present invention, the gap in domestic multifunctional fiber preparation technology can be effectively filled.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

The zirconium phosphate nano-powder in each embodiment of the present invention is a commercially available product with a particle size of 100-700 nm, and the nano-carbon powder is a commercially available product with a carbon nanotube length of 200-700 nm and a nano-carbon black particle size of 100 nm. -500 nm, the particle size of nano-graphite is 200-700 nm.

Example 1:

A kind of preparation method of multifunctional polylactic acid fiber, concrete steps are:

The first step: Add 19.5g α-ZrP to 100 ml tetrahydrofuran, ultrasonically and mechanically stir, the ultrasonic power is 50W, the time is 20min; the speed of mechanical stirring is 200r/min, the time is 20min; 1.7g copper chloride is added In the solution, react for 6h; dropwise add the silane coupling agent KH550 to continue the reaction, the mass ratio of the amount of KH550 added to α-ZrP is 0.5:1; add nitric acid with a mass fraction of 80% to treat the multi-walled carbon nanotubes; the reaction temperature at 80°C, and the reaction time was 12 h. E51 was added to modify the acidified multi-walled carbon nanotubes; the molar ratio of acidified carbon material to epoxy modifier E51 was 1:5, the reaction temperature was 80 °C, and the reaction time was 12 h. The molar ratio of epoxy-modified multi-walled carbon nanotubes to KH550-α-ZrP is 1:1; the temperature is raised to 80°C, and the reaction is continued for 16h; washed with acetone for 3 times, and dried in a filter vacuum oven at 60°C for 12h;

The second step: blend and granulate the above-mentioned multifunctional nano-clusters and polylactic acid at a mass ratio of 3:97 at 180°C~230°C, dry them, and finally perform melt spinning (spinning temperature is 210~260°C ) spun into multifunctional polylactic acid fibers. The size of the multifunctional powder in the fiber is 300-700 nm. The antibacterial rate of the fiber against Escherichia coli is >90%, the antibacterial rate against Staphylococcus aureus is >85%, and the antibacterial rate against Candida albicans is >60%. The washing resistance of the fabric is more than 80 times. The volume resistivity of the fiber is less than 108Ω·cm.

Example 2:

A kind of preparation method of multifunctional polylactic acid fiber, concrete steps are:

The first step: Add 19.5g α-ZrP to 100 ml DMF, ultrasonically and mechanically stir, the ultrasonic power is 35W, the time is 60 min; the speed of mechanical stirring is 300r/min, the time is 15min; 1.6g copper sulfate is added In the solution, react for 12 h; dropwise add silane coupling agent KH550 to continue the reaction, the mass ratio of the amount of KH550 added to α-ZrP is 1:1; add nitric acid with a mass fraction of 80% to treat the multi-walled carbon nanotubes; react The temperature was 75°C, and the reaction time was 24 h. E51 was added to modify the acidified multi-walled carbon nanotubes; the molar ratio of acidified carbon material to epoxy modifier E51 was 1:5, the reaction temperature was 75 °C, and the reaction time was 24 h. The molar ratio of epoxy-modified multi-walled carbon nanotubes to KH550-α-ZrP is 1:1; the temperature is raised to 80°C, and the reaction is continued for 16h; washed with acetone for 3 times, and dried in a filter vacuum oven at 60°C for 12h;

The second step: blend and granulate the above-mentioned multifunctional nano-clusters and polylactic acid at a mass ratio of 2:98 at 180°C~230°C, dry them, and finally perform melt spinning (spinning temperature is 210~260°C ) spun into multifunctional polylactic acid fibers. The size of the multifunctional powder in the fiber is 500-700 nm. The antibacterial rate of the fiber against Escherichia coli is >85%, the antibacterial rate against Staphylococcus aureus is >80%, and the antibacterial rate against Candida albicans is >60%. The washing resistance of the fabric is more than 80 times. The volume resistivity of the fiber is less than 108Ω·cm.

Example 3:

A kind of preparation method of multifunctional polylactic acid fiber, concrete steps are:

Step 1: Add 19.5g α-ZrP to 100 ml tetrahydrofuran, ultrasonically and mechanically stir, the ultrasonic power is 50W, and the time is 30min; the speed of mechanical stirring is 300r/min, and the time is 30min; 0.85g silver nitrate is added to the solution During the reaction for 18 h; the silane coupling agent KH550 was added dropwise to continue the reaction, and the mass ratio of the amount of KH550 added to α-ZrP was 1:1; the mass fraction of 80% was added to treat nano-carbon black with nitric acid; the reaction temperature was 80 °C, and the reaction time was 12 h. E51 was added to modify acidified nano-carbon black; the molar ratio of acidified carbon material to epoxy modifier E51 was 1:5, the reaction temperature was 80 °C, and the reaction time was 24 h. The molar ratio of epoxy-modified multi-walled carbon nanotubes to KH550-α-ZrP is 1:1; the temperature is raised to 80°C, and the reaction is continued for 16 hours; washed with acetone for 3 times, and dried in a filter vacuum oven at 60°C for 12 hours ;

The second step: blend and granulate the above-mentioned multifunctional nano-clusters and polylactic acid at a mass ratio of 3:97 at 180°C~230°C, dry them, and finally perform melt spinning (spinning temperature is 210~260°C ) spun into multifunctional polylactic acid fibers. The size of the multifunctional powder in the fiber is 200-500 nm. The antibacterial rate of the fiber against Escherichia coli is >90%, the antibacterial rate against Staphylococcus aureus is >90%, and the antibacterial rate against Candida albicans is >70%. The washing resistance of the fabric is more than 80 times. The volume resistivity of the fiber is less than 109Ω·cm.

Example 4:

A kind of preparation method of multifunctional polylactic acid fiber, concrete steps are:

The first step: Add 39g α-ZrP to 100 ml DMF, ultrasonically and mechanically stir, the ultrasonic power is 35 W, the time is 60min; the speed of mechanical stirring is 300r/min, the time is 60min; 1.35g copper chloride and 0.11g of germanium chloride were added to the solution, and reacted for 12 h; the silane coupling agent KH550 was added dropwise to continue the reaction, and the mass ratio of the amount of KH550 added to α-ZrP was 1:1; Multi-walled carbon nanotubes; the reaction temperature is 75°C, and the reaction time is 18 h. E51 was added to modify the acidified multi-walled carbon nanotubes; the molar ratio of acidified carbon material to epoxy modifier E51 was 1:10, the reaction temperature was 75 °C, and the reaction time was 24 h. The molar ratio of epoxy-modified multi-walled carbon nanotubes to KH550-α-ZrP is 1:1; the temperature is raised to 80°C, and the reaction is continued for 16h; washed with acetone for 3 times, and dried in a filter vacuum oven at 60°C for 12h;

The second step: blend and granulate the above-mentioned multifunctional nano-clusters and polylactic acid at a mass ratio of 2:98 at 250°C~275°C, dry them, and finally perform melt spinning (spinning temperature is 270~290°C ) spun into multifunctional polylactic acid fibers. The size of the multifunctional powder in the fiber is 300-700 nm. The antibacterial rate of the fiber against Escherichia coli is >90%, the antibacterial rate against Staphylococcus aureus is >85%, and the antibacterial rate against Candida albicans is >60%. The washing resistance of the fabric is more than 80 times. The volume resistivity of the fiber is less than 10 ⁸ Ω·cm. The amount of negative ions produced by friction method is 400-1000 per cubic centimeter.

Example 5:

A kind of preparation method of multifunctional polylactic acid fiber, concrete steps are:

The first step: 39 g α-ZrP was added to 100 ml tetrahydrofuran, ultrasonically and mechanically stirred, the ultrasonic power was 50W, and the time was 30min; the speed of mechanical stirring was 300r/min, and the time was 30min; 1.7g silver nitrate and 0.2 g germanium chloride was added to the solution and reacted for 12 h; the silane coupling agent KH550 was added dropwise to continue the reaction, the mass ratio of the amount of KH550 added to α-ZrP was 0.5:1; the mass fraction of 60% nitric acid was added to treat nano-graphite ; The reaction temperature was 80°C, and the reaction time was 24 h. E51 modified acidified nano-graphite was added; the molar ratio of acidified carbon material to epoxy modifier E51 was 1:10, the reaction temperature was 80 °C, and the reaction time was 18 h. The molar ratio of epoxy-modified multi-walled carbon nanotubes to KH550-α-ZrP is 1:1; the temperature is raised to 80°C, and the reaction is continued for 16h; washed with acetone for 3 times, and dried in a filter vacuum oven at 60°C for 12h;

Step 2: Blend and granulate the above-mentioned multifunctional nano-clusters and polylactic acid at a mass ratio of 0.5:99.5 at 180°C~230°C, dry them, and finally perform melt spinning (spinning temperature is 210~260°C ) spun into multifunctional polylactic acid fibers. The size of the multifunctional powder in the fiber is 500-700 nm. The antibacterial rate of the fiber against Escherichia coli is >95%, the antibacterial rate against Staphylococcus aureus is >90%, and the antibacterial rate against Candida albicans is >70%. The washing resistance of the fabric is more than 80 times. The volume resistivity of the fiber is less than 10 ¹⁰ Ω·cm. The amount of negative ions produced by friction method is 400-1000 per cubic centimeter.

Claims (6)

1. a preparation method of multifunctional polylactic acid fiber, is characterized in that comprising the following steps: Step 1: Put functional metal ions into α-ZrP through ion exchange to form functional α-ZrP, then use KH550 to modify functional α-ZrP, acidify the carbon material to obtain acidified carbon material, use E51 epoxy modifier modifies the acidified carbon material to obtain a modified carbon material, and the functional α-ZrP modified by KH550 is added to the modified carbon material to form a multifunctional nano-cluster ; The second step: blending and granulating the multifunctional nano-clusters and the polylactic acid matrix at 180-230° C., drying, and finally spinning into multifunctional polylactic acid fibers by melt spinning. 2. the preparation method of a kind of multifunctional polylactic acid fiber according to claim 1 is characterized in that described functional metal ion is at least in copper chloride, copper sulfate, copper nitrate, silver nitrate and germanium chloride A sort of. 3. the preparation method of a kind of multifunctional polylactic acid fiber according to claim 1 is characterized in that described carbon material is at least one in carbon nanotube, nano carbon black and nano graphite. 4. the preparation method of a kind of multifunctional polylactic acid fiber according to claim 1 is characterized in that the functional α-ZrP of described KH550 modification and the mass ratio of the carbon material of modification are 1:1- 10. 5. The preparation method of a kind of multifunctional polylactic acid fiber according to claim 1, characterized in that the size of the multifunctional nano-clusters is 300-700 nm. 6. the preparation method of a kind of multifunctional polylactic acid fiber according to claim 1 is characterized in that the mass ratio of described multifunctional nano-clusters and polylactic acid matrix is 0.5-3:99.5-97.