Anti-oil fabric and preparation method thereof

Abstract

The invention belongs to the technical field of nuclear power station radiation protection, aims to solve the problems that at present, nuclear power disposable degradable protective clothing is poor in oil stain resistance, a finishing agent is prone to migration and poor in stability, and discloses an oil stain resistant fabric and a preparation method thereof.The method comprises the steps that firstly, polyvinyl alcohol non-woven fabric and gamma-ray irradiation non-woven fabric are prepared, and hydroxyl radicals are produced; the activated polyvinyl alcohol non-woven fabric is soaked in a solution containing double-bond fluoride for free radical grafting reaction, redundant solution is extruded out, drying and cooling are conducted, then rolling is conducted, and the water-repellent and oil-stain-resistant degradable fabric is prepared. According to the preparation method of the degradable polyvinyl alcohol fabric with the stable water-repellent and oil-stain-resistant functions, the oil-stain-resistant performance of the polyvinyl alcohol fabric is remarkably improved, after the fabric is used, rapid degradation can be achieved through the processes of dissolution, filtration, catalytic oxidation and the like, and the fabric is environmentally friendly and free of pollution.

Description

Technical Field

[0001] The present application belongs to the field of nuclear power plant radiation protection technology, and in particular relates to an oil-resistant fabric and a preparation method thereof. Background Art

[0002] Spunlace nonwovens made from polyvinyl alcohol fibers not only possess high tensile strength, excellent breathability, and are soft and comfortable, but can also be made into a variety of disposable protective clothing, work clothes, shoe covers, caps, and other products in the nuclear power industry. These products are dissolved into a liquid form through a dedicated, efficient degradation system and ultimately completely oxidized to CO2 and H2O through the Fenton reaction, minimizing nuclear power waste.

[0003] Polyvinyl alcohol molecules contain many alcoholic hydroxyl groups, which are highly polar and can form hydrogen bonds with water. Therefore, they can dissolve in polar water. However, their waterproof performance, especially their anti-oil performance, is very poor. The operation of nuclear power plants may involve some environments with serious oil dripping or oil pollution, and the application of such protective products is limited.

[0004] At present, the main method used at home and abroad to improve the waterproof and oil-proof properties of fabrics is finishing. C8 type fluorine-containing fabric finishing agent has become the mainstream product on the market due to its extremely low surface energy and excellent performance, but it has problems such as easy migration, high toxicity, and difficulty in degradation. Summary of the Invention

[0005] The purpose of this application is to provide an oil-resistant fabric and a preparation method thereof, to solve the problems of poor oil resistance and easy migration stability of current nuclear power disposable degradable protective clothing, and to provide a preparation method of a degradable fabric with stable water-repellent and oil-resistant functions, which is suitable for protective products such as disposable protective clothing for nuclear power plants.

[0006] In order to achieve the above objectives, this application provides the following technical solutions:

[0007] In a first aspect, the present application provides a method for preparing an oil-resistant fabric, comprising:

[0008] Step 1: preparing polyvinyl alcohol nonwoven fabric;

[0009] Step 2: irradiating the nonwoven fabric with gamma rays to produce hydroxyl radicals;

[0010] Step 3: soaking the activated polyvinyl alcohol nonwoven fabric in a solution containing double bond fluoride to perform a free radical grafting reaction;

[0011] Step 4: squeeze out excess solution, dry, cool and then roll up to obtain water-repellent, oil-resistant and biodegradable fabric.

[0012] As an practicable manner, in step 1, the polyvinyl alcohol nonwoven fabric is prepared by a hydroentanglement process.

[0013] As an practicable manner, the grammage is 40 gsm to 70 gsm.

[0014] As an practicable method, in step 2, the radioactive gamma source is selected from 60 Co, as an implementable method, has a dose rate of 2-3 kGy / h, an irradiation time of 10-25 min, and a cumulative irradiation dose of 700-900 Gy.

[0015] As an practicable manner, in step 3, the double bond fluoride is one or more of heptadecafluorodecyl methacrylate, dodecafluoroheptyl methacrylate, and tridecafluorooctyl methacrylate.

[0016] As an practicable manner, in step 3, the soaking liquid is a 5% N,N-dimethylformamide solution of double bond fluoride.

[0017] As an practicable manner, in step 3, the grafting reaction temperature is 70° C. to 90° C., and the reaction time is 1.5 h to 2 h.

[0018] As an practicable manner, in step 3, the drying temperature is 160°C.

[0019] In a second aspect, the present application provides an oil-resistant fabric prepared using the above method.

[0020] Compared with the prior art, the oil-resistant fabric and preparation method provided by this application have the following beneficial effects:

[0021] The method provided in this application is a method for preparing a biodegradable polyvinyl alcohol fabric with stable water and oil repellency. First, a PVA nonwoven fabric is irradiated with gamma rays. The hydroxyl groups on the PVA side chains are activated into hydroxyl radicals, which react with double-bonded fluorides in the presence of an initiator to undergo free radical polymerization, thereby grafting low-surface-energy fluorine elements onto the molecular chains, imparting water and oil repellency to the fabric.

[0022] This application can significantly improve the oil and dirt resistance of polyvinyl alcohol fabrics by introducing low-surface-energy fluorine elements, thereby broadening their application scenarios; the functional structure is covalently bonded to polyvinyl alcohol, and the modified polyvinyl alcohol non-woven fabric has excellent performance stability, and there is no problem of performance degradation caused by migration and leakage of the finishing agent over time; after use, the fabric can be rapidly degraded through processes such as dissolution, filtration, and catalytic oxidation, which is environmentally friendly and pollution-free. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solution of this application, the following is a brief introduction to the drawings required for the technical description.

[0024] Figure 1This is a flow chart of the method for preparing the oil-resistant fabric provided in this application. DETAILED DESCRIPTION

[0025] The following is further explained in detail through specific implementation methods.

[0026] The present application provides a method for preparing an oil-resistant fabric, which uses gamma-ray irradiation to activate side chain hydroxyl groups, and then reacts with double-bond fluorides to produce a polyvinyl alcohol fabric with stable water and oil repellency. The specific method includes:

[0027] Step 1: preparing polyvinyl alcohol nonwoven fabric by hydroentanglement process;

[0028] Step 2: γ-ray irradiation of nonwoven fabrics completely activates the hydroxyl groups on the molecular chain to produce hydroxyl free radicals;

[0029] Step 3: soaking the activated polyvinyl alcohol nonwoven fabric in a solution containing double bond fluoride to perform a free radical grafting reaction;

[0030] Step 4: squeeze out the excess solution with a roller, dry at 160°C, and roll up after cooling to obtain the water-repellent, oil-resistant and biodegradable fabric.

[0031] In step 1, the polyvinyl alcohol nonwoven fabric is prepared by a hydroentanglement process, and has a gram weight of 40 gsm to 70 gsm.

[0032] In step 2, the radioactive gamma source is selected 60 Co, the dose rate is 2-3 kGy / h, the irradiation time is 10-25 min, and the cumulative irradiation dose is 700-900 Gy.

[0033] In step 3, the double bond fluoride is one or more of heptadecafluorodecyl methacrylate, dodecafluoroheptyl methacrylate, and tridecafluorooctyl methacrylate.

[0034] In step 3, the soaking liquid is a 5% N,N-dimethylformamide solution of double bond fluoride.

[0035] In step 3, the grafting reaction temperature is 70° C. to 90° C., and the reaction time is 1.5 h to 2 h.

[0036] Example 1

[0037] Prepare 65gsm spunlace polyvinyl alcohol nonwoven fabric by 60Irradiation with a Coγ source for 20 minutes with a dose of 833 Gy can activate the side chain hydroxyl groups of polyvinyl alcohol into hydroxyl free radicals. After complete activation, the non-woven fabric is immersed in a 5% N,N-dimethylformamide solution of heptadecafluorodecyl methacrylate and reacted at 80°C for 2 hours to obtain a fluorine-modified polyvinyl alcohol non-woven fabric through free radical polymerization. The excess solution is squeezed out by a padder, the solvent is dried at 160°C, and the non-woven fabric is rolled up after cooling to obtain a water-repellent, oil-resistant and degradable protective fabric.

[0038] Example 2

[0039] Prepare 45gsm spunlace polyvinyl alcohol nonwoven fabric by 60 The hydroxyl groups on the side chains of polyvinyl alcohol were activated into hydroxyl radicals by Coγ source irradiation for 20 minutes with a dose of 788 Gy. After complete activation, the non-woven fabric was immersed in a 5% dodecafluoroheptyl methacrylate N,N-dimethylformamide solution and reacted at 80°C for 2 hours to obtain fluorine-modified polyvinyl alcohol non-woven fabric through free radical polymerization. The excess solution was squeezed out by a roller, the solvent was dried at 160°C, and the fabric was rolled up after cooling to obtain a water-repellent, oil-resistant and degradable protective fabric.

[0040] Example 3

[0041] Prepare 55gsm spunlace polyvinyl alcohol nonwoven fabric by 60 Irradiation with a Coγ source for 20 minutes with a dose of 816 Gy can activate the side chain hydroxyl groups of polyvinyl alcohol into hydroxyl free radicals. After complete activation, the non-woven fabric is immersed in a 5% N,N-dimethylformamide solution of tridecafluorooctyl methacrylate and reacted at 80°C for 2 hours to obtain a fluorine-modified polyvinyl alcohol non-woven fabric through free radical polymerization. The excess solution is squeezed out by a roller, the solvent is dried at 160°C, and the non-woven fabric is rolled up after cooling to obtain a water-repellent, oil-resistant and degradable protective fabric.

[0042] Comparative Example 1

[0043] Spunlace polyvinyl alcohol nonwoven fabric with a grammage of 65gsm.

[0044] Comparative Example 2

[0045] 65gsm spunlace polyvinyl alcohol nonwoven fabric treated with C8 fluorinated water and oil repellent finishing agent.

[0046] Comparative Example 3

[0047] Prepare 55gsm spunlace polyvinyl alcohol nonwoven fabric by 60Irradiation with a Coγ source for 10 minutes with a dose of 423 Gy can activate the side chain hydroxyl groups of polyvinyl alcohol into hydroxyl free radicals. After complete activation, the non-woven fabric is immersed in a 5% N,N-dimethylformamide solution of heptadecafluorodecyl methacrylate and reacted at 80°C for 2 hours to obtain a fluorine-modified polyvinyl alcohol non-woven fabric through free radical polymerization. The excess solution is squeezed out by a roller, the solvent is dried at 160°C, and the non-woven fabric is rolled up after cooling to obtain a water-repellent, oil-resistant and degradable protective fabric.

[0048] The oil resistance of the fabrics in the examples of this application was evaluated using the corresponding standard GB / T 19977. The oil resistance of the examples and comparative examples was tested and characterized immediately and six months later according to the standard. The test results are shown in Tables 1 and 2.

[0049] Table 1 Test results of oil resistance performance of samples in Example

[0050]

[0051] Table 2 Oil resistance test results of the example samples after 6 months

[0052]

[0053]

[0054] As can be seen from Example 1 and Comparative Example 3 in Table 1, the 10-minute irradiation dose did not fully activate the hydroxyl groups on the molecules, resulting in an insufficient amount of low-surface-energy substances grafted onto the chains, which in turn led to a low oil-resistance rating for the fabric. Comparison of Example 1 and Comparative Example 1 revealed that the specially treated polyvinyl alcohol nonwoven fabric exhibited significantly improved water and oil repellency. It was also found that the oil-resistance of Comparative Example 2 significantly degraded after six months, while the oil-resistance of the present invention's examples showed essentially no degradation. This is because the fluorine atoms are covalently bonded to the polyvinyl alcohol, resulting in excellent performance stability for the modified polyvinyl alcohol nonwoven fabric, eliminating the problem of performance degradation caused by migration and leakage of the finishing agent over time.

[0055] By free radical grafting modification of polyvinyl alcohol nonwovens, the fabric is given excellent water and oil repellency, high performance stability, and a long storage cycle, which expands its application areas and scenarios. It can also be rapidly degraded through a dedicated and efficient system to minimize nuclear power waste.

[0056] In addition, the present application also provides an oil-resistant fabric prepared using the above method.

[0057] The above description is only a specific implementation method of the present application, but the scope of protection of the present application is not limited thereto. Any changes or replacements that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed in this application should be covered by the scope of protection of the present application.

Claims

1. A method for preparing an oil-resistant fabric, characterized in that: include: Step 1: preparing polyvinyl alcohol nonwoven fabric; Step 2: irradiating the nonwoven fabric with gamma rays to produce hydroxyl radicals; Step 3: soaking the activated polyvinyl alcohol nonwoven fabric in a solution containing double bond fluoride to perform a free radical grafting reaction; Step 4: squeeze out excess solution, dry, cool and then roll up to obtain water-repellent, oil-resistant and biodegradable fabric.

2. The method for preparing oil-resistant fabric according to claim 1, characterized in that: In step 1, the polyvinyl alcohol nonwoven fabric is prepared by a hydroentanglement process.

3. The method for preparing oil-resistant fabric according to claim 2, characterized in that: The gram weight is 40gsm~70gsm.

4. The method for preparing oil-resistant fabric according to claim 1, characterized in that: In step 2, select 60 Co was used as the radioactive gamma source.

5. The method for preparing oil-resistant fabric according to claim 4, characterized in that: The dose rate is 2-3 kGy / h, the irradiation time is 10-25 min, and the cumulative irradiation dose is 700-900 Gy.

6. The method for preparing oil-resistant fabric according to claim 1, characterized in that: In step 3, the double bond fluoride is one or more of heptadecafluorodecyl methacrylate, dodecafluoroheptyl methacrylate, and tridecafluorooctyl methacrylate.

7. The method for preparing oil-resistant fabric according to claim 1, characterized in that: In step 3, the soaking liquid is a 5% N,N-dimethylformamide solution of double bond fluoride.

8. The method for preparing oil-resistant fabric according to claim 1, characterized in that: In step 3, the grafting reaction temperature is 70° C. to 90° C., and the reaction time is 1.5 h to 2 h.

9. The method for preparing oil-resistant fabric according to claim 1, characterized in that: In step 3, the drying temperature is 160°C.

10. An oil-resistant fabric, characterized in that: The method is as described in any one of claims 1 to 9.

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