CN111549392A - A kind of preparation method of antibacterial polyphenylene sulfide fiber - Google Patents

Abstract

The invention provides a preparation method of antibacterial polyphenylene sulfide fiber. The method adopts polyphenylene sulfide antibacterial master batch to prepare antibacterial polyphenylene sulfide fiber, and the polyphenylene sulfide antibacterial master batch is calculated in weight percentage. , consists of the following raw materials: 20% to 30% of antibacterial powder, 0.2% to 0.3% of antioxidant, 4% to 7% of dispersant, 62.7% to 75.8% of polyphenylene sulfide powder, The sum of the percentages by weight is 100%; the antibacterial powder, in percentage by weight, is composed of the following raw materials: 80% of the polymer-encapsulated CePO ₄ nano-powder, and 20% of the Ce(OH) ₄ nano-powder. The antibacterial polyphenylene sulfide masterbatch prepared by the invention is used for spinning, and the spun antibacterial polyphenylene sulfide fiber has excellent mechanical properties and excellent antibacterial properties. The antibacterial fabric prepared by blending with ordinary polyphenylene sulfide fiber in a certain proportion has a high bacteriostatic rate, which can greatly reduce the production cost of the antibacterial fabric.

Description

A kind of preparation method of antibacterial polyphenylene sulfide fiber

technical field

The invention belongs to the field of antibacterial modification of fibers, relates to polyphenylene sulfide fibers, and in particular relates to a preparation method of antibacterial polyphenylene sulfide fibers.

Background technique

In recent years, polyphenylene sulfide fibers have been widely used in the textile industry due to their good flame retardancy, chemical corrosion resistance, high temperature resistance and physical and mechanical properties. However, with the improvement of people's health awareness, the hygienic performance of textiles has also received more and more attention. Since the beginning of human social activities, the widespread existence and spread of microorganisms such as bacteria has always been an important threat to human health. The porous structure of textiles is more likely to become a breeding ground for bacteria and fungi, which in turn affects people's health. Therefore, the research and development of antibacterial textiles has practical significance.

The technologies for manufacturing antibacterial functional fibers include masterbatch method blending modification technology, in-situ polymerization method, finishing coating method, etc. The post-finishing and coating method is used to prepare antibacterial fibers. Although it is easy to produce on a large scale, it produces a large amount of waste water and pollutes the environment. The fabrics produced have a hard hand and have poor antibacterial durability. The in-situ polymerization method for preparing antibacterial fibers is complicated and difficult to control. , the production cost is high; the masterbatch blending modification technology is to mix the antibacterial powder with the resin before spinning, prepare the antibacterial masterbatch through a twin-screw extruder, and then use it for melt spinning to prepare antibacterial fibers. The antibacterial fiber prepared by the masterbatch blending technology has a short technological process, the method is simple and easy to operate, and the antibacterial durability and washing resistance of the fiber are excellent. When preparing antibacterial polyphenylene sulfide fibers, due to the high spinning temperature, the stability of antibacterial powder is required to be high.

The prior art discloses a polymer-based cerium-doped nano-zinc oxide composite antibacterial agent for fabrics and a preparation method thereof (application publication number: CN105648745A). The method prepares a polymer-based cerium-doped nano-zinc oxide composite by an in-situ method Antibacterial agent, cerium ion doping effectively improves the photocatalytic antibacterial performance of zinc oxide. However, this type of antibacterial agent is still subject to the influence of light conditions, and is suitable for the finishing coating of fabrics, and the antibacterial durability of the prepared antibacterial fabrics is poor.

The prior art discloses a nano-mesoporous cerium oxide-loaded antibacterial agent and a preparation method thereof (application publication number: CN101138342A). Cerium oxide intensifies the antibacterial properties of silver, and at the same time, it can withstand high temperature and obtain better antibacterial effect. The antibacterial agent can be widely used in ceramics, plastics, textiles and other fields, but is loaded with precious metal silver, which is not only complicated in process but also high in cost.

SUMMARY OF THE INVENTION

In view of the deficiencies in the prior art, the purpose of the present invention is to provide a preparation method of antibacterial polyphenylene sulfide fiber, which solves the deficiencies in the antibacterial and mechanical properties of the antibacterial polyphenylene sulfide fiber in the prior art and the high cost technical issues.

In order to solve the above-mentioned technical problems, the application adopts the following technical solutions to realize:

A preparation method of antibacterial polyphenylene sulfide fiber, characterized in that the method adopts polyphenylene sulfide antibacterial master batch to prepare antibacterial polyphenylene sulfide fiber, and the polyphenylene sulfide antibacterial master batch is calculated in weight percentage , consists of the following raw materials: 10% to 30% of antibacterial powder, 0.1% to 0.3% of antioxidant, 2% to 7% of dispersant, 69.7% to 87.9% of polyphenylene sulfide powder, The sum of the weight percentages is 100%;

The antibacterial powder, in terms of weight percentage, is composed of the following raw materials: the CePO ₄ nano-powder encapsulated by the polymer is 70% to 85%, the Ce(OH) ₄ nano-powder is 15% to 30%, and the raw material The sum of the weight percentages is 100%.

The present invention also has the following technical features:

Preferably, the polyphenylene sulfide antibacterial masterbatch is composed of the following raw materials in weight percentage: 20% to 30% of antibacterial powder, 0.2% to 0.3% of antioxidant, and 4% to 0.3% of dispersant. 7%, the polyphenylene sulfide powder is 62.7% to 75.8%, and the sum of the weight percentages of the raw materials is 100%;

The antibacterial powder, in weight percentage, is composed of the following raw materials: 80% of the CePO ₄ nano-powder encapsulated by the polymer, and 20% of the Ce(OH) ₄ nano-powder.

The antioxidant, in weight percent, is composed of the following raw materials: 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl) Benzene is 70% and dioctadecyl thiodipropionate is 30%.

Specifically, the method specifically includes the following steps:

Step 1: Separate the antibacterial polyphenylene sulfide masterbatch and the polyphenylene sulfide chips, respectively, and vacuum dry the polyphenylene sulfide powder in a vacuum drying oven, first drying at 120 °C for 3 hours, and then drying at 140 °C for 5 hours. Always keep it at 0.05~1.0MPa, and the moisture in the antibacterial polyphenylene sulfide masterbatch and polyphenylene sulfide chips after drying should be less than 0.003%;

Step 2, adding the antibacterial polyphenylene sulfide masterbatch to the melt spinning machine according to the proportion that the total weight of the antibacterial powder in the antibacterial polyphenylene sulfide masterbatch accounts for 2% to 3% of the total weight of the antibacterial polyphenylene sulfide fiber of the final product. spinning in

Step 3: Air-cooling and solidifying the filaments extruded from the spinning machine, integrating the filaments into fiber bundles by oiling, guiding the fiber bundles to the drafting machine, and winding them on the tube after drafting and shaping to obtain specifications. Antibacterial polyphenylene sulfide fiber of 72D/36f.

The melt spinning process conditions are as follows: the melt spinning temperature from zone one to zone four is 255°C, 320°C, 325°C, and 330°C, respectively, and the temperature of the hot plate in the drafting zone is 60°C, 105°C, and 120°C, respectively. , the winding speed is 1000m/min.

Preferably, the preparation process of the antibacterial powder is as follows: first, the CePO ₄ nano-powder is subjected to surface treatment to obtain a polymer-encapsulated CePO ₄ nano-powder; secondly, the polymer-encapsulated CePO ₄ nano-powder is The powder was mixed with Ce(OH) ₄ nanometer powder to obtain antibacterial powder.

Preferably, the surface treatment process includes: using an aluminate coupling agent to pretreat the CePO ₄ nano-powder. Weigh 10~15g CePO ₄ nano-powder and disperse it in 200ml deionized water to make a suspension. After 180 mg of aluminate coupling agent was weighed and dissolved in n-butanol, it was added dropwise to the suspension. During the dropwise addition, the suspension should be placed in a 60°C water bath and stirred at a speed of 60rpm. After the dropwise addition, the temperature and stirring speed should be maintained for 2h. Then the solid product is washed to neutrality with absolute ethanol and dried to obtain pretreated CePO4 nano _- powder;

Weigh 50~100mg of 2,6-diphenylphenol and dissolve it in 100ml of ethanol solution, add ₂ ~6g of pretreated CePO4 nano-powder to form a suspension, place the suspension in a water bath at 50°C, and use Stir at a speed of 120 rpm, at the same time add 1~2 mg of cuprous bromide/2,2'-bipyridine complex and introduce oxygen. After 5 hours of reaction, the suspension is centrifuged and washed with ethanol solution containing 30% sulfuric acid. The separated solid is washed with water and dried to obtain a polymer-encapsulated CePO ₄ nano-powder.

Preferably, the preparation process of the polyphenylene sulfide antibacterial masterbatch is:

First, the polyphenylene sulfide powder and antibacterial powder were vacuum-dried in a vacuum drying oven, first dried at 120 °C for 2 hours, then raised to 140 °C for 4 hours, and the vacuum degree was always maintained at 0.05~1.0MPa. After drying, polyphenylene The moisture in the sulfide powder should be less than 0.003%;

Secondly, after mixing the antibacterial powder, dispersant, antioxidant and the dried polyphenylene sulfide powder uniformly, the antibacterial polyphenylene sulfide is prepared by blending, extruding, water cooling and dicing through a twin-screw extruder. masterbatch. The processing conditions of the twin-screw extruder are as follows: the screw temperature is 220°C, 297°C, 302°C and 302°C from the first zone to the fourth zone, the head temperature is 307°C, and the screw speed is 210rpm.

Compared with the prior art, the present invention has the following beneficial technical effects:

(I) The present invention uses the surface-treated rare earth compound CePO ₄ nanometer powder as the antibacterial powder. Commonly used inorganic antibacterial agents such as TiO ₂ , ZnO, CuO, etc. have a single antibacterial effect. To ensure the antibacterial effect, they are often loaded with antibacterial active substances such as precious metal ions and elemental substances, resulting in complicated production process and high cost. CePO ₄ nano-powder has low toxicity to mammalian cells and has a unique antibacterial mechanism, which can not only trigger the production of reactive oxygen species to kill bacteria, but also induce physical damage to bacterial cells, so it can show no need to load other antibacterial substances. Excellent antibacterial properties.

(II) The present invention uses a two-step method for surface treatment of nano-powders, and uses polymers to encapsulate CePO ₄ nano-powders, which not only reduces the agglomeration of nano-powders, but also improves the bond between the nano-powders and the polyphenylene sulfide matrix. Compatibility, reduce the adverse effects on the mechanical properties of fiber products.

(III) In the preparation process of the masterbatch of the present invention, a hyperdispersant is selected. One end of the hyperdispersant contains an anchoring group, which is fixed on the surface of CePO ₄ nano-powder through chemical bonding, and the other end has a polymer segment to reduce the agglomeration of CePO ₄ nano-powder during processing through steric hindrance, which can significantly improve the antibacterial mother. The problem of agglomeration of inorganic nanopowders in particles is serious.

(IV) The antibacterial polyphenylene sulfide masterbatch prepared by the invention is used for spinning, and the spun antibacterial polyphenylene sulfide fiber has excellent mechanical properties and excellent antibacterial properties. The antibacterial fabric prepared by blending with ordinary polyphenylene sulfide fiber in a certain proportion has a high bacteriostatic rate, which can greatly reduce the production cost of the antibacterial fabric.

The present invention will be further explained in detail below in conjunction with the examples.

Detailed ways

The weight average molecular weight of the polyphenylene sulfide powder in the present invention is 35,000 to 55,000.

The weight average molecular weight of the polyphenylene sulfide chips in the present invention is 35,000 to 55,000.

The particle size of the CePO ₄ nano-powder in the present invention is 350 nm to 450 nm.

The particle size of the Ce(OH) ₄ nano-powder in the present invention is 300 nm to 425 nm.

The coupling agent in the present invention is an aluminate coupling agent, and the brand name is DL-414.

The dispersant in the present invention adopts the hyperdispersant with the trade name of DP330 or the hyperdispersant with the trade mark of DP340.

Following the above technical solutions, specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent transformations made on the basis of the technical solutions of the present application all fall into the protection scope of the present invention. . The present invention will be described in further detail below in conjunction with the embodiments.

Example 1:

The present embodiment provides a preparation method of antibacterial polyphenylene sulfide fiber, which is characterized in that the method adopts polyphenylene sulfide antibacterial masterbatch to prepare antibacterial polyphenylene sulfide fiber, and the polyphenylene sulfide antibacterial masterbatch is calculated by weight. In terms of percentage, it is composed of the following raw materials: 20% of antibacterial powder, 0.2% of antioxidant, 4% of dispersant, and 75.8% of polyphenylene sulfide powder.

The preparation process of polyphenylene sulfide antibacterial masterbatch is as follows:

First, the polyphenylene sulfide powder and antibacterial powder were vacuum-dried in a vacuum drying oven, first dried at 120 °C for 2 hours, then raised to 140 °C for 4 hours, and the vacuum degree was always maintained at 0.05~1.0MPa. After drying, polyphenylene The moisture in the sulfide powder should be less than 0.003%;

Secondly, after mixing the antibacterial powder, dispersant, antioxidant and the dried polyphenylene sulfide powder uniformly, the antibacterial polyphenylene sulfide is prepared by blending, extruding, water cooling and dicing through a twin-screw extruder. masterbatch. The processing conditions of the twin-screw extruder are as follows: the screw temperature is 220°C, 297°C, 302°C, and 302°C from the first zone to the fourth zone, the head temperature is 307°C, and the screw speed is 210rpm.

Specifically, the method specifically includes the following steps:

Step 1: Separate the antibacterial polyphenylene sulfide masterbatch and the polyphenylene sulfide chips, respectively, and vacuum dry the polyphenylene sulfide powder in a vacuum drying oven, first drying at 120 °C for 3 hours, and then drying at 140 °C for 5 hours. Always keep it at 0.05~1.0MPa, and the moisture in the antibacterial polyphenylene sulfide masterbatch and polyphenylene sulfide chips after drying should be less than 0.003%;

Step 2, adding the antibacterial polyphenylene sulfide masterbatch to the melt spinning machine according to the proportion that the total weight of the antibacterial powder in the antibacterial polyphenylene sulfide master batch accounts for 2% of the total weight of the antibacterial polyphenylene sulfide fiber of the final product. Silk;

The melt spinning process conditions are: the melt spinning temperature from zone one to zone four is 255°C, 320°C, 325°C, and 330°C, respectively, and the temperature of the hot plate in the drawing zone is 60°C, 105°C, and 120°C, respectively. The speed is 1000m/min.

Step 3: Air-cooling and solidifying the filaments extruded from the spinning machine, integrating the filaments into fiber bundles by oiling, guiding the fiber bundles to the drafting machine, and winding them on the tube after drafting and shaping to obtain specifications. Antibacterial polyphenylene sulfide fiber of 72D/36f.

Specifically, the antibacterial powder, in weight percentage, is composed of the following raw materials: 80% of the polymer-encapsulated CePO ₄ nano-powder, and 20% of the Ce(OH) ₄ nano-powder.

The preparation process of the antibacterial powder is as follows: first, the CePO ₄ nano-powder is subjected to surface treatment to obtain a polymer-encapsulated CePO ₄ nano-powder; secondly, the polymer-encapsulated CePO ₄ nano-powder is mixed with Ce(OH) _4. The nano powders are mixed to obtain antibacterial powders.

The surface treatment process includes: pretreatment of CePO ₄ nano-powder with aluminate coupling agent. Weigh 10~15g CePO ₄ nano powder and disperse it in 200ml deionized water to make a suspension. After 180 mg of aluminate coupling agent was weighed and dissolved in n-butanol, it was added dropwise to the suspension. During the dropwise addition, the suspension should be placed in a 60°C water bath and stirred at a speed of 60rpm. After the dropwise addition, the temperature and stirring speed should be maintained for 2h. Then the solid product is washed to neutrality with absolute ethanol and dried to obtain pretreated CePO4 nano _- powder;

Weigh 50~100mg of 2,6-diphenylphenol and dissolve it in 100ml of ethanol solution, add ₂ ~6g of pretreated CePO4 nano-powder to form a suspension, place the suspension in a water bath at 50°C, and use Stir at a speed of 120 rpm, at the same time add 1~2 mg of cuprous bromide/2,2'-bipyridine complex and introduce oxygen. After 5 hours of reaction, the suspension is centrifuged and washed with ethanol solution containing 30% sulfuric acid. The separated solid is washed with water and dried to obtain a polymer-encapsulated CePO ₄ nano-powder.

Specifically, the antioxidant, in parts by weight, is composed of the following raw materials: 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl ) 70% for benzene and 30% for dioctadecyl thiodipropionate.

Antibacterial performance test: The fiber was processed into a thin plain weave fabric, and the antibacterial performance test was carried out according to the method of GB/T20944.3-2008. The test results are shown in Table 1.

Example 2:

The present embodiment provides a preparation method of antibacterial polyphenylene sulfide fiber, which is characterized in that the method adopts polyphenylene sulfide antibacterial masterbatch to prepare antibacterial polyphenylene sulfide fiber, and the polyphenylene sulfide antibacterial masterbatch is calculated by weight. In terms of percentage, it is composed of the following raw materials: 30% of antibacterial powder, 0.3% of antioxidant, 7% of dispersant, and 62.7% of polyphenylene sulfide powder.

The preparation process of the polyphenylene sulfide antibacterial masterbatch is the same as that in Example 1.

The specific steps of the preparation method of the antibacterial polyphenylene sulfide fiber of the present embodiment are basically the same as those of the embodiment 1, and the difference is only that the addition amount of the masterbatch is different. In this embodiment, the antibacterial polyphenylene sulfide masterbatch is added to the melt spinning machine according to the proportion that the total weight of the antibacterial powder in the antibacterial polyphenylene sulfide masterbatch accounts for 3% of the total weight of the antibacterial polyphenylene sulfide fiber of the final product. spinning.

The antibacterial powder of this example is the same as the antibacterial powder of Example 1.

The preparation process of the antibacterial powder in this example is the same as the preparation process of the antibacterial powder in Example 1.

The antioxidant in this example is the same as that in Example 1.

Antibacterial performance test: The fiber was processed into a thin plain weave fabric, and the antibacterial performance test was carried out according to the method of GB/T20944.3-2008. The test results are shown in Table 1.

Example 3:

This embodiment provides a preparation method of antibacterial polyphenylene sulfide fiber, which adopts polyphenylene sulfide antibacterial masterbatch to prepare antibacterial polyphenylene sulfide fiber, and the polyphenylene sulfide antibacterial masterbatch and the polyphenylene sulfide of Example 2 The thioether antibacterial masterbatch is the same.

The preparation process of the polyphenylene sulfide antibacterial masterbatch is the same as that in Example 2.

The specific steps of the preparation method of the antibacterial polyphenylene sulfide fiber of this embodiment are the same as those of embodiment 2.

The antibacterial powder of this example is the same as the antibacterial powder of Example 2.

The preparation process of the antibacterial powder in this example is the same as the preparation process of the antibacterial powder in Example 2.

The antioxidant in this example is the same as that in Example 1.

The difference lies in the antibacterial performance test of this example: the antibacterial polyphenylene sulfide fiber prepared in this example and the ordinary polyphenylene sulfide fiber without antibacterial modification are blended and processed into a thin plain weave fabric, in parts by weight, by the following Raw material composition: 90% antibacterial polyphenylene sulfide fiber, 10% ordinary polyphenylene sulfide fiber. And according to GB/T20944.3-2008 method to carry out antibacterial performance test, the test results are shown in Table 1.

Comparative Example 1:

This comparative example provides a preparation method of antibacterial polyphenylene sulfide fiber, which uses polyphenylene sulfide antibacterial masterbatch to prepare antibacterial polyphenylene sulfide fiber. The difference between the polyphenylene sulfide antibacterial masterbatch of 1 is that no antibacterial powder is added in this comparative example, and the same amount of polyphenylene sulfide powder is used for the antibacterial powder in the formula.

The preparation process of the polyphenylene sulfide antibacterial masterbatch of this comparative example is basically the same as that of Example 1.

The preparation method of the antibacterial polyphenylene sulfide fiber of this comparative example is basically the same as that of Example 1.

The antioxidant of this comparative example is the same as that of Example 1.

Antibacterial performance test: The fiber was processed into a thin plain weave fabric, and the antibacterial performance test was carried out according to the method of GB/T20944.3-2008. The test results are shown in Table 1.

Comparative Example 2:

This comparative example provides a preparation method of antibacterial polyphenylene sulfide fiber, which uses polyphenylene sulfide antibacterial masterbatch to prepare antibacterial polyphenylene sulfide fiber. The polyphenylene sulfide antibacterial masterbatch of 1 is basically the same, the difference is that the preparation steps of the antibacterial powder in this comparative example are different, and the CePO ₄ nano-powder is not subjected to polymer encapsulation treatment in this comparative example.

The preparation process of the polyphenylene sulfide antibacterial masterbatch of this comparative example is basically the same as that of Example 1.

The preparation method of the antibacterial polyphenylene sulfide fiber of this comparative example is basically the same as that of Example 1.

The antioxidant of this comparative example is the same as that of Example 1.

Antibacterial performance test: The fiber was processed into a thin plain weave fabric, and the antibacterial performance test was carried out according to the method of GB/T20944.3-2008. The test results are shown in Table 1.

Comparative Example 3:

This comparative example provides a preparation method of antibacterial polyphenylene sulfide fiber, which uses polyphenylene sulfide antibacterial masterbatch to prepare antibacterial polyphenylene sulfide fiber. The difference between the polyphenylene sulfide antibacterial masterbatch of 1 is that no dispersant is added in this comparative example, and the dispersant in the formula is replaced by the same amount of polyphenylene sulfide powder.

The preparation process of the polyphenylene sulfide antibacterial masterbatch of this comparative example is basically the same as that of Example 1.

The preparation method of the antibacterial polyphenylene sulfide fiber of this comparative example is basically the same as that of Example 1.

The antibacterial powder of this comparative example is the same as the antibacterial powder of Example 2.

The preparation process of the antibacterial powder of this comparative example is the same as the preparation process of the antibacterial powder in Example 2.

The antioxidant of this comparative example is the same as that of Example 1.

Antibacterial performance test: The fiber was processed into a thin plain weave fabric, and the antibacterial performance test was carried out according to the method of GB/T20944.3-2008. The test results are shown in Table 1.

Comparative Example 4:

This comparative example provides a preparation method of antibacterial polyphenylene sulfide fiber, which uses polyphenylene sulfide antibacterial masterbatch to prepare antibacterial polyphenylene sulfide fiber. The difference between the polyphenylene sulfide antibacterial masterbatch of 1 is that the antibacterial powders in this comparative example are different, and the antibacterial powders in this comparative example are all CePO4 nano _- powders encapsulated by an equal amount of polymer.

The preparation process of the polyphenylene sulfide antibacterial masterbatch of this comparative example is basically the same as that of Example 1.

The preparation method of the antibacterial polyphenylene sulfide fiber of this comparative example is basically the same as that of Example 1.

The antioxidant of this comparative example is the same as that of Example 1.

Antibacterial performance test: The fiber was processed into a thin plain weave fabric, and the antibacterial performance test was carried out according to the method of GB/T20944.3-2008. The test results are shown in Table 1.

Comparative Example 5:

This comparative example provides a preparation method of antibacterial polyphenylene sulfide fiber, which uses polyphenylene sulfide antibacterial masterbatch to prepare antibacterial polyphenylene sulfide fiber. The polyphenylene sulfide antibacterial masterbatch of 2 is the same.

The preparation process of the polyphenylene sulfide antibacterial masterbatch of this comparative example is basically the same as that of Example 2.

The preparation method of the antibacterial polyphenylene sulfide fiber of this comparative example is basically the same as that of Example 2.

The antibacterial powder of this comparative example is the same as the antibacterial powder of Example 2.

The preparation process of the antibacterial powder of this comparative example is the same as the preparation process of the antibacterial powder in Example 2.

The antioxidant of this comparative example is the same as that of Example 2.

The difference lies in the antibacterial performance test of this comparative example: the antibacterial polyphenylene sulfide fiber prepared in this example and the ordinary polyphenylene sulfide fiber without antibacterial modification are blended and processed into a thin plain fabric, in parts by weight, by the following Raw material composition: 70% antibacterial polyphenylene sulfide fiber, 30% ordinary polyphenylene sulfide fiber. And according to GB/T20944.3-2008 method to carry out antibacterial performance test, the test results are shown in Table 1.

Table 1 Performance test results

It can be seen from Table 1 that the compatibility between the CePO ₄ nano-powder encapsulated by the polymer of the present invention and the polyphenylene sulfide matrix is significantly improved, and the tensile strength and elongation at break of the spun fibers are greatly improved. Fiber elasticity, wearability and feel are better.

As can be seen from Table 1, the antibacterial polyphenylene sulfide fiber prepared by using the antibacterial powder of the present invention has excellent antibacterial properties, and when used to prepare fabrics, it can be mixed with ordinary polyphenylene sulfide fibers without antibacterial modification. to reduce production costs. When the mixing ratio of ordinary fibers is 30%, the antibacterial rate of the fabric is still higher than the minimum standard value of antibacterial rate specified in GB/T20944.3-2008 for antibacterial fabrics. In addition, the prepared fabric also has excellent washing resistance. After 50 times of washing, the bacteriostatic rate of the three types of bacteria does not decrease by more than 5%.

It can be seen from Table 1 that the hyperdispersant in the present invention plays a key role in the dispersion of the antibacterial powder in the polyphenylene sulfide matrix. The mechanical properties and antibacterial properties of the fibers spun by the antibacterial polyphenylene sulfide masterbatch added with dispersant are better than those spun by the antibacterial masterbatch without hyperdispersant.

Claims (8)

1. The preparation method of the antibacterial polyphenylene sulfide fiber is characterized in that the antibacterial polyphenylene sulfide master batch is adopted to prepare the antibacterial polyphenylene sulfide fiber, and the antibacterial polyphenylene sulfide master batch comprises the following raw materials in percentage by weight: 10 to 30 percent of antibacterial powder, 0.1 to 0.3 percent of antioxidant, 2 to 7 percent of dispersant, 69.7 to 87.9 percent of polyphenylene sulfide powder, and the sum of the weight percentages of the raw materials is 100 percent;

the antibacterial powder comprises the following raw materials in percentage by weight: polymer encapsulated CePO₄70% -85% of nano powder, Ce (OH)₄15 to 30 percent of nano powder, and the sum of the weight percentages of the raw materials is 100 percent.

2. The preparation method of the antibacterial polyphenylene sulfide fiber of claim 1, wherein the antibacterial polyphenylene sulfide master batch comprises the following raw materials by weight percent: 20 to 30 percent of antibacterial powder, 0.2 to 0.3 percent of antioxidant, 4 to 7 percent of dispersant, 62.7 to 75.8 percent of polyphenylene sulfide powder, and the sum of the weight percentages of the raw materials is 100 percent;

the antibacterial powder comprises the following raw materials in percentage by weight: polymer encapsulated CePO₄80% of nano-powder, Ce (OH)₄The content of the nano powder is 20 percent.

3. The method for preparing antibacterial polyphenylene sulfide fiber according to claim 1, wherein the antioxidant comprises the following raw materials in percentage by weight: 70% of 1, 3, 5-trimethyl-2, 4, 6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and 30% of dioctadecyl thiodipropionate.

4. The method for preparing antibacterial polyphenylene sulfide fiber according to claim 1, comprising the steps of:

respectively drying the antibacterial polyphenylene sulfide master batch and the polyphenylene sulfide slice in a vacuum drying oven in vacuum for 3h at 120 ℃, then drying for 5h at 140 ℃, wherein the vacuum degree is always kept at 0.05-1.0 MPa, and the moisture content in the dried antibacterial polyphenylene sulfide master batch and the dried polyphenylene sulfide slice is lower than 0.003%;

secondly, adding the antibacterial polyphenylene sulfide master batch into a melt spinning machine for spinning according to the proportion that the total weight of the antibacterial powder in the antibacterial polyphenylene sulfide master batch accounts for 2-3% of the total weight of the antibacterial polyphenylene sulfide fiber of the final product;

and thirdly, air cooling and solidifying the fiber yarns extruded from the spinning machine, oiling the fiber yarns to integrate fiber bundles, guiding the fiber bundles to a drafting machine, drafting and shaping the fiber bundles, and then winding the fiber bundles on a pipe barrel to obtain the antibacterial polyphenylene sulfide fibers with the specification of 72D/36 f.

5. The method for preparing antibacterial polyphenylene sulfide fiber according to claim 4, wherein the melt spinning process conditions are as follows: the melt spinning temperature is 255 ℃, 320 ℃, 325 ℃ and 330 ℃ respectively from one zone to four zones, the hot plate temperature of the drawing zone is 60 ℃, 105 ℃ and 120 ℃ respectively, and the winding speed is 1000 m/min.

6. The method for preparing antibacterial polyphenylene sulfide fiber according to claim 1, wherein the preparation process of the antibacterial powder is as follows: firstly, CePO is mixed₄The nanometer powder is processed to prepare polymer encapsulated CePO by surface treatment₄Nano powder; second, polymer encapsulated CePO₄Nano powder and Ce (OH)₄Mixing the nanometer powder to obtain the antibacterial powder.

7. The method for preparing antibacterial polyphenylene sulfide fiber according to claim 6, wherein the surface treatment process comprises: using an aluminate coupling agent to CePO₄Pretreating the nano powder, and weighing 10-15 g of CePO₄Dispersing the nano powder in 200ml of deionized water to prepare a suspension; weighing 180mg of aluminate coupling agent, dissolving in n-butanol, dropwise adding into the suspension, placing the suspension in a 60 ℃ water bath during dropwise adding, stirring at the speed of 60rpm, continuously maintaining the temperature and the stirring speed for 2h after dropwise adding, washing the solid product with absolute ethyl alcohol to be neutral, and drying to obtain the pretreated CePO₄Nano powder;

weighing 50-100 mg of 2, 6-diphenylphenol, dissolving in 100ml of ethanol solution, adding 2-6 g of pretreated CePO₄Forming a suspension by the nanometer powder, placing the suspension in a water bath kettle at 50 ℃, stirring at the speed of 120rpm, simultaneously adding 1-2 mg of cuprous bromide/2, 2' -bipyridyl complex, introducing oxygen, reacting for 5 hours, centrifugally separating the suspension, washing the separated solid with 30% ethanol solution containing sulfuric acid, washing with water, and drying to obtain the polymer encapsulated CePO₄And (3) nano powder.

8. The method for preparing the antibacterial polyphenylene sulfide fiber according to claim 1, wherein the preparation process of the antibacterial polyphenylene sulfide master batch comprises the following steps:

firstly, performing vacuum drying on polyphenylene sulfide powder and antibacterial powder in a vacuum drying oven, drying for 2 hours at 120 ℃, then drying for 4 hours at 140 ℃, wherein the vacuum degree is always kept at 0.05-1.0 MPa, and the moisture in the dried polyphenylene sulfide powder is lower than 0.003%;

secondly, uniformly mixing the antibacterial powder, the dispersing agent and the antioxidant with the dried polyphenylene sulfide powder, and then blending, extruding, water-cooling and granulating the mixture by a double-screw extruder to prepare the polyphenylene sulfide antibacterial masterbatch, wherein the processing conditions of the double-screw extruder are as follows: the screw temperatures were 220 deg.C, 297 deg.C, 302 deg.C, 307 deg.C for the head and 210rpm for the screw from zone one to zone four.