A method for preparing titanium-coupled long-acting antibacterial polyester fibers

Abstract

The application discloses a preparation method of titanium-coupled long-acting antibacterial polyester fibers. First, ultrasonic alcohol washing-high temperature alkali immersion composite pretreatment is carried out, and then titanium-based long-acting antibacterial polyester fibers are prepared. 0.5-1.5 parts by weight of titanium dioxide and 1-3 parts by weight of polyhexamethylene guanidine PHMG are taken into a jar, 95-99 parts by weight of distilled water is injected into the jar, a small amount of magnetic sub is put into the jar, and the jar is placed on a temperature-controlled magnetic stirrer to stir for 0.5-1.5 hours. Then, the polyester fibers treated by the pretreatment process are put into the jar, and normal-temperature stirring is carried out for 1-3 hours. After the reaction is completed, the polyester fibers are taken out, and normal-temperature drying is carried out, so that the titanium-coupled long-acting antibacterial polyester fibers are obtained. The preparation method is simple, green and environment-friendly, and the prepared product has long-term bacteriostatic effect.

Description

[0001] The present application is a divisional application of the following application: Preparation method of copper and titanium coupled long-acting antibacterial polyester fiber based on efficient pretreatment process; Application number: 202110217604.1; Filing date: February 26, 2021. TECHNICAL FIELD

[0002] The present application relates to the field of chemical technology, and in particular to a preparation method of functional polyester fiber. BACKGROUND

[0003] In recent years, cotton textiles with persistent antibacterial, safe and comfortable properties have been widely used in various fields of people's life, such as clothing, household textiles, medical textile industry, etc. Therefore, the development of polyester / cotton textiles with durable antibacterial properties under daily visible light is of great significance to daily life, safe home and medical environment. However, polyester fibers with antibacterial functional properties face the bottleneck of difficulty in grafting polyhexamethylene guanidine (PHMG).

[0004] Currently, the research on antibacterial textiles mainly focuses on the antibacterial modification of fabrics. The main antibacterial modification on the market is cotton, but compared with cotton, polyester fiber is named polyethylene terephthalate, and the chemical structure has fewer hydroxyl groups. Generally, it is not as easy to react as cotton, so in order to make it react chemically, it is necessary to hydrolyze the polyester fiber to expose the hydroxyl and carboxyl groups to increase the reaction probability.

[0005] In order to solve this problem, researchers turn their attention to using a coupling agent to help grafting of the antibacterial agent. Copper-containing compounds are also a commonly used antibacterial agent, which can be well complexed with PHMG to produce a new type of antibacterial agent. Its antibacterial mechanism is that copper ions hinder the electron transfer system and damage the cell membrane, so this new type of antibacterial agent has broad-spectrum bactericidal effect and durability. At the same time, titanium dioxide has photocatalytic ability, which can decompose microorganisms and toxins produced by microorganisms under the action of light. Therefore, grafting polyhexamethylene guanidine onto polyester fiber with titanium dioxide makes polyester fiber have long-acting antibacterial effect, inhibits the reproduction of microorganisms on textiles, and makes textiles have good antibacterial effect. Titanium dioxide can use solar energy to play an antibacterial and antifouling role. Its antibacterial mechanism mainly lies in that under the action of photocatalysis, a large number of chemically active hydroxyl radicals and oxygen radicals are generated on the surface, which can oxidize organic matter in microorganisms and destroy microorganisms. However, the photocatalytic effect of titanium dioxide under visible light is weak, and the light response range is narrow, which seriously affects its further popularization and application. SUMMARY

[0006] The technical problem to be solved by the present application is to provide a preparation method of copper and titanium coupled long-acting antibacterial polyester fiber based on efficient pretreatment process.

[0007] To solve the above technical problems, the technical solutions adopted by the present application are as follows.

[0008] A preparation method of copper and titanium coupled long-acting antibacterial polyester fiber based on an efficient pretreatment process, which comprises the following steps: A, ultrasonic alcohol washing-high temperature alkali immersion composite pretreatment process: in an ultrasonic reaction container, polyester fiber cloth is immersed in anhydrous ethanol, the ultrasonic intensity is set to 0.2-0.4 W / cm 2 , the ultrasonic frequency is 150-250 KHz, and the polyester fiber cloth is washed by ultrasonic for 20-40 min, and then the polyester fiber cloth is placed on a sterile workbench for drying / drying; then the polyester fiber cloth is immersed in a 8-12% sodium hydroxide solution, the sodium hydroxide solution is preheated to 70-90 DEG C and kept constant temperature in water bath, and the polyester fiber cloth is immersed for 40-80 min, and then washed with distilled water for several times until neutral, and dried for standby.

[0009] As a preferred technical solution of the present application, the specific process parameters of step A are: in an ultrasonic reaction container, polyester fiber cloth is immersed in anhydrous ethanol, the ultrasonic intensity is set to 0.25-0.35 W / cm 2 , the ultrasonic frequency is 175-225 KHz, and the polyester fiber cloth is washed by ultrasonic for 25-35 min, and then the polyester fiber cloth is placed on a sterile workbench for drying / drying; then the polyester fiber cloth is immersed in a 9-11% sodium hydroxide solution, the sodium hydroxide solution is preheated to 75-85 DEG C and kept constant temperature in water bath, and the polyester fiber cloth is immersed for 50-70 min, and then washed with distilled water for several times until neutral, and dried for standby.

[0010] As a preferred technical solution of the present application, the specific process parameters of step A are: in an ultrasonic reaction container, polyester fiber cloth is immersed in anhydrous ethanol, the ultrasonic intensity is set to 0.30 W / cm 2 , the ultrasonic frequency is 200 KHz, and the polyester fiber cloth is washed by ultrasonic for 30 min, and then the polyester fiber cloth is placed on a sterile workbench for drying / drying; then the polyester fiber cloth is immersed in a 10% sodium hydroxide solution, the sodium hydroxide solution is preheated to 80 DEG C and kept constant temperature in water bath, and the polyester fiber cloth is immersed for 60 min, and then washed with distilled water for several times until neutral, and dried for standby.

[0011] As a preferred technical solution of the present application, in step A, the weight ratio of anhydrous ethanol to polyester fiber is (6-12):1.

[0012] As a preferred technical solution of the present application, the method further comprises the following subsequent steps: B, preparation of copper-based long-acting antibacterial polyester fiber: first, prepare a complexing solution, take 5 parts by weight of CuSO4 and 1 part by weight of polyhexamethylene guanidine PHMG in a jar, put it into a magnetic stirrer, heat and stir until the temperature inside the jar reaches 70-90℃, start timing for 4-6h, then add the prepared complexing solution to the standby polyester fiber cloth treated in the previous step, and react at 70-90℃ for 4-6h; after the reaction is completed, take out the polyester fiber cloth and put it into a forced air drying oven at 60-80℃ for 0.5-1.5h, and it is obtained.

[0013] As a preferred technical solution of the present application, in step B, first, prepare a complexing solution, take 5 parts by weight of CuSO4 and 1 part by weight of polyhexamethylene guanidine PHMG in a jar, put it into a magnetic stirrer, heat and stir until the temperature inside the jar reaches 80℃, start timing for 5h, then add the prepared complexing solution to the standby polyester fiber cloth treated in the previous step, and react at 80℃ for 2h; after the reaction is completed, take out the polyester fiber cloth and put it into a forced air drying oven at 70℃ for 1h, and it is obtained.

[0014] As a preferred technical solution of the present application, the method further comprises the following subsequent steps: B, preparation of titanium-based long-acting antibacterial polyester fiber: take 0.5-1.5 parts by weight of titanium dioxide and 1-3 parts by weight of polyhexamethylene guanidine PHMG into a jar, and inject 95-99 parts by weight of distilled water, put a small amount of magnetic stirrer, and place it on a temperature-controlled magnetic stirrer for stirring for 0.5-1.5h; then put the polyester fiber treated by the previous treatment process into this jar, and stir at room temperature for 1-3h; after the reaction is completed, take out the polyester fiber and dry it at room temperature to obtain it.

[0015] As a preferred technical solution of the present application, in step B, take 1 part by weight of titanium dioxide and 2 parts by weight of polyhexamethylene guanidine PHMG into a jar, and inject 97 parts by weight of distilled water, put a small amount of magnetic stirrer, and place it on a temperature-controlled magnetic stirrer, stir at room temperature at 300r / min for 1h; then put the polyester fiber treated in step C into this jar, and stir at room temperature for 2h; after the reaction is completed, take out the polyester fiber and dry it at room temperature to obtain it.

[0016] As a preferred technical solution of the present application, the method further comprises the following subsequent steps: C, washing of polyester fiber: put the antibacterial polyester fiber prepared in step B into distilled water, and place it in an ultrasonic cleaning machine for ultrasonic cleaning for 2-8min, which is recorded as the first washing; according to this step, wash 0, 3, 6, and 9 times.

[0017] As a preferred technical solution of the present application, the method further comprises the following subsequent step: C, cleaning of the polyester fiber: the antibacterial polyester fiber prepared in step B is placed in distilled water and ultrasonic cleaning is performed in an ultrasonic cleaning machine for 5 minutes, which is recorded as one cleaning; the cleaning is performed 0, 3, 6, 9 times according to this step.

[0018] The beneficial effects produced by the above technical solution are that one core innovation of the present application is the creation of the ultrasonic alcohol washing-high temperature alkali immersion combined pretreatment process, and the time of alcohol washing, the time of alkali treatment, the concentration of alkali solution and other combined treatment measures are very important for the polyester fiber. The best process condition obtained by the present application is that when the polyester fiber cloth is washed in anhydrous ethanol under ultrasonic action for 30 minutes, the alkali treatment time is 60 minutes, and the alkali concentration is 10%, the surface structure of the polyester fiber can be better loosened, and the tensile strength and breaking strength of the polyester fiber will not be greatly damaged. This treatment process is also very beneficial to the subsequent reaction of the polyester fiber with the antibacterial finishing agent, and the operation method is simple, low-toxic, and has very outstanding practical effects and application prospects.

[0019] For the copper complexed antibacterial polyester fiber, it is found that the alkali treatment time of the polyester fiber cloth has a great influence on its antibacterial property. The polyester fiber cloth prepared under a treatment time of 60 minutes has good antibacterial effect on E. coli and S. aureus.

[0020] In summary, the preparation method of the present application is simple, the raw materials are safe and non-toxic, green and environmentally friendly, especially the prepared product has long-lasting antibacterial effect, which meets the green development concept, improves the application range of polyester fiber, and has outstanding practical effects and application prospects. BRIEF DESCRIPTION OF DRAWINGS

[0021] DRAWINGS

[0022] Figure 1 The antibacterial performance control picture of Example 1 includes the following detection items: control, i.e. untreated polyester cloth, no washing, washing 10 times, washing 30 times, washing 50 times or washing 60 times, washing 80 times, washing 100 times, and the rest of the examples are similar.

[0023] Figure 2 The antibacterial performance control picture of Example 2.

[0024] Figure 3 The antibacterial performance control picture of Example 3.

[0025] Figure 4 The antibacterial performance control picture of Example 4.

[0026] Figure 5 The antibacterial performance control picture of Example 5.

[0027] Figure 6 Bacteriostatic performance control picture for Example 6.

[0028] Figure 7 Bacteriostatic performance control picture for Example 7.

[0029] Figure 8 Picture of alcohol wash treatment experiment.

[0030] Figure 9 Picture of alkali wash treatment experiment.

[0031] Figure 10 Picture of water wash treatment experiment.

[0032] Figure 11 Picture of titanium dioxide treatment experiment. DETAILED DESCRIPTION

[0033] The following examples illustrate the present application. The various raw materials and equipment used in the present application are all conventional commercially available products, and can be directly obtained by market purchase.

[0034] In the following description of the examples, specific details are set forth in order to provide a thorough understanding of the embodiments of the application. However, persons having ordinary skill in the art will readily recognize that embodiments of the application can be practiced without these specific details. In other instances, well-known structures, devices, circuits, and processes have not been described in detail so as not to unnecessarily obscure aspects of the application.

[0035] It should be understood that the term "comprises" when used in this specification and the appended claims indicates the presence of the described features, integers, steps, operations, elements, and / or components, but does not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof.

[0036] It should also be understood that the term "and / or" when used in this specification and the appended claims indicates that the associated listed items can be present one or more of the associated listed items, and that the combinations of the associated listed items are also included.

[0037] In addition, in the description of the application and the appended claims, the terms "first", "second", "third", etc. are used only to distinguish descriptions, and cannot be understood as indicating or implying relative importance.

[0038] Reference in the specification to "one embodiment" or "some embodiments" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. The appearances of the phrase "in one embodiment" or "in some embodiments" in various places in the specification are not necessarily all referring to the same embodiment, although it can. The terms "including," "comprising," "having" and variations thereof are meant to encompass the items listed thereafter and equivalents thereof as well as additional items. The terms "coupled" and "connected," and variations thereof, are intended to encompass a connection between two members, directly or indirectly, which is rigid or flexible, fixed or moveable, or temporary or permanent.

[0039] Example 1:

[0040] A, alcohol washing of polyester fabric: Put the polyester fabric into a beaker, add anhydrous ethanol to cover the polyester fabric, and ultrasonically clean for 30 min. After taking out, place it in a clean place to dry naturally.

[0041] B, alkali treatment of polyester fabric: Weigh 10 g of NaOH and 90 mL of distilled water to prepare a 10% sodium hydroxide solution in a jar, and place a magnet in the jar. Place the jar in a water bath, and when the internal temperature of the jar reaches 80°C, add the polyester fabric in step A and stir for 30 min. After taking out, wash with distilled water until neutral, and place it in a forced air drying oven at 70°C for standby.

[0042] C, preparation of complexing solution: Weigh 5 g of CuSO4 and 1 g of PHMG into a jar, and place a magnet in the jar. Heat and stir until the internal temperature of the jar reaches 80°C, and then start timing for 5 h.

[0043] D, preparation of long-acting antibacterial polyester fiber: Add the standby polyester fabric in step B to the prepared complexing solution and react at 80°C for 2 h. After the reaction is completed, take out the polyester fabric and place it in a forced air drying oven at 70°C for 1 h.

[0044] E, test of antibacterial performance: The polyester fabric prepared in step D is not washed, washed 10 times, 30 times, and 50 times, respectively, and detected according to the absorption method in Chinese textile industry standard FZ / T 73023-2006, and verified with E. coli, still having good antibacterial property. (The results are shown in the attached drawings of the specification)

[0045] Wash number Control No wash Wash 10 times Wash 30 times Wash 50 times Number of bacteria 5.3 x 10 3 ]] 0 1.2 x 10 3 ]]> 4.5 x 10 3 ]]> 5.1 x 10 3 ]]>

[0046] Example 2:

[0047] A, alcohol washing of polyester fabric: Put the polyester fabric into a beaker, add anhydrous ethanol to cover the polyester fabric, and ultrasonically clean for 30 min. After taking out, place it in a clean place to dry naturally.

[0048] B. Alkali treatment of polyester fabric: 10 g of NaOH was weighed, 90 mL of distilled water was added to prepare a 10% sodium hydroxide solution in a jar, a magnet was added, the jar was placed in a water bath, and when the internal temperature of the jar reached 80°C, the polyester fabric in step A was added and stirred for 45 min. After taking out, it was washed to neutral with distilled water, and was placed in a forced air drying oven at 70°C for drying.

[0049] C. Preparation of complex solution: 5 g of CuSO4 and 1 g of PHMG were weighed in a jar, a magnet was added, and heating and stirring were started when the internal temperature of the jar reached 80°C, and the timing was started for 5 h.

[0050] D. Preparation of long-acting antibacterial polyester fabric: the prepared complex solution was added to the standby polyester fabric in step B at 80°C for 2 h. After the reaction was completed, the polyester fabric was taken out and placed in a forced air drying oven at 70°C for 1 h.

[0051] E. Test of antibacterial performance: the polyester fabric prepared in step D was not washed, washed for 10 times, 30 times, and 50 times, respectively, and was detected according to the absorption method in Chinese textile industry standard FZ / T 73023-2006, and was verified with E. coli, and still had good antibacterial property. (The results are shown in the attached drawings of the specification)

[0052] Wash number Control No wash Wash 10 times Wash 30 times Wash 50 times Number of bacteria 5.9 x 10 3 ]]> No wash 2.5 x 10 2 ]]> 6.0 x 10 2 ]]> 5.1 x 10 3 ]]>

[0053] Example 3:

[0054] A. Alcohol washing of polyester fabric: the polyester fabric was placed in a beaker, anhydrous ethanol was added until the polyester fabric was immersed, and ultrasonic cleaning was performed for 30 min. After taking out, it was naturally dried in a clean place.

[0055] B. Alkali treatment of polyester fabric: 10 g of NaOH was weighed, 90 mL of distilled water was added to prepare a 10% sodium hydroxide solution in a jar, a magnet was added, the jar was placed in a water bath, and when the internal temperature of the jar reached 80°C, the polyester fabric in step A was added and stirred for 60 min. After taking out, it was washed to neutral with distilled water, and was placed in a forced air drying oven at 70°C for drying.

[0056] C. Preparation of complex solution: 5 g of CuSO4 and 1 g of PHMG were weighed in a jar, a magnet was added, and heating and stirring were started when the internal temperature of the jar reached 80°C, and the timing was started for 5 h.

[0057] D. Preparation of long-acting antibacterial polyester fabric: the prepared complex solution was added to the standby polyester fabric in step B at 80°C for 2 h. After the reaction was completed, the polyester fabric was taken out and placed in a forced air drying oven at 70°C for 1 h.

[0058] E, the test of bacteriostatic performance: the polyester fabric prepared in step D is not washed, washed 10 times, 30 times, 50 times, respectively, according to the absorption method in Chinese textile industry standard FZ / T 73023-2006, and verified by escherichia coli, still has good antibacterial property. (Results see the attached drawings of the specification)

[0059] Wash number Control No wash Wash 10 times Wash 30 times Wash 50 times Number of bacteria 5.7 x 10 3 ]]> 0 0 0 0

[0060] Example 4:

[0061] A, alcohol washing of polyester fabric: put the polyester fabric into a beaker, add anhydrous ethanol to cover the polyester fabric, ultrasonic cleaning for 30 min, and then put it in a clean place to dry naturally.

[0062] B, alkali treatment of polyester fabric: weigh 10g NaOH, and 90ML distilled water to prepare 10% sodium hydroxide solution into a jar, put a magnet, and put the jar in a water bath, when the temperature inside the jar is 80℃, add the polyester fabric in step A and stir for 60 min. After taking out, wash with distilled water to neutral, put into the air drying oven at 70℃ for drying.

[0063] C, preparation of complexing solution: weigh 5g CuSO4 and 1g PHMG into a jar, put a magnet, heat and stir until the temperature inside the jar is 80℃, start timing for 5h.

[0064] D, preparation of long-acting antibacterial polyester fiber: add the standby polyester fabric in step B to the prepared complexing solution and react at 80℃ for 1h. After the reaction, take out the polyester fabric and put it into the air drying oven at 70℃ for 1h.

[0065] E, the test of bacteriostatic performance: the polyester fabric prepared in step D is not washed, washed 10 times, 30 times, 50 times, respectively, according to the absorption method in Chinese textile industry standard FZ / T 73023-2006, and verified by escherichia coli, still has good antibacterial property. (Results see the attached drawings of the specification)

[0066] Wash number Control No wash Wash 10 times Wash 30 times Wash 50 times Number of bacteria 5.2 x 10 3 ]]> 0 0 0 0

[0067] Example 5:

[0068] A, alcohol washing of polyester fabric: put the polyester fabric into a beaker, add anhydrous ethanol to cover the polyester fabric, ultrasonic cleaning for 30 min, and then put it in a clean place to dry naturally.

[0069] B. Alkali treatment of polyester fabric: 10 g of NaOH was weighed and dissolved in 90 mL of distilled water to form a 10% NaOH solution, which was then placed in a jar and a magnet was added. The jar was placed in a water bath, and when the temperature inside the jar reached 80°C, the polyester fabric from step A was added and stirred for 60 min. After removal, the fabric was washed with distilled water until neutral, and then placed in a forced air drying oven at 70°C for drying.

[0070] C. Preparation of complexing solution: 5 g of CuSO4 and 1 g of PHMG were weighed into a jar, a magnet was added, and heating and stirring were started. The temperature inside the jar was maintained at 80°C for 5 h.

[0071] D. Preparation of long-acting antibacterial polyester fabric: The prepared complexing solution was added to the standby polyester fabric from step B, and the mixture was reacted at 80°C for 0.5 h. After the reaction was completed, the polyester fabric was removed and placed in a forced air drying oven at 70°C for 1 h.

[0072] E. Test of antibacterial performance: The polyester fabric prepared in step D was not washed, washed 10 times, washed 30 times, and washed 50 times, respectively, and the absorption method in the Chinese textile industry standard FZ / T 73023-2006 was used for detection. Escherichia coli was used for verification, and the fabric still had good antibacterial properties. (The results are shown in the attached drawings)

[0073] Wash number Control No wash Wash 10 times Wash 30 times Wash 50 times Number of bacteria 5.3 x 10 3 ]]> 0 0 0 0

[0074] Example 6:

[0075] A. Alcohol washing of polyester fabric: The polyester fabric was placed in a beaker, anhydrous ethanol was added until the fabric was covered, and ultrasonic cleaning was performed for 30 min. After removal, the fabric was placed in a clean place to dry naturally.

[0076] B. Alkali treatment of polyester fabric: 10 g of NaOH was weighed and dissolved in 90 mL of distilled water to form a 10% NaOH solution, which was then placed in a jar and a magnet was added. The jar was placed in a water bath, and when the temperature inside the jar reached 80°C, the polyester fabric from step A was added and stirred for 60 min. After removal, the fabric was washed with distilled water until neutral, and then placed in a forced air drying oven at 70°C for drying.

[0077] C. Preparation of complexing solution: 5 g of CuSO4 and 1 g of PHMG were weighed into a jar, a magnet was added, and heating and stirring were started. The temperature inside the jar was maintained at 80°C for 5 h.

[0078] D. Preparation of long-acting antibacterial polyester fabric: The prepared complexing solution was added to the standby polyester fabric from step B, and the mixture was reacted at 80°C for 2 h. After the reaction was completed, the polyester fabric was removed and placed in a forced air drying oven at 70°C for 1 h.

[0079] E, the test of bacteriostatic performance: the polyester fabric prepared in step D is not washed, washed 60 times, 80 times, 100 times, respectively, according to the absorption method in China textile industry standard FZ / T 73023-2006, and verified by escherichia coli, still has good antibacterial property. (The results are shown in the drawings of the specification)

[0080] Wash number Control No wash Wash 60 times Wash 80 times Wash 100 times Number of bacteria 5.5 x 10 3 ]]> 0 0 0 0

[0081] Example 7:

[0082] A, alcohol washing of polyester fabric: put the polyester fabric into a beaker, add anhydrous ethanol to cover the polyester fabric, and ultrasonic clean for 30 min. After taking out, put it in a clean place and dry naturally.

[0083] B, alkali treatment of polyester fabric: weigh 10g NaOH, and 90ML distilled water to prepare 10% sodium hydroxide solution into a jar, put into a magnetic son, put the jar in a water bath, when the temperature inside the jar is 80℃, add the polyester fabric in step A and stir for 30 min. After taking out, wash with distilled water to neutral, put into a blast drying oven and dry at 70℃ for standby.

[0084] C, preparation of complexing solution: weigh 5g CuSO4 and 1g PHMG into a jar, put into a magnetic son, heat and stir until the temperature inside the jar is 80℃, start timing for 5h.

[0085] D, preparation of long-acting antibacterial polyester fiber: add the standby polyester fabric in step B to the prepared complexing solution and react at 80℃ for 2h. After the reaction, take out the polyester fabric and put it into a blast drying oven and dry at 70℃ for 1h.

[0086] E, the test of bacteriostatic performance: the polyester fabric prepared in step D is not washed, washed 60 times, 80 times, 100 times, respectively, according to the absorption method in China textile industry standard FZ / T 73023-2006, and verified by escherichia coli, still has good antibacterial property. (The results are shown in the drawings of the specification)

[0087] Wash number Control No wash Wash 60 times Wash 80 times Wash 100 times Number of bacteria 2.9 x 10 3 ]]> 0 0 0 0

[0088] Example 8, preparation of bacteriostatic polyester fiber (I)

[0089] A certain weight of polyester fiber is prepared, which is placed in a beaker, and anhydrous ethanol is added until the polyester fiber can be immersed, and it is placed in an ultrasonic wave for 30 min, and then the polyester fiber is taken out and dried, and placed for standby; 10 g of NaOH and 90 mL of distilled water (i.e. 10% sodium hydroxide solution) are placed in a wide-mouth bottle, and a magnet is added to the wide-mouth bottle. Then the wide-mouth bottle is placed in a water bath, and when the liquid temperature in the wide-mouth bottle reaches 80℃, the alcohol-washed polyester fiber is added, and heated and stirred for 1 h; the alkali-washed polyester fiber is taken out and placed in a beaker containing distilled water, and washed 3-4 times with distilled water until the solution is neutral. Then it is placed in a forced air drying oven for normal temperature drying. 1 g of titanium dioxide and 2 g of polyhexamethylene guanidine (PHMG) are placed in a wide-mouth bottle, and 97 g of distilled water is injected, and a small amount of magnet is added, and stirred at room temperature for 1 h. The alkali-washed polyester fiber is then placed in this wide-mouth bottle, and stirred at room temperature for 2 h. After the reaction is completed, the polyester fiber is taken out and placed in a forced air drying oven for normal temperature drying. A piece is cut off as a sample that is washed 0 times; then the remaining cloth is placed in a beaker containing 250 mL of distilled water, and the beaker is placed in an ultrasonic cleaner for 5 min, which is one washing. According to this step, 0, 3, 6, and 9 times of washing are performed. After washing is completed, they are placed in a forced air drying oven for normal temperature drying, and polyester fiber with antibacterial properties is obtained.

[0090] Example 9, Preparation of Antibacterial Polyester Fiber (Two)

[0091] A certain weight of polyester fiber is prepared, which is placed in a beaker, and anhydrous ethanol is added until the polyester fiber can be immersed, and it is placed in an ultrasonic wave for 30 min, and then the polyester fiber is taken out and dried, and placed for standby; 10 g of NaOH and 90 mL of distilled water (i.e. 10% sodium hydroxide solution) are placed in a wide-mouth bottle, and a magnet is added to the wide-mouth bottle. Then the wide-mouth bottle is placed in a water bath, and when the liquid temperature in the wide-mouth bottle reaches 80℃, the alcohol-washed polyester fiber is added, and heated and stirred for 1 h; the alkali-washed polyester fiber is taken out and placed in a beaker containing distilled water, and washed 3-4 times with distilled water until the solution is neutral. Then it is placed in a forced air drying oven for normal temperature drying. 1 g of titanium dioxide and 2 g of polyhexamethylene guanidine (PHMG) are placed in a wide-mouth bottle, and 97 g of distilled water is injected, and a small amount of magnet is added, and stirred at room temperature for 1 h. The alkali-washed polyester fiber is then placed in this wide-mouth bottle, and stirred at room temperature for 2 h. After the reaction is completed, the polyester fiber is taken out and placed in a forced air drying oven for normal temperature drying. A piece is cut off as a sample that is washed 0 times; then the remaining cloth is placed in a beaker containing 250 mL of distilled water, and the beaker is placed in an ultrasonic cleaner for 5 min, which is one washing. According to this step, 0, 3, 6, and 9 times of washing are performed. After washing is completed, they are placed in a forced air drying oven for normal temperature drying, and polyester fiber with antibacterial properties is obtained.

[0092] Example 10, Preparation of Antibacterial Polyester Fiber (Three)

[0093] A certain weight of polyester fiber is prepared, which is placed in a beaker, and anhydrous ethanol is added until the polyester fiber can be immersed, and it is placed in an ultrasonic bath for 30 min, and then the polyester fiber is taken out and dried, and placed for standby; 10 g of NaOH and 90 mL of distilled water (i.e. 10% sodium hydroxide solution) are placed in a wide-mouth bottle, and a magnet is added to the wide-mouth bottle. Then the wide-mouth bottle is placed in a water bath, and when the liquid temperature inside the wide-mouth bottle reaches 80°C, the alcohol-washed polyester fiber is added, and heated and stirred for 1 h; the alkali-washed polyester fiber is taken out and placed in a beaker containing distilled water, and washed 3-4 times with distilled water until the solution is neutral. Then it is placed in a forced air drying oven for normal temperature drying. 1 g of titanium dioxide and 2 g of polyhexamethylene guanidine (PHMG) are placed in a wide-mouth bottle, and 97 g of distilled water is injected, and a small amount of magnet is added, and stirred at room temperature for 1 h. The alkali-washed polyester fiber is placed in this wide-mouth bottle, and stirred at room temperature for 0.5 h. After the reaction is completed, the polyester fiber is taken out and placed in a forced air drying oven for normal temperature drying, and a piece is cut off as a sample that has not been washed; then the remaining cloth is placed in a beaker containing 250 mL of distilled water, and the beaker is placed in an ultrasonic cleaner for 5 min, which is one washing. According to this step, 0, 3, 6, and 9 times of washing are performed. After washing is completed, they are placed in a forced air drying oven for normal temperature drying, and then labeled and placed separately, which are polyester fibers with antibacterial properties.

[0094] Example 11, Preparation of Antibacterial Polyester Fiber (Four)

[0095] A certain weight of polyester fiber is prepared, which is placed in a beaker, and anhydrous ethanol is added until the polyester fiber can be immersed, and it is placed in an ultrasonic bath for 30 min, and then the polyester fiber is taken out and dried, and placed for standby; 10 g of NaOH and 90 mL of distilled water (i.e. 10% sodium hydroxide solution) are placed in a wide-mouth bottle, and a magnet is added to the wide-mouth bottle. Then the wide-mouth bottle is placed in a water bath, and when the liquid temperature inside the wide-mouth bottle reaches 80°C, the alcohol-washed polyester fiber is added, and heated and stirred for 1 h; the alkali-washed polyester fiber is taken out and placed in a beaker containing distilled water, and washed 3-4 times with distilled water until the solution is neutral. Then it is placed in a forced air drying oven for normal temperature drying. 1 g of titanium dioxide and 2 g of polyhexamethylene guanidine (PHMG) are placed in a wide-mouth bottle, and 97 g of distilled water is injected, and a small amount of magnet is added, and stirred at room temperature for 1 h. The alkali-washed polyester fiber is placed in this wide-mouth bottle, and stirred at room temperature for 0.5 h. After the reaction is completed, the polyester fiber is taken out and placed in a forced air drying oven for normal temperature drying, and a piece is cut off as a sample that has not been washed; then the remaining cloth is placed in a beaker containing 250 mL of distilled water, and the beaker is placed in an ultrasonic cleaner for 5 min, which is one washing. According to this step, 0, 3, 6, and 9 times of washing are performed. After washing is completed, they are placed in a forced air drying oven for normal temperature drying, and then labeled and placed separately, which are polyester fibers with antibacterial properties.

[0096] Example 12, Preparation of Antibacterial Polyester Fabric (Five)

[0097] Prepare a certain weight of polyester fabric, put it into a beaker, and add anhydrous ethanol to be able to immerse the polyester fabric, put it into an ultrasonic bath for 30 min, then take out the polyester fabric and dry it, and place it for standby; weigh 10 g of NaOH and 90 mL of distilled water (i.e. 10% sodium hydroxide solution) into a jar, and add a magnet to the jar. Then place the jar in a water bath, and when the temperature of the liquid inside the jar reaches 80°C, add the alcohol-washed polyester fabric, and heat and stir for 1 h; take out the alkali-washed polyester fabric, put it into a beaker containing distilled water, and wash it 3-4 times with distilled water until the solution is neutral. Then place it in a forced air drying oven for normal temperature drying. Weigh 1 g of titanium dioxide and 0.5 g of polyhexamethylene guanidine (PHMG) into a jar, and inject 98.5 g of distilled water, add a small amount of magnet, and stir for 1 h at room temperature. Then put the alkali-washed polyester fabric into this jar, and stir for 2 h at room temperature. After the reaction is completed, take out the polyester fabric, place it in a forced air drying oven for normal temperature drying, and cut a piece as a sample for 0 times of washing; then put the remaining fabric into a beaker containing 250 mL of distilled water, and place the beaker in an ultrasonic cleaner for 5 min, which is one time of washing. Follow this procedure for 0, 3, 6, and 9 times of washing. After washing is completed, label and place in a forced air drying oven for normal temperature drying, which is the polyester fabric with antibacterial properties.

[0098] Example 13, Antibacterial Test Sample Detection Using Absorption Method for Examples 8-12

[0099] ① Preparation of inoculum: 1 mL of the bacterial suspension was taken into a test tube containing 9 mL of nutrient broth, mixed well, 1 mL of the mixture was taken into 9 mL of nutrient broth, mixed well, 1 mL of the mixture was taken into 9 mL of PBS (0.03 mol / L), mixed well, 1 mL of the mixture was taken into 9 mL of PBS (0.03 mol / L), mixed well, and used as soon as possible (all operations were carried out in a clean bench, which should be turned on for about half an hour before use). ② Inoculation and culture: 0.2 mL of the inoculum was accurately taken with a pipette and inoculated on the prepared sample (antibacterial cloth), the cloth was hung in a wide-mouth bottle with a sterilized copper wire, and the bottle was tightly sealed (all operations were carried out in a clean bench). The culture was carried out in a thermostat at 37℃±1℃ for 18h±1h. ③ Elution and dilution: (all operations were carried out in a clean bench) a. Elution of the untreated sample and the antibacterial sample: the cloth was taken out of the wide-mouth bottle with a forceps and put into a test tube containing 20 mL of cold physiological saline, the test tube was tightly sealed, and the sample was shaken with a mixer or beaten by hand for about 10 seconds. b. 1 mL of the eluate was accurately taken with a pipette and added into 9 mL of physiological saline, and the above steps were repeated to prepare a dilution series. ④ Plate culture: about 25 mL of culture medium was poured into a sterilized plate, and the medium was allowed to solidify. 1 mL of the prepared dilution was accurately taken with a pipette and dropped onto the surface of the culture medium, which was evenly spread with a spreader. The plate was inverted and cultured in a thermostat at 37℃±1℃ for 24h±1h.

[0100] The antibacterial rate was calculated, and the results of Examples 8-11 are shown in the following table.

[0101]

[0102] The antibacterial rate was calculated, and the results of Example 12 are shown in the following table.

[0103]

[0104] As can be seen from the antibacterial results in the above table, the polyester fiber grafted with polyhexamethylene guanidine and titanium dioxide has a strong antibacterial effect on E. coli.

[0105] The above examples are only used to illustrate the technical solutions of the present application, but not limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can be modified, or some technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application, and should be included in the protection scope of the present application.

Claims

1. A method for preparing titanium-coupled long-acting antibacterial polyester fibers based on an efficient pretreatment process, characterized in that the method further comprises the following subsequent steps: B, preparation of titanium-based long-acting antibacterial polyester fibers: 0.5-1.5 parts by weight of titanium dioxide and 1-3 parts by weight of polyhexamethylene guanidine PHMG are weighed into a jar, 95-99 parts by weight of distilled water is injected, a small amount of magnet is placed, and it is placed on a temperature-controlled magnetic stirrer for stirring for 0.5-1.5 h; then the polyester fibers treated by the pretreatment process are placed in the jar, and stirred at room temperature for 1-3 h; after the reaction is completed, the polyester fibers are taken out and dried at room temperature to obtain the titanium-coupled long-acting antibacterial polyester fibers. The method first carries out the following pretreatment before the antibacterial preparation of polyester fiber: A, ultrasonic alcohol washing-high temperature alkali immersion composite pretreatment process: in the ultrasonic reaction container, immerse polyester fiber cloth in anhydrous ethanol, set ultrasonic intensity 0.25-0.35 W / cm 2 , ultrasonic frequency 175-225 KHz, ultrasonic washing 25-35 min, and place the polyester fiber cloth on a sterile operation table for drying / air drying; then immerse the polyester fiber cloth in a 9-11% sodium hydroxide solution, which is preheated to 75-85 DEG C and kept constant temperature in a water bath, immerse for 50-70 min, wash with distilled water for several times to neutral after taking out, and dry / air dry for standby use; In step A, the weight ratio of anhydrous ethanol to polyester fibers is (6-12):

1. In step B, 1 part by weight of titanium dioxide and 2 parts by weight of polyhexamethylene guanidine PHMG are weighed into a jar, 97 parts by weight of distilled water is injected, a small amount of magnet is placed, and it is placed on a temperature-controlled magnetic stirrer for stirring at 300 r / min at room temperature for 1 h; then the polyester fibers treated in step C are placed in the jar, and stirred at room temperature for 2 h; after the reaction is completed, the polyester fibers are taken out and dried at room temperature to obtain the titanium-coupled long-acting antibacterial polyester fibers.

2. A process for the preparation of titanium coupled long lasting antimicrobial polyester fibre based on efficient pre-treatment process as claimed in claim 1, wherein: The method further comprises the following subsequent step: C, washing of polyester fibers: the antibacterial polyester fibers prepared in step B are placed in distilled water, and ultrasonic cleaning is performed in an ultrasonic cleaning machine for 2-8 min, which is recorded as one washing; the washing is performed 0, 3, 6, and 9 times according to this step.

3. A method for preparing titanium-coupled long-lasting antibacterial polyester fiber based on an efficient pretreatment process according to claim 1 or 2, characterized in that: The method further comprises the following subsequent step: C, washing of polyester fibers: the antibacterial polyester fibers prepared in step B are placed in distilled water, and ultrasonic cleaning is performed in an ultrasonic cleaning machine for 5 min, which is recorded as one washing; the washing is performed 0, 3, 6, and 9 times according to this step.

4. A process for the preparation of titanium coupled long lasting antimicrobial polyester fiber based on efficient pre-treatment process as claimed in claim 3, wherein: ​ 5. A process for the preparation of titanium coupled long lasting antimicrobial polyester fiber based on efficient pre-treatment process as claimed in claim 1, wherein: The specific process parameters of Step A are as follows: the polyester fiber cloth is immersed in anhydrous ethanol in an ultrasonic reaction vessel, the ultrasonic intensity is set to 0.30 W / cm 2 , the ultrasonic frequency is 200 KHz, and the polyester fiber cloth is ultrasonically washed for 30 min, and then is dried on a sterile workbench; then the polyester fiber cloth is immersed in a 10% sodium hydroxide solution which is preheated to 80°C and kept constant in a water bath, and is immersed for 60 min, and after being taken out, is washed with distilled water for multiple times until neutral, and is dried for standby use.

Images