WO2017092233A1

WO2017092233A1 - Antibacterial polyester fiber based on silver-containing zirconium phosphate, and method for preparation thereof

Info

Publication number: WO2017092233A1
Application number: PCT/CN2016/081472
Authority: WO
Inventors: 朱美芳; 相恒学; 陈伟; 夏维; 孙宾
Original assignee: 东华大学
Priority date: 2015-12-01
Filing date: 2016-05-09
Publication date: 2017-06-08
Also published as: CN105332078A; CN105332078B

Abstract

The present invention provides an antibacterial polyester fiber based on a silver-containing zirconium phosphate, and a method for preparation thereof. The antibacterial polyester fiber based on a silver-containing zirconium phosphate is characterized in that it comprises a polyester matrix, said polyester matrix having dispersed therein a silver-containing zirconium phosphate powder. The preparation method comprises: preparing a silver-containing zirconium phosphate nanopowder; adding the silver-containing zirconium phosphate nanopowder, terephthalic acid, and a diol to a polyester reactor to prepare a silver-containing zirconium phosphate antibacterial polyester by in situ polymerization; using melt direct spinning to prepare an antibacterial polyester fiber based on a silver-containing zirconium phosphate, or pelletizing the silver-containing zirconium-phosphate antibacterial polyester to obtain a silver-containing zirconium-phosphate antibacterial polyester masterbatch, and using a masterbatch blending spinning method to prepare an antibacterial polyester fiber based on a silver-containing zirconium phosphate. The antibacterial polyester fiber prepared in the present invention has the feature of a long-lasting highly effective antibacterial function.

Description

Antibacterial polyester fiber based on silver-loaded zirconium phosphate and preparation method thereof

Technical field

The invention belongs to the field of preparation of antibacterial polyester fibers, in particular to a high-efficiency and durable antibacterial polyester fiber based on silver-loaded zirconium phosphate and a preparation method thereof.

Background technique

With the advancement of science and technology and the improvement of living standards, people's awareness of the safety protection of the living environment has increased. Among them, antibacterial coatings, antibacterial plastic household items, antibacterial clothing and home textiles have received widespread attention. In particular, in terms of safety protection against skin contact, bacteriostatic and odor-resistant are particularly important. Currently, antibacterial agents include organic antibacterial agents, organometallic antibacterial agents, compound antibacterial agents, nano metal antibacterial agents, and inorganic powder metal-loaded antibacterial agents.

Among the above antibacterial agents, silver-loaded zirconium phosphate is a hot spot of concern and application. The structure of zirconium phosphate is a three-dimensional structure in which [PO ₄ ] tetrahedron and [ZrO ₆ ] octahedron are formed by sharing oxygen atoms in the apex angle thereof, have an effective pore structure, and have a hydroxyl group on the surface. The invention patent CN 102239887 B discloses a preparation method of a nano-scale zirconium phosphate-loaded silver composite inorganic antibacterial agent; the invention patent CN 102763678 B discloses a preparation method of a cubic zirconium phosphate-loaded silver antibacterial powder; the invention patent CN 1240288 C discloses Method for preparing layered zirconium phosphate-loaded silver powder; invention patent CN 100345486 C discloses a nano-layered zirconium phosphate-loaded silver inorganic antibacterial powder and a novel preparation method thereof; the invention patent CN 1281689C discloses a modification Zirconium phosphate-supported silver powder and a preparation method thereof. The above invention patents all use the method of metal ion replacement to load silver ions in the zirconium phosphate matrix, and the preparation process is complicated.

In the field of preparation of antibacterial polyester fibers, the invention patent CN 102691129 B discloses an antibacterial polyester fiber, a production method thereof and the use thereof, which are prepared by mixing an antibacterial component with a polyester resin to prepare a masterbatch, and then melt spinning with a polyester resin. The spinning cycle is long. The national invention patent CN 101005762 B discloses the use of a zirconium phosphate or a copper-loaded zirconium phosphate or a salt to achieve an antibacterial effect by surface coating.

Summary of the invention

The technical problem to be solved by the invention is to provide a high-efficiency and durable antibacterial polyester fiber based on silver-loaded zirconium phosphate and a preparation method thereof. The silver-loaded zirconium phosphate prepared by the method has high silver content, and the preparation method is simple and easy, and the prepared antibacterial Polyester fiber has the characteristics of long-lasting antibacterial effect.

In order to solve the above technical problems, the present invention provides an antibacterial polyester fiber based on silver-loaded zirconium phosphate, characterized in that it comprises a polyester matrix in which a silver-loaded zirconium phosphate powder is dispersed.

The invention also provides a preparation method of the above-mentioned silver-loaded zirconium phosphate-based antibacterial polyester fiber, which comprises:

Step 1: Dispersing the zirconium phosphate powder and the polyfluorenyl compound in an organic solvent; then adding silver nitrate, stirring for 12 to 24 hours, removing the organic solvent by spray drying, and placing the obtained powder in an environment of 800 to 1200 ° C Calcination for 1 to 6 hours to obtain a silver-loaded zirconium phosphate nanopowder;

Step 2: Add mesoporous silver-loaded zirconium phosphate nano powder, terephthalic acid (PTA), glycol and lanthanide catalyst to the polyester reactor, and prepare the silver-loaded zirconium phosphate antibacterial polyester by in-situ polymerization. Preparation of antibacterial polyester fiber based on silver-loaded zirconium phosphate by bulk spinning, or granulation of silver-loaded zirconium phosphate antibacterial polyester to obtain silver-loaded zirconium phosphate antibacterial polyester masterbatch, prepared by master batch blending Antibacterial polyester fiber of silver zirconium phosphate.

Preferably, the silver-loaded zirconium phosphate nano powder has a silver content of 3 to 8% and a diameter of 200 to 800 nm.

Preferably, the polyhydrazino compound is one or more of ethylene glycol dimercaptoacetate, 1,3-dimercaptopropane, pentaerythritol tetradecyl acetate, and pentaerythritol tetrakis-mercaptopropionate.

Preferably, the mass ratio of the mesoporous zirconium phosphate powder, the polyfluorenyl compound and the silver nitrate is from 100:1 to 6:8-20.

Preferably, the organic solvent is one of ethanol, acetone, dichloromethane and chloroform.

Preferably, the specific step of dispersing the mesoporous zirconium phosphate powder and the polyfluorenyl compound in the organic solvent is: adding the mesoporous zirconium phosphate powder and the polyfluorenyl compound to the organic solvent, and sealing the ultrasonic dispersion 0.5 to 2 hour.

Preferably, the content of the silver-loaded zirconium phosphate in the silver-loaded zirconium phosphate antibacterial polyester masterbatch is 3% to 20%.

Preferably, the glycol is one of ethylene glycol, propylene glycol and butylene glycol.

Preferably, the conditions of the melt direct spinning are: spinning temperature 265 to 285 ° C, spinning speed 1000 ~ 4000m / min.

Preferably, the mass ratio of the silver-loaded zirconium phosphate in the silver-loaded zirconium phosphate-based antibacterial polyester fiber obtained by the melt direct spinning is 3% to 7%.

Preferably, the specific step of the masterbatch blend spinning is: granulating the silver-loaded zirconium phosphate antibacterial polyester masterbatch and the polyester chip by a twin-screw granulator, and then melt-spinning to obtain a silver-loaded zirconium phosphate Antibacterial polyester fiber.

More preferably, the mass ratio of the silver-loaded zirconium phosphate antibacterial polyester masterbatch and the polyester chip is from 1 to 10:100.

More preferably, the melt spinning conditions are a spinning temperature of 265 to 285 ° C and a spinning speed of 1000 to 4000 m/min.

Preferably, the temperature of the in-situ polymerization is 250 to 280 ° C, the polymerization pressure is controlled to 0.25 MPa, and the time is 2 to 3 hours.

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

(1) In the present invention, the polyfluorenyl compound can be efficiently dispersed in the pores and on the surface of the zirconium phosphate, and the mercapto group is first bonded to the hydroxyl group on the surface of the zirconium phosphate; when the silver nitrate is added, the unreacted mercapto group is not reacted. The silver ions can be effectively bonded, so that a large amount of silver ions enter the mesopores of the zirconium phosphate well and bond to the surface of the zirconium phosphate to form high-silver-loaded zirconium phosphate particles.

(2) After the completion of the silver-carrying task of the polyfluorenyl compound in the present invention, including the unreacted mercapto group, it can be removed in the calcination treatment.

(3) The invention adopts the method of in-situ polymerization to prepare the silver-loaded zirconium phosphate antibacterial polyester masterbatch, and the functional nanoparticles have stable performance and no discoloration in the polymerization and processing steps.

(4) The content of the silver-loaded zirconium phosphate in the antibacterial polyester masterbatch prepared by the invention is controllable, and the antibacterial polyester fiber can be prepared by means of melt direct spinning or blend spinning.

detailed description

The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are not intended to limit the scope of the invention. In addition, it should be understood that various changes and modifications may be made by those skilled in the art in the form of the present invention.

The mesoporous zirconium phosphate nanopowder used in each embodiment of the present invention is a commercially available product, and the particle size is 200 to 800 nm, and a pore diameter of 4 to 15 nm.

Example 1

An antibacterial polyester fiber based on silver-loaded zirconium phosphate, comprising a polyester matrix in which a silver-loaded zirconium phosphate powder is dispersed.

The above preparation method of the silver-loaded zirconium phosphate-based antibacterial polyester fiber is as follows:

(1) 100 g of mesoporous zirconium phosphate nanopowder and 3 g of pentaerythritol tetradecyl acetate were added to 100 mL of chloroform, and the ultrasonic dispersion (ultrasound frequency: 40 KHz) was sealed at room temperature for 2 hours; then 20 g of silver nitrate was added. Stir at 500 r/min for 24 hours. The chloroform solvent was removed by spray drying, and the obtained powder was calcined at 1200 ° C for 3 hours to obtain a silver-loaded zirconium phosphate nano powder having a silver content of 8% and a diameter of 200 to 800 nm.

(2) 200 g of silver-loaded zirconium phosphate nanopowder, 540 g of purified terephthalic acid, 260 g of ethylene glycol, and 0.2 g of ethylene glycol oxime were added to the polyester reactor to be polymerized in situ (polymerization temperature was 250-280 ° C, The polymerization pressure was controlled to 0.25 MPa, and the polymerization esterification time was 2 hours. The silver-loaded zirconium phosphate antibacterial polyester was obtained and granulated to obtain a silver-loaded zirconium phosphate antibacterial polyester masterbatch, wherein the mass ratio of the silver-loaded zirconium phosphate was 20%.

(3) The silver-loaded zirconium phosphate antibacterial polyester masterbatch and the PET resin pellet were granulated by a twin-screw granulator at a mass ratio of 1:100, granulated at a temperature of 275 ° C, and then melt-spun (spun temperature 285 ° C, An antibacterial polyester fiber was prepared at a spinning speed of 3000 m/min. The fiber has an antibacterial rate of >95% against Escherichia coli, an antibacterial rate of >90% against Staphylococcus aureus, an antibacterial rate of >60% against Candida albicans, and 20 times of water washing at 40 ° C for the above three bacteria. Antibacterial properties are maintained above 95%.

Example 2

(1) 100 g of mesoporous zirconium phosphate nanopowder and 6 g of 1,3-1,3-dimercaptopropane were added to 100 mL of dichloromethane, and the ultrasonic dispersion (ultrasound frequency: 40 KHz) was closed at room temperature for 0.5 hour; then 10 g of nitric acid was added. Silver, stirred (500r/min) for 12 hours. The dichloromethane solvent was removed by spray drying, and the obtained powder was calcined at 800 ° C for 6 hours to obtain a silver-loaded zirconium phosphate nano powder having a silver content of 4% and a diameter of 200 to 800 nm.

(2) 50 g of silver-loaded zirconium phosphate nanopowder, 640 g of purified terephthalic acid, 310 g of ethylene glycol, and 0.25 g of ethylene glycol hydrazine are added to the polyester reactor to be polymerized in situ (polymerization temperature is 250 to 280 ° C, Aggregate pressure control 0.25 MPa, polymerization esterification time 3 hours) A silver-loaded zirconium phosphate antibacterial polyester was obtained and granulated to obtain a silver-loaded zirconium phosphate antibacterial polyester masterbatch, wherein the mass ratio of the silver-loaded zirconium phosphate was 5%.

(3) The silver-loaded zirconium phosphate antibacterial polyester masterbatch and the PET resin pellet were granulated by a twin-screw granulator at a mass ratio of 1:10, granulated at a temperature of 265 ° C, and then melt-spun (spinning temperature of 280 ° C, An antibacterial polyester fiber was prepared at a spinning speed of 1000 m/min.

The fiber has an antibacterial rate of >99% against Escherichia coli, an antibacterial rate of >90% against Staphylococcus aureus, an antibacterial rate of >60% against Candida albicans, and 20 times of water washing at 40 °C for the above three bacteria. Antibacterial properties are maintained above 95%.

Example 3

(1) 100 g of mesoporous zirconium phosphate nanopowder and 1 g of ethylene glycol dimercaptoacetate were added to 100 mL of ethanol, and the ultrasonic dispersion (ultrasound frequency: 40 KHz) was sealed at room temperature for 1 hour; then 15 g of silver nitrate was added and stirred. (500r/min) for 24 hours. The ethanol was removed by spray drying, and then the obtained powder was calcined at 1200 ° C for 3 hours to obtain a silver-loaded zirconium phosphate nano powder having a diameter of 200 to 800 nm and having a silver content of 6%.

(2) 70g of silver-loaded zirconium phosphate, 583g of purified terephthalic acid, 347g of propylene glycol, and 0.25g of ethylene glycol oxime were added to the polyester reactor for in-situ polymerization (polymerization temperature was 250-280 ° C, polymerization pressure control 0.25) MPa, polymerization time 2 hours) to obtain silver-loaded zirconium phosphate antibacterial polyester, directly prepared by spinning melt spinning (spinning temperature 280 ° C, spinning speed 2000 m / min), the quality of the silver-loaded zirconium phosphate The content is 7%.

The fiber has an antibacterial rate of >97% against Escherichia coli, an antibacterial rate of >90% against Staphylococcus aureus, an antibacterial rate of >65% against Candida albicans, and 20 times of water washing at 40 °C for the above three bacteria. Antibacterial properties are maintained above 95%.

Example 4

(1) Add 100 g of mesoporous zirconium phosphate nanopowder and 5 g of 1,3-dimercaptopropane to 100 mL of C In the ketone, the ultrasonic dispersion (ultrasound frequency: 40 KHz) was sealed at room temperature for 2 hours; then 8 g of silver nitrate was added and stirred (500 r/min) for 24 hours. The acetone was removed by spray drying, and then the obtained powder was calcined at 1,100 ° C for 6 hours to obtain a silver-loaded zirconium phosphate nano powder having a diameter of 200 to 400 nm and having a silver content of 3%.

(2) Adding 30 g of silver-loaded zirconium phosphate, 570 g of purified terephthalic acid, 400 g of butanediol, and 0.26 g of ethylene glycol oxime to a polyester reactor for in-situ polymerization (polymerization temperature of 250-280 ° C, polymerization pressure) Controlling 0.25 MPa and polymerizing the esterification time for 2 hours) to obtain a silver-loaded zirconium phosphate antibacterial polyester, and directly preparing the antibacterial polyester fiber through melt direct spinning (spinning temperature: 265-285 ° C, spinning speed: 1000-4000 m/min). The mass ratio of the silver-loaded zirconium phosphate is 3%.

The fiber has an antibacterial rate of >93% against Escherichia coli, an antibacterial rate of >90% against Staphylococcus aureus, an antibacterial rate of >60% against Candida albicans, and 20 times of water washing at 40 °C for the above three bacteria. Antibacterial properties are maintained above 95%.

Claims

An antibacterial polyester fiber based on silver-loaded zirconium phosphate, characterized in that it comprises a polyester matrix in which a silver-loaded zirconium phosphate powder is dispersed.
The method for preparing a silver-loaded zirconium phosphate-based antibacterial polyester fiber according to claim 1, comprising:

Step 1: Dispersing the mesoporous zirconium phosphate powder and the polyfluorenyl compound in an organic solvent; then adding silver nitrate, stirring for 12 to 24 hours, removing the organic solvent by spray drying, and placing the obtained powder in an environment of 800 to 1200 ° C After calcination for 1 to 6 hours, a silver-loaded zirconium phosphate nanopowder is obtained;

Step 2: Adding silver-loaded zirconium phosphate nano powder, terephthalic acid (PTA), glycol and ruthenium catalyst to the polyester reactor to prepare silver-loaded zirconium phosphate antibacterial polyester by in-situ polymerization, using melt straight Spinning preparation of antibacterial polyester fiber based on silver-loaded zirconium phosphate, or granulating silver-loaded zirconium phosphate antibacterial polyester to obtain silver-loaded zirconium phosphate antibacterial polyester masterbatch, preparing silver-based phosphoric acid by master batch blending Zirconium antibacterial polyester fiber.
The method for preparing a silver-loaded zirconium phosphate-based antibacterial polyester fiber according to claim 2, wherein the silver-loaded zirconium phosphate nanopowder has a silver content of 3 to 8% and a diameter of 200 to 800 nm.
The method for preparing a silver-loaded zirconium phosphate-based antibacterial polyester fiber according to claim 2, wherein the polyhydrazino compound is ethylene glycol dimercaptoacetate, 1,3-dimercaptopropane, and pentaerythritol. One or more of thioglycolate and pentaerythritol tetrakis-mercaptopropionate.
The method for preparing a silver-loaded zirconium phosphate-based antibacterial polyester fiber according to claim 2, wherein the mesoporous zirconium phosphate powder, the polythiol compound and the silver nitrate have a mass ratio of 100:1 to 6 : 8 to 20.
The method for preparing a silver-loaded zirconium phosphate-based antibacterial polyester fiber according to claim 2, wherein the content of the silver-loaded zirconium phosphate in the silver-loaded zirconium phosphate antibacterial polyester masterbatch is 3% to 20 %.
The method according to claim 2, wherein the diol is one of ethylene glycol, propylene glycol and butylene glycol.
The method for preparing a silver-loaded zirconium phosphate-based antibacterial polyester fiber according to claim 2, wherein the silver-loaded zirconium phosphate in the silver-loaded zirconium phosphate-based antibacterial polyester fiber obtained by direct melt spinning The mass content is 3% to 7%.