Preparation method of antibacterial anti-ultraviolet cool polyester master batch and fiber

Abstract

The invention discloses an antibacterial anti-ultraviolet cool-feeling polyester master batch which is prepared from an imidazolate framework ZIF-8 prepared from zinc nitrate hexahydrate and 2-methylimidazole, jade powder, polyester chip powder, a dispersing agent and an antioxidant through melting granulation, and the polyester master batch with antibacterial, anti-ultraviolet and cool-feeling functions is obtained. The polyester master batch has antibacterial, anti-ultraviolet and cool-feeling functions, and fibers prepared from the polyester master batch still have excellent antibacterial, anti-ultraviolet and cool-feeling properties after being washed for 50 times, and show good washing resistance.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of multifunctional polyester masterbatch and fiber, and in particular to a preparation method of antibacterial and anti-ultraviolet cool-feeling polyester masterbatch and fiber. Background Art

[0002] With the advancement of science and technology, functional textiles have also emerged, and people's demand for textiles with antibacterial, UV-resistant, cool and other properties has increased dramatically. Polyester fiber is an important variety of synthetic fiber, with the characteristics of being strong and durable, good elasticity, not easy to deform, crisp, easy to wash and dry quickly, etc. Functional finishing of polyester fiber can effectively meet people's needs for the wearability and functionality of textiles.

[0003] Currently, the commonly used antibacterial and UV-proof cool fiber products are mainly obtained by post-finishing. This method is simple to operate and low in cost. It is more commonly used in the printing and dyeing industry, but it has the disadvantages of poor washing resistance and short-lasting effect. Summary of the invention

[0004] In order to solve certain technical problems existing in the prior art, one of the purposes of the present application is to provide an antibacterial, anti-ultraviolet and cool polyester masterbatch, which can make the polyester masterbatch have antibacterial, anti-ultraviolet and cool functions, and the fiber prepared by the polyester masterbatch still has excellent antibacterial, anti-ultraviolet and cool properties after 50 washings, showing good water washing resistance.

[0005] The second purpose of the present application is to provide a method for preparing antibacterial and anti-ultraviolet cool polyester fibers. The functional polyester fibers prepared by the masterbatch addition method can evenly disperse the functional powder into the fiber body without affecting the feel of the fiber / fabric, and the function is long-lasting and the operation is flexible and convenient.

[0006] In order to solve the above existing technical problems, one of the purposes of this application is achieved by adopting the following technical solution:

[0007] The invention discloses an antibacterial, anti-ultraviolet and cool-feeling polyester masterbatch, comprising an imidazole ester skeleton ZIF-8 prepared by taking zinc nitrate hexahydrate and 2-methylimidazole as raw materials, jade powder, polyester chip powder, a dispersant and an antioxidant, and the polyester masterbatch with antibacterial, anti-ultraviolet and cool-feeling functions is obtained by melt granulation.

[0008] The imidazolate skeleton ZIF-8 is an organic metal framework made by the reaction of zinc nitrate hexahydrate and 2-methylimidazole. It has a regular dodecahedral structure and has excellent absorption and reflection functions for ultraviolet rays. At the same time, the imidazolate skeleton ZIF-8 can release zinc ions, which are effective antibacterial ions that are beneficial to the human body. Jade powder, as a commonly used and effective cooling material, also has an antibacterial effect. After combining with the skeleton structure of ZIF-8, it can show better cooling and antibacterial effects. However, due to the characteristics of the imidazole ester skeleton ZIF-8 and jade powder itself and the fiber structure characteristics, it is difficult to effectively combine them through conventional processes. As a result, even if they are improved through post-treatment, their functional effects will inevitably be greatly reduced after multiple washings. In the present application, the imidazole ester skeleton ZIF-8, jade powder, polyester chip powder, dispersant and antioxidant are mixed to prepare a polyester masterbatch with antibacterial, anti-ultraviolet and cooling functions, so that the polyester masterbatch has excellent functional characteristics. After being applied to fiber production, it can effectively avoid the problem of excessive reduction in antibacterial, anti-ultraviolet and cooling functions due to washing and other reasons, and also solves the problem that the current fiber needs to increase post-treatment to achieve antibacterial, anti-ultraviolet and cooling functions.

[0009] Preferably, the preparation steps of the antibacterial and anti-ultraviolet cool feeling polyester masterbatch include:

[0010] Step 1: preparing imidazole ester framework ZIF-8 by using zinc nitrate hexahydrate and 2-methylimidazole as raw materials;

[0011] Step 2: Mix and grind the imidazolate framework ZIF-8 and jade powder to obtain a mixed powder;

[0012] Step 3: Blend the obtained mixed powder with polyester chip powder, dispersant and antioxidant to obtain a mixture, and use a twin-screw extruder to melt extrude and pelletize to obtain a functional polyester masterbatch containing imidazole ester skeleton ZIF-8 and jade powder.

[0013] Preferably, the preparation method of the imidazole ester framework ZIF-8 comprises:

[0014] S1. Dissolve 6-40 g of zinc nitrate hexahydrate in 200-1000 ml of methanol to obtain solution I.

[0015] S2, dissolving 7-48 g of dimethylimidazole in 200-1500 ml of methanol to obtain solution II;

[0016] S3. Mix solution I and solution II, ultrasonicate for 30 to 60 minutes, and then stand at room temperature for 12 to 24 hours; centrifuge the obtained product at 6000 to 8000 r / min for 15 to 30 minutes, wash the obtained solid with methanol 3 to 5 times, and then dry it at 60 to 80°C.

[0017] Preferably, the imidazolate framework ZIF-8 and jade powder in step 2 have a particle size of nanometer level after grinding.

[0018] Preferably, the mixed powder in step 2 comprises 40 to 50 parts of imidazole ester framework ZIF-8 and 50 to 60 parts of jade powder.

[0019] Preferably, the mixture in step 3 comprises 30 to 40 parts of mixed powder, 60 to 70 parts of polyester chip powder, 1 to 5 parts of dispersant and 0.5 to 1 part of antioxidant.

[0020] Preferably, the dispersant includes one or more of sodium polyacrylate, sodium hexametaaluminate, polyvinyl pyrrolidone, sodium dodecylbenzene sulfonate, sodium hexametaphosphate, and polyethylene glycol-400.

[0021] Preferably, the antioxidant includes one or more of antioxidant 1010, antioxidant 264, antioxidant 1076, and antioxidant 5057.

[0022] The second purpose of this application is achieved by the following technical solution:

[0023] A method for preparing antibacterial and anti-ultraviolet cool polyester fiber comprises an antibacterial and anti-ultraviolet cool polyester masterbatch. The antibacterial and anti-ultraviolet cool polyester fiber is prepared by melt spinning the antibacterial and anti-ultraviolet cool polyester masterbatch and common polyester chips.

[0024] Preferably, the preparation method of the polyester fiber is: put the antibacterial and anti-ultraviolet cooling polyester masterbatch and ordinary polyester chips into a static mixer and mix them evenly, then feed them into a screw extruder, extrude them into filaments after melting, and cool them to obtain the antibacterial and anti-ultraviolet cooling polyester fiber.

[0025] Preferably, the mass ratio of the antibacterial and anti-ultraviolet cool-feeling polyester masterbatch to the common polyester chips is 10-12:88-90.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] Through the compound use of ZIF-8 and jade powder materials, they are blended and granulated with polyester chip powder to prepare polyester masterbatch with antibacterial and anti-ultraviolet cooling function, and then blended and spun with ordinary polyester chips to obtain antibacterial and anti-ultraviolet cooling polyester fiber. After weaving, the obtained fiber has an antibacterial rate of more than 99% against Escherichia coli, Staphylococcus aureus and Candida albicans; UPF is increased from 13 to 213, UVA transmittance is reduced from 48.3% to 2.9%, and the cooling coefficient can reach 0.236 J / (cm2·s), and it has excellent water washability, and the antibacterial and anti-ultraviolet cooling performance is long-lasting. DETAILED DESCRIPTION

[0028] The preferred embodiments of the present invention are described in detail to make the advantages and features of the present invention easier to be understood by those skilled in the art, thereby making a clearer and more specific definition of the protection scope of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments.

[0029] Embodiment 1:

[0030] Dissolve 10 g of zinc nitrate hexahydrate in 400 ml of methanol to obtain solution I; dissolve 12 g of dimethylimidazole in 500 ml of methanol to obtain solution II; mix solution I and solution II, ultrasonicate for 35 min, and let stand at room temperature for 12 h; centrifuge the obtained product at 6000 r / min for 15 min, wash the obtained solid three times with methanol, and then dry it at 60°C.

[0031] 40 parts of the prepared imidazole ester framework ZIF-8 and 60 parts of jade powder were mixed and ground to prepare a mixed powder.

[0032] 30 parts of mixed powder, 68.5 parts of polyester chip powder, 1 part of sodium polyacrylate and 0.5 parts of antioxidant 5057 are blended to obtain a mixture, which is melt-extruded and pelletized using a twin-screw extruder to obtain a functional polyester masterbatch containing an imidazole skeleton ZIF-8 and jade powder.

[0033] 10 parts of functional polyester masterbatch and 90 parts of common polyester chips are put into a static mixer and mixed evenly, and then fed into a screw extruder, extruded into filaments after melting, and cooled to obtain antibacterial and anti-ultraviolet cool polyester fibers.

[0034] Example 2

[0035] Dissolve 20 g of zinc nitrate hexahydrate in 600 ml of methanol to obtain solution I; dissolve 24 g of dimethylimidazole in 900 ml of methanol to obtain solution II; mix solution I and solution II, ultrasonicate for 45 min, and let stand at room temperature for 15 h; centrifuge the obtained product at 7000 r / min for 20 min, wash the obtained solid 4 times with methanol, and then dry it at 70°C.

[0036] 45 parts of the prepared imidazole ester framework ZIF-8 were mixed and ground with 55 parts of jade powder to obtain a mixed powder.

[0037] 35 parts of mixed powder, 61.2 parts of polyester chip powder, 3 parts of sodium polyacrylate and 0.8 parts of antioxidant 5057 were blended, melt-extruded and pelletized using a twin-screw extruder to obtain a functional polyester masterbatch containing an imidazole skeleton ZIF-8 and jade powder.

[0038] 11 parts of functional polyester masterbatch and 89 parts of common polyester chips are put into a static mixer and mixed evenly to obtain a mixture, which is then fed into a screw extruder and extruded into filaments after being melted. After cooling, the antibacterial and anti-ultraviolet cool polyester fiber is obtained.

[0039] Example 3

[0040] Dissolve 30 g of zinc nitrate hexahydrate in 800 ml of methanol to obtain solution I; dissolve 36 g of dimethylimidazole in 1200 ml of methanol to obtain solution II; mix solution I and solution II, ultrasonicate for 55 min, and let stand at room temperature for 20 h; centrifuge the obtained product at 8000 r / min for 25 min, wash the obtained solid with methanol 5 times, and then dry it at 80°C.

[0041] 50 parts of the prepared imidazole ester framework ZIF-8 were mixed and ground with 50 parts of jade powder to obtain a mixed powder.

[0042] 40 parts of mixed powder, 54 parts of polyester chip powder, 5 parts of sodium polyacrylate and 1 part of antioxidant 5057 are blended to obtain a mixture, which is melt-extruded and pelletized using a twin-screw extruder to obtain a functional polyester masterbatch containing an imidazole skeleton ZIF-8 and jade powder.

[0043] 12 parts of functional polyester masterbatch and 88 parts of common polyester chips were put into a static mixer and mixed evenly, then fed into a screw extruder, extruded into filaments after being melted, and then cooled to obtain antibacterial and anti-ultraviolet cool polyester fibers.

[0044] Comparative Example 1

[0045] Dissolve 20 g of zinc nitrate hexahydrate in 600 ml of methanol to obtain solution I; dissolve 24 g of dimethylimidazole in 900 ml of methanol to obtain solution II; mix solution I and solution II, ultrasonicate for 45 min, and let stand at room temperature for 15 h; centrifuge the obtained product at 7000 r / min for 20 min, wash the obtained solid 4 times with methanol, and then dry it at 70°C.

[0046] 45 parts of the prepared imidazole ester framework ZIF-8 and 55 parts of jade powder were mixed and ground to prepare a mixed powder. The mixed powder was dispersed in deionized water at 3.8% owf to prepare a mixed suspension.

[0047] Ordinary polyester chips are put into a static mixer, fed into a screw extruder, and extruded into filaments after being melted. After cooling, polyester fibers are obtained, and polyester fabrics are woven.

[0048] Alkali weight reduction treatment: Sodium hydroxide is used to perform alkali weight reduction treatment on polyester fabric. Smaller grooves appear on the surface of polyester fabric, which is conducive to the combination of imidazolate skeleton ZIF-8 and jade powder particles with the fabric.

[0049] The etched polyester fabric was immersed in a 3.8% owf mixed solution and ultrasonicated for 2 hours. After standing for 24 hours, the fabric was washed three times with deionized water and dried to obtain a finished polyester fabric.

[0050] Compared with Examples 1-3, the polyester was not modified by the masterbatch blending method, and the imidazolate skeleton ZIF-8 and jade powder were coated on the fiber surface by a simple dip coating method.

[0051] Comparative Example 2

[0052] Ordinary polyester chips are put into a static mixer, fed into a screw extruder, extruded into filaments after being melted, and then cooled to obtain ordinary polyester fibers.

[0053] The yarns obtained from the following examples and comparative examples were woven into 25×25 cm fabrics using a semi-automatic shaft sample loom for testing of antibacterial, anti-ultraviolet and cooling properties.

[0054] (I) Antibacterial test

[0055] According to GB / T 20944.3-2008 "Evaluation of Antibacterial Properties of Textiles Part 3: Oscillation Method", the antibacterial properties of functional polyester fibers were tested. 0.75g of Examples 1-3, Comparative Examples 1-2 and blank samples were placed in 250ml conical flasks, 70ml of 0.03mol / L PBS buffer was added, and 5ml of inoculated bacterial solution was added to the conical flasks with a pipette. The conical flasks were shaken at 150r / min for 18h at 24°C. The live bacteria concentration of the bacterial solution in the conical flasks before and after shaking was measured, and the antibacterial rate was calculated to evaluate the antibacterial effects of Examples 1-3 and Comparative Examples 1-2 on Staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC25922) and Candida albicans (ATCC 10231) before washing. When the antibacterial rate of the sample on Staphylococcus aureus and Escherichia coli is ≥70%, and the antibacterial rate on Candida albicans is ≥60%, the sample has an antibacterial effect. The antibacterial test results are shown in Table 1.

[0056] Table 1: Antibacterial performance test analysis table

[0057]

[0058] (II) Anti-ultraviolet performance test

[0059] The UV protection standard is usually evaluated by the UV protection factor. The higher the UPF value, the better the UV protection effect. According to my country's national standard GB / T 18830-2009 "Evaluation of UV protection performance of textiles", only when the UPF value of the sample is greater than 40 and the UVA transmittance is less than 5%, can it be called an "UV protection product".

[0060] The UV-2000 UV protection tester was used to test the anti-ultraviolet performance of the fabric. Five 150×150 mm specimens were selected from each fabric sample in Examples 1-3 and Comparative Examples 1-2, and six points were evenly selected on the fabric for testing. The anti-ultraviolet performance results are shown in Table 2.

[0061] Table 2: Anti-ultraviolet performance test analysis table

[0062]

[0063] (III) Coolness test

[0064] The cooling performance of textiles is usually evaluated by the instantaneous cooling performance (Qmax) of the sample. When Qmax ≥ 0.15, it indicates that the fabric has instantaneous cooling performance. 200×200mm samples of the fabrics prepared in Examples 1-3 and Comparative Examples 1-2 were taken respectively, and the cooling coefficient was tested according to "GBT 35263-2017 Testing and Evaluation of the Instantaneous Cooling Performance of Textiles", wherein the temperature of the heat detection plate was 35°C and the temperature of the sample carrier was 20°C.

[0065] Then, each group of samples was machine washed at room temperature, the washing time was 10 minutes, the water level was full, the stirring speed was 180r / min, the drying speed was 650r / min, the drying time was 6 minutes, and then naturally air-dried. After 50 cycles of washing and air-drying, the antibacterial properties, anti-ultraviolet properties and cooling properties of the samples were tested again. The cooling properties are shown in Table 3.

[0066] Table 3: Cooling performance test analysis table

[0067]

[0068] It can be seen from Tables 1 to 3 that, relative to the conventional polyester fiber of Comparative Example 2, the samples in Examples 1-3 of the present invention all have excellent antibacterial, anti-ultraviolet and cooling properties, and their UPF and cooling coefficient increase with the increase of the content of imidazolate skeleton ZIF-8 and jade powder, indicating that the addition of imidazolate skeleton ZIF-8 and jade powder makes the polyester fiber multifunctional, effectively improves the antibacterial, anti-ultraviolet and cooling properties of the polyester fabric, and still has good performance after washing 50 times, while the performance of Comparative Example 1 is greatly reduced after washing. This is mainly because the imidazolate skeleton ZIF-8 and jade powder in Examples 1-3 are modified by the masterbatch blending method to modify the polyester fiber, which has better washing resistance than the post-finishing method.

[0069] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. An antibacterial and anti-ultraviolet cool feeling polyester masterbatch, characterized in that: The invention comprises an imidazole ester skeleton ZIF-8 prepared by taking zinc nitrate hexahydrate and 2-methylimidazole as raw materials, jade powder, polyester chip powder, a dispersant and an antioxidant, and a polyester masterbatch with antibacterial, anti-ultraviolet and cooling functions is obtained by melt granulation.

2. The antibacterial and anti-ultraviolet cool feeling polyester masterbatch according to claim 1, characterized in that: The preparation steps of the antibacterial and anti-ultraviolet cool feeling polyester masterbatch include: Step 1: preparing imidazole ester framework ZIF-8 by using zinc nitrate hexahydrate and 2-methylimidazole as raw materials; Step 2: Mix and grind the imidazolate framework ZIF-8 and jade powder to obtain a mixed powder; Step 3: Blend the obtained mixed powder with polyester chip powder, dispersant and antioxidant to obtain a mixture, and use a twin-screw extruder to melt extrude and pelletize to obtain a functional polyester masterbatch containing imidazole ester skeleton ZIF-8 and jade powder.

3. The antibacterial and anti-ultraviolet cool feeling polyester masterbatch according to claim 2, characterized in that: The preparation method of the imidazole ester framework ZIF-8 comprises: S1. Dissolve 6-40 g of zinc nitrate hexahydrate in 200-1000 ml of methanol to obtain solution I. S2, dissolving 7-48 g of dimethylimidazole in 200-1500 ml of methanol to obtain solution II; S3. Mix solution I and solution II, ultrasonicate for 30 to 60 minutes, and then stand at room temperature for 12 to 24 hours; centrifuge the obtained product at 6000 to 8000 r / min for 15 to 30 minutes, wash the obtained solid with methanol 3 to 5 times, and then dry it at 60 to 80°C.

4. The antibacterial and anti-ultraviolet cool feeling polyester masterbatch according to claim 2, characterized in that: The imidazolate framework ZIF-8 and jade powder in the step 2 have a particle size of nanometer level after grinding.

5. The antibacterial and anti-ultraviolet cool feeling polyester masterbatch according to claim 2, characterized in that: The mixed powder in step 2 includes 40 to 50 parts of imidazole ester framework ZIF-8 and 50 to 60 parts of jade powder.

6. The antibacterial and anti-ultraviolet cool feeling polyester masterbatch according to claim 2, characterized in that: The mixture in step 3 includes 30-40 parts of mixed powder, 60-70 parts of polyester chip powder, 1-5 parts of dispersant and 0.5-1 part of antioxidant.

7. The antibacterial and anti-ultraviolet cool feeling polyester masterbatch according to claim 1, characterized in that: The dispersant includes one or more of sodium polyacrylate, sodium hexametaaluminate, polyvinyl pyrrolidone, sodium dodecylbenzene sulfonate, sodium hexametaphosphate, and polyethylene glycol-400.

8. The antibacterial and anti-ultraviolet cool feeling polyester masterbatch according to claim 1, characterized in that: The antioxidant includes one or more of antioxidant 1010 , antioxidant 264 , antioxidant 1076 , and antioxidant 5057 .

9. A method for preparing an antibacterial and anti-ultraviolet cool feeling polyester fiber, characterized in that: The invention comprises the antibacterial and anti-ultraviolet cool-feeling polyester masterbatch as claimed in any one of claims 1 to 8, wherein the antibacterial and anti-ultraviolet cool-feeling polyester fiber is prepared by melt-spinning the antibacterial and anti-ultraviolet cool-feeling polyester masterbatch and common polyester chips.

10. The method for preparing the antibacterial and anti-ultraviolet cool feeling polyester fiber according to claim 9, characterized in that: The mass ratio of the antibacterial and anti-ultraviolet cool-feeling polyester masterbatch to the common polyester chips is 10-12:88-90.

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