WO2017092234A1

WO2017092234A1 - Mesoporous zirconium-phosphate loaded nano-silver antibacterial polyester fiber and method for preparation thereof

Info

Publication number: WO2017092234A1
Application number: PCT/CN2016/081473
Authority: WO
Inventors: 朱美芳; 周家良; 陈伟; 俞森龙; 孙宾; 周哲
Original assignee: 东华大学
Priority date: 2015-12-01
Filing date: 2016-05-09
Publication date: 2017-06-08
Also published as: CN105332087B; CN105332087A

Abstract

Provided is a mesoporous zirconium-phosphate loaded nano-silver antibacterial polyester fiber and method for preparation thereof. The mesoporous zirconium-phosphate loaded nano-silver antibacterial polyester fiber comprises a polyester matrix; said polyester matrix has dispersed therein a Ag@ mesoporous zirconium phosphate. The method for preparing the mesoporous zirconium-phosphate loaded nano-silver antibacterial polyester fiber comprises: preparing a silver @ mesoporous zirconium phosphate sol precursor; the described silver @ mesoporous zirconium phosphate sol precursor, terephthalic acid (PTA), a diol, a stabilizing agent, and a catalyst are added in proportion to a polyester reactor; performing in situ polymerization and oxidation-reduction reaction to prepare a mesoporous zirconium phosphate-nano-silver antibacterial composite material, and drying and performing melt spinning to make a mesoporous zirconium-phosphate loaded nano-silver antibacterial polyester fiber.

Description

[Invention name established by ISA according to Rule 37.2] Mesoporous zirconium phosphate loaded nano silver antibacterial polyester fiber and preparation method thereof

Technical field

The invention belongs to the field of preparation of antibacterial fibers, in particular to a mesoporous zirconium phosphate loaded nano silver antibacterial polyester fiber and a preparation method thereof.

Background technique

The ecological environment such as extreme environment and environmental pollution in today's society is seriously deteriorating, and the special living micro-environment such as confined space leads to the urgent demand for functional protective textiles. At present, the fibers for preparing textiles do not have antibacterial ability, and under certain conditions, the bacteria are provided with an environment for survival and reproduction, which threatens human health. The main method for solving the fiber antibacterial problem is to prepare a modified fiber having an antibacterial effect by using a nanoparticle having an antibacterial effect and a polymer matrix to be compositely modified. The fiber will gradually release the antibacterial component during use to achieve the purpose of antibacterial. At present, antibacterial fiber is widely used and has a large demand. However, the current technology cannot effectively solve the problems of excessive addition of functional components, difficulty in dispersion, unstable high-temperature processing, and low production rate of continuous production, resulting in the inability of antibacterial fibers to form an effective scale. Production is difficult to meet the broad needs of the current market.

At present, the main method for realizing the antibacterial function of fibers is through surface modification technology and blend modification technology. The former is to make the antibacterial component adhere to the surface of the fiber or the fabric by forming a chemical bond with the surface of the fiber or the fabric by the antibacterial component, thereby achieving an antibacterial effect. Patent CN101942759A is a silver nitrate which is added to an adsorption solution of a fiber in a solution containing silver nitrate, and an antibacterial fiber or fabric having a surface-attached silver obtained by reduction of the adsorbed fiber. This method does not form a uniform and stable antibacterial coating, and the antibacterial time is limited, and the antibacterial effect cannot be achieved. The whole process is too complicated and it is easy to pollute the environment. In the latter, the antibacterial component is directly or modified and added to the polymer, and the antibacterial masterbatch is prepared by screw extrusion, and the antibacterial fiber is prepared by melt spinning. The patent CN101440533 is an antibacterial component by using nano bamboo charcoal and nano silver as an antibacterial component, and is prepared by using one of polyester or polypropylene or nylon as a carrier, and preparing antibacterial fiber by screw extrusion. However, this method has a large addition amount and an uneven distribution of the antibacterial components, and it is difficult to achieve continuous production.

Summary of the invention

The object of the present invention is to provide an antibacterial polyester fiber with a small amount of antibacterial component added and uniform distribution Its preparation method.

In order to achieve the above object, the present invention provides a mesoporous zirconium phosphate-loaded nanosilver antibacterial polyester fiber characterized by comprising a polyester matrix in which Ag@ mesoporous zirconium phosphate is dispersed.

Preferably, the Ag@ mesoporous zirconium phosphate has a size of 200 to 700 nm.

Preferably, the mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is from 0.5:99.5 to 3:97.

Preferably, the polyester matrix is one of polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate.

The invention also provides the preparation method of the above-mentioned mesoporous zirconium phosphate-loaded nano silver antibacterial polyester fiber, characterized in that the specific steps include:

The first step: treating mesoporous zirconium phosphate with fuming sulfuric acid to obtain mesoporous zirconium phosphate having a sulfonic acid group on the surface, and ultrasonically stirring the silver ion compound and the diol to obtain a sol containing silver ions, and the surface is coated a mesoporous zirconium phosphate having a sulfonic acid group is added to a sol containing silver ions, and stirred at 20 to 100 ° C for 1 to 3 hours to obtain a silver@mesoporous zirconium phosphate sol precursor;

Step 2: The above-mentioned silver@mesoporous zirconium phosphate sol precursor, terephthalic acid (PTA), glycol, stabilizer and catalyst are added to the polyester reactor in proportion for in-situ polymerization and redox reaction. Preparation of mesoporous zirconium phosphate-nanosilver antibacterial composite material, drying and spinning into mesoporous zirconium phosphate loaded nano silver antibacterial polyester fiber by melt spinning

Preferably, the specific step of treating mesoporous zirconium phosphate by using fuming sulfuric acid is: the mass fraction of fuming sulfuric acid is 50% to 98%, the reaction temperature is 40-80 ° C, and the reaction time is 20-80 min.

Preferably, the mesoporous zirconium phosphate having a sulfonic acid group on the surface, the mass ratio of the silver ion compound to the glycol is from 60 to 90:0.5 to 5:5 to 39.5.

Preferably, the silver ion compound is one or more of silver chloride, silver bromide, silver iodide, silver hydroxide, silver sulfide, and silver sulfate.

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

Preferably, the reaction process of the in-situ polymerization and the redox reaction is 180-240 ° C, 300 Kpa, and the reaction is carried out for 2-5 h under N ₂ atmosphere, and the reaction is carried out for 2-6 h under conditions of 260-285 ° C and less than 150 Pa.

The antibacterial fiber prepared by the invention is based on conventional polymer polymerization, using a compound containing silver as a precursor of an antibacterial component, and adding a sol to a polymerization system by using a sol to form a sol, using a sulfonated mesoporous zirconium phosphate Adsorption of pores and ionic bonding of sulfonic acid groups with silver ions to make mesoporous zirconium phosphate pores Silver ions are supported on the surface, and nano-silver is formed by in-situ oxidation reduction in the polymerization process to prepare a nano-silver antibacterial composite.

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

(1) The pore adsorption of the sulfonated mesoporous zirconium phosphate and the ionic bond between the sulfonic acid group and the silver ion in the present invention, so that the mesoporous zirconium phosphate pores and the surface are loaded with silver ions, thereby realizing silver ions in mesoporous zirconium phosphate The payload in .

(2) The mesoporous zirconium phosphate of the present invention supports silver ions, and the formation of nano silver and the formation of functional composite materials are realized in one step by using reaction heat in the polymerization process, thereby realizing good dispersion of the antibacterial functional components in the matrix.

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

(4) The method of the invention has simple operation, high efficiency, low cost, long-lasting utility and broad application prospect. The antibacterial fiber prepared by the invention can be effectively applied in the fields of masks, home textiles, garments, large airplanes, high-speed rails, astronauts, military combat apparel and the like. The industrialization of the antibacterial fiber of the invention can effectively fill the blank of the domestic antibacterial fiber preparation technology.

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 in each of the embodiments of the present invention is a commercially available product having a particle diameter of 100 to 700 nm and a pore diameter of 10 to 60 nm.

Example 1

A mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber comprising a PET polyester matrix, wherein the polyester matrix is dispersed with Ag@ mesoporous zirconium phosphate, and the size of the Ag@ mesoporous zirconium phosphate is 200 to 700 nm. The mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is 3:97.

The preparation method of the above-mentioned mesoporous zirconium phosphate-loaded nano silver antibacterial polyester fiber, the specific steps are as follows:

(1) Treatment of mesoporous zirconium phosphate with sulfonic acid groups by treating mesoporous zirconium phosphate with fuming sulfuric acid. The specific steps of treating mesoporous zirconium phosphate with fuming sulfuric acid are: sulphuric acid with a mass fraction of 98% The pore zirconium phosphate mass ratio was 10:1, the reaction temperature was 40 ° C, and the reaction was carried out for 20 min.

(2) taking silver nitrate, ethylene glycol and mesoporous zirconium phosphate with a sulfonic acid group at a mass ratio of 0.5:39.5:60, adding silver nitrate and ethylene glycol at room temperature, stirring ultrasonic speed to 400 rpm, and ultrasonic ( Frequency 35KHZ, output power 80%) 2h, a sol containing silver ions was obtained, and the mesoporous zirconium phosphate having a sulfonic acid group on the surface was added to a sol containing silver ions, and stirred at 30 ° C for 2 hours to obtain silver. @Mesoporous zirconium phosphate sol precursor;

(3) The above-mentioned silver@mesoporous zirconium phosphate sol precursor mass fraction is 3%, purified terephthalic acid (PTA), ethylene glycol mass fraction is 32%, stabilizer dimethyl phosphate mass fraction is 50 ppm, and catalyst The ethylene glycol oxime is 300 ppm, and the sum of the mass fractions of the above raw materials is 100%, and is added to the polyester reactor in proportion for in-situ polymerization and redox reaction (reaction process is 230 ° C, 300 kpa reaction 2 h; 275 ° C, 150 pa) Reaction 2h) Preparation of mesoporous zirconium phosphate-nanosilver antibacterial composite sections, drying, controlling the water content of 50-100ppm (mass content), spinning into mesopores by melt spinning method (spinning temperature of 270 ~ 285 ° C) Zirconium phosphate loaded nano-silver antibacterial polyester fiber. The fiber has an antibacterial rate of >95% against Escherichia coli, an antibacterial rate of >90% against Staphylococcus aureus, and an antibacterial rate of >60% against Candida albicans. The number of washable fabrics is >100 times.

Example 2

A mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber comprising a PBT polyester matrix, wherein the polyester matrix is dispersed with Ag@ mesoporous zirconium phosphate, and the size of the Ag@ mesoporous zirconium phosphate is 200 to 700 nm. The mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is 3:97.

(1) Treating mesoporous zirconium phosphate with sulfonic acid group on the surface by using fuming sulfuric acid to treat mesoporous zirconium phosphate. The specific steps of treating mesoporous zirconium phosphate with fuming sulfuric acid are: sulphuric acid with a mass fraction of 50% The pore zirconium phosphate mass ratio was 10:1, the reaction temperature was 40 ° C, and the reaction was carried out for 80 min. .

(2) taking silver nitrate, ethylene glycol and mesoporous zirconium phosphate with a sulfonic acid group at a mass ratio of 0.5:5:94.5, adding silver nitrate and ethylene glycol at room temperature, stirring ultrasonic speed to 300 rpm, and ultrasonic ( Frequency 35KHZ, output power 100%) 1h, a sol containing silver ions was obtained, and the mesoporous zirconium phosphate having a sulfonic acid group on the surface was added to a sol containing silver ions, and stirred at 80 ° C for 1 h to obtain silver. @Mesoporous zirconium phosphate sol precursor;

(3) The above-mentioned silver@mesoporous zirconium phosphate sol precursor (mass fraction 3%), purified terephthalic acid (PTA), butanediol (mass fraction 32%), stabilizer dimethyl phosphate (quality) The fraction is 50ppm) and the catalyst ethylene glycol oxime (mass fraction is 300ppm), the sum of the mass fractions of the above raw materials is 100%, according to The ratio was added to the polyester reactor for in-situ polymerization and redox reaction (220 ° C, 300 kpa reaction for 3 h; 280 ° C, 130 pa reaction for 2 h) to prepare mesoporous zirconium phosphate-nanosilver antibacterial composite sections, dried, and controlled moisture content at 50 When it is ~100 ppm (mass content), it is spun into a mesoporous zirconium phosphate-loaded nanosilver antibacterial polyester fiber by a melt spinning method (spinning temperature of 240 to 260 ° C). The fiber has an antibacterial rate of >98% against Escherichia coli, an antibacterial rate of >91% against Staphylococcus aureus, and an antibacterial rate of >70% against Candida albicans. The number of washable fabrics is >100 times.

Example 3

A mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber comprising a PET polyester matrix, wherein the polyester matrix is dispersed with Ag@ mesoporous zirconium phosphate, and the size of the Ag@ mesoporous zirconium phosphate is 200 to 700 nm. The mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is 0.5:99.5.

(2) taking silver sulfate, propylene glycol and mesoporous zirconium phosphate with a sulfonic acid group at a mass ratio of 5:39.5:54.5, and adding silver sulfate and propylene glycol at room temperature to stir the fuming sulfuric acid with an ultrasonic mass fraction of 80%. The mass ratio of mesoporous zirconium phosphate is 20:1, the reaction temperature is 50 ° C, and the reaction is carried out for 60 min to obtain a sol containing silver ions, and the mesoporous zirconium phosphate having a sulfonic acid group on the surface is added to the sol containing silver ions. , stirring at 40 ° C for 3 h, obtaining a silver @ mesoporous zirconium phosphate sol precursor;

(3) The above silver@mesoporous zirconium phosphate sol precursor (mass fraction 0.5%), purified terephthalic acid (PTA), ethylene glycol (mass fraction 33%), stabilizer trimethyl phosphate (quality) The fraction is 50ppm) and the catalyst ethylene glycol oxime (mass fraction is 300ppm), the sum of the mass fractions of the above raw materials is 100%, and is added to the polyester reactor in proportion for in-situ polymerization and redox reaction (225°C, 300kpa) Reaction 2h; 280 ° C, 100pa reaction 1.5h) Preparation of mesoporous zirconium phosphate-nanosilver antibacterial composite sections, drying, control of water content of 50 ~ 100ppm (mass content), by melt spinning method (spinning conditions of 275 ~ 290 ° C) spun into mesoporous zirconium phosphate loaded nano-silver antibacterial polyester fiber. The fiber has an antibacterial rate of >90% against Escherichia coli, an antibacterial rate of >88% against Staphylococcus aureus, and an antibacterial rate of >65% against Candida albicans. The number of washable fabrics is >80 times.

Example 4

A mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber, including a PTT polyester matrix, said poly Ag@ mesoporous zirconium phosphate is dispersed in the ester matrix, and the Ag@ mesoporous zirconium phosphate has a size of 200 to 700 nm. The mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is 0.5:99.5.

(1) Treatment of mesoporous zirconium phosphate with sulfonic acid groups by treating mesoporous zirconium phosphate with fuming sulfuric acid. The specific steps of treating mesoporous zirconium phosphate with fuming sulfuric acid are: sulphuric acid with a mass fraction of 98% The pore zirconium phosphate mass ratio was 10:1, the reaction temperature was 80 ° C, and the reaction was carried out for 40 min.

(2) taking silver sulfate, butanediol and mesoporous zirconium phosphate with a sulfonic acid group at a mass ratio of 5:5:90, adding silver sulfate and butanediol at room temperature, stirring ultrasonic speed to 200 rpm, and ultrasonic ( Frequency 53KHZ, output power 70%) 1.5h, a sol containing silver ions was obtained, and the mesoporous zirconium phosphate having a sulfonic acid group on the surface was added to a sol containing silver ions, and stirred at 50 ° C for 2 h to obtain Silver@mesoporous zirconium phosphate sol precursor;

(3) The above silver@mesoporous zirconium phosphate sol precursor (mass fraction 0.5%), purified terephthalic acid (PTA), propylene glycol (mass fraction 33%), stabilizer trimethyl phosphate (mass fraction (50ppm)) and the catalyst ethylene glycol oxime (mass fraction: 300ppm), the sum of the mass fractions of the above raw materials is 100%, and is added to the polyester reactor in proportion for in-situ polymerization and redox reaction (210 ° C, 300 kPa) Reaction 3h; 285 ° C, 150pa reaction 3h) Preparation of mesoporous zirconium phosphate-nanosilver antibacterial composite sections, drying, control of water content of 50 ~ 100ppm (mass content), by melt spinning method (spinning conditions of 235 ~ 255 °C) Spinning into mesoporous zirconium phosphate loaded nanosilver antibacterial polyester fiber. The fiber has an antibacterial rate of >90% against Escherichia coli, an antibacterial rate of >90% against Staphylococcus aureus, and an antibacterial rate of >65% against Candida albicans. The number of washable fabrics is >80 times.

Example 5

A mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber comprising a PET polyester matrix, wherein the polyester matrix is dispersed with Ag@ mesoporous zirconium phosphate, and the size of the Ag@ mesoporous zirconium phosphate is 200 to 700 nm. The mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is 2:98.

(1) Treatment of mesoporous zirconium phosphate with sulfonic acid group by treatment of mesoporous zirconium phosphate with fuming sulfuric acid. The specific steps of treating mesoporous zirconium phosphate with fuming sulfuric acid are: sulphuric acid with a mass fraction of 75% The pore zirconium phosphate mass ratio was 20:1, the reaction temperature was 40 ° C, and the reaction was carried out for 80 min.

(2) taking silver nitrate, isosorbide and mesoporous zirconium phosphate with a sulfonic acid group at a mass ratio of 0.5:39.5:60, adding silver nitrate and isosorbide at room temperature, stirring ultrasonic speed to 400 rpm, ultrasonic ( Frequency Rate 53KHZ, output power 100%) 2h, to obtain a sol containing silver ions, the mesoporous zirconium phosphate with a sulfonic acid group on the surface was added to a sol containing silver ions, and stirred at 75 ° C for 2 h to obtain silver. @Mesoporous zirconium phosphate sol precursor;

(3) The above-mentioned silver@mesoporous zirconium phosphate sol precursor mass fraction is 2%), purified terephthalic acid (PTA), ethylene glycol (mass fraction (33%), stabilizer dimethyl phosphate (mass fraction) 50 ppm)) and the catalyst ethylene glycol (mass fraction (300 ppm), the sum of the mass fractions of the above raw materials is 100%, and is added to the polyester reactor in proportion for in-situ polymerization and redox reaction (235 ° C, 300kpa reaction for 2.5h; 280°C, 100pa reaction for 2h) Preparation of mesoporous zirconium phosphate-nanosilver antibacterial composite sections, drying, control of water content of 50-100ppm (mass content), by melt spinning method (spinning condition is 270) ～285°C) is spun into mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber. The fiber has an antibacterial rate of >99% against Escherichia coli, an antibacterial rate of >95% against Staphylococcus aureus, and an antibacterial rate against Candida albicans. >70%. Washing times of fabrics >100 times.

Claims

A mesoporous zirconium phosphate-loaded nanosilver antibacterial polyester fiber characterized by comprising a polyester matrix in which Ag@ mesoporous zirconium phosphate is dispersed.
The mesoporous zirconium phosphate-loaded nanosilver antibacterial polyester fiber according to claim 1, wherein the Ag@ mesoporous zirconium phosphate has a size of 200 to 700 nm.
The mesoporous zirconium phosphate-loaded nanosilver antibacterial polyester fiber according to claim 1, wherein the mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is from 0.5:99.5 to 3:97.
The mesoporous zirconium phosphate-loaded nanosilver antibacterial polyester fiber according to claim 1, wherein the polyester matrix is polyethylene terephthalate, polybutylene terephthalate and polypair. One of propylene terephthalate.
The method for preparing a mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber according to any one of claims 1 to 4, wherein the specific steps include:

The first step: treating mesoporous zirconium phosphate with fuming sulfuric acid to obtain mesoporous zirconium phosphate having a sulfonic acid group on the surface, and ultrasonically stirring the silver ion compound and the diol to obtain a sol containing silver ions, and the surface is coated a mesoporous zirconium phosphate having a sulfonic acid group is added to a sol containing silver ions, and stirred at 20 to 100 ° C for 1 to 3 hours to obtain a silver@mesoporous zirconium phosphate sol precursor;

Step 2: The above-mentioned silver@mesoporous zirconium phosphate sol precursor, terephthalic acid (PTA), glycol, stabilizer and catalyst are added to the polyester reactor in proportion for in-situ polymerization and redox reaction. The mesoporous zirconium phosphate-nanosilver antibacterial composite was prepared, dried and spun into a mesoporous zirconium phosphate-loaded nanosilver antibacterial polyester fiber.

The method for preparing a mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber according to claim 5, wherein the specific step of treating the mesoporous zirconium phosphate with fuming sulfuric acid is: the mass fraction of the fuming sulfuric acid is 50% to 98%, the reaction temperature is 40 to 80 ° C, and the reaction time is 20 to 80 min.
The method for preparing a mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber according to claim 5, wherein the surface has a sulfonic acid group-containing mesoporous zirconium phosphate, a silver ion compound and a glycol mass ratio It is 60 to 90: 0.5 to 5: 5 to 39.5.
The method for preparing a mesoporous zirconium phosphate-loaded nanosilver antibacterial polyester fiber according to claim 5, wherein the silver ion compound is silver chloride, silver bromide, silver iodide, silver hydroxide, silver sulfide, and One or more of silver sulfate.
The method for preparing a mesoporous zirconium phosphate-loaded nanosilver antibacterial polyester fiber according to claim 5, It is characterized in that the diol is one or more of ethylene glycol, propylene glycol, butylene glycol and isosorbide.
The method for preparing a mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber according to claim 5, wherein the in-situ polymerization and the redox reaction are carried out at a temperature of 180 to 240 ° C, 300 KPa, and a N 2 atmosphere. The reaction is carried out for 2 to 5 hours, and the reaction is carried out for 2 to 6 hours at 260 to 285 ° C and below 150 Pa.