Multifunctional nanofiber waterproof and moisture permeable film, preparation method and application thereof

Abstract

The application relates to the technical field of waterproof and moisture-permeable films, and discloses a multifunctional nanofiber waterproof and moisture-permeable film and a preparation method and application thereof, the preparation method is as follows: based on urethane group reaction, Vilsmeier-Haack reaction and Schiff base reaction mechanism, with dodecyl isocyanate, N, N-dihydroxyethyl aniline and polyhexamethylene guanidine hydrochloride as raw materials, a urethane group functional reagent is prepared; with a mixed solvent of N, N-dimethylacetamide and acetone, the urethane group functional reagent, a spinning auxiliary agent and polyurethane are made into a spinning liquid, and a multifunctional nanofiber waterproof and moisture-permeable film is prepared through electrostatic spinning technology; the multifunctional nanofiber waterproof and moisture-permeable film prepared by the application has excellent waterproof and moisture-permeable performance, and the antibacterial rate reaches 99.6%, and the multifunctional nanofiber waterproof and moisture-permeable film can be used as a functional layer of sports product storm jackets, mountaineering clothes and diving clothes.

Description

Technical Field

[0001] This invention relates to the field of waterproof and breathable membrane technology, and in particular to a multifunctional nanofiber waterproof and breathable membrane, its preparation method, and its application. Background Technology

[0002] Waterproof and breathable membranes, as the core functional layer of waterproof and breathable fabrics, are widely used in sports products such as rain jackets, mountaineering clothing, and diving suits. They effectively resist the penetration of external water while promptly wicking away moisture from the skin, greatly improving the comfort of the garments. Furthermore, due to the characteristics of waterproof and breathable membranes used in sports products, antibacterial treatment of these membranes is of great significance.

[0003] Currently, the mainstream waterproof and breathable material on the market is biaxially oriented polytetrafluoroethylene (PTFE) membrane. Although it has excellent overall waterproof and breathable performance, it has disadvantages such as high technical difficulty in preparation, high price, and difficulty in degradation after disposal. Summary of the Invention

[0004] This invention is based on electrospinning technology and uses green and environmentally friendly polyurethane elastomer with excellent comprehensive performance and independently developed urethane-based functional reagents with both antibacterial and hydrophobic functions as raw materials to prepare a multifunctional nanofiber waterproof and breathable membrane.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A method for preparing a multifunctional nanofiber waterproof and breathable membrane includes the following steps:

[0007] Amination of dodecyl isocyanate and N,N-dihydroxyethyl aniline yields phenylated alkyl long-chain terminal urethane monomers.

[0008] Based on the Vilsmeier-Haack reaction mechanism, an aldehyde functional group is introduced onto the phenyl functional group in the phenylated alkyl long-chain capped urethane monomer to obtain an aldehyde-modified alkyl long-chain capped urethane monomer.

[0009] Based on the Schiff base reaction mechanism, aldehyde-modified alkyl long-chain end-capped urethane monomers are grafted onto polyhexamethylene guanidine hydrochloride to obtain urethane functional reagents.

[0010] A multifunctional nanofiber waterproof and breathable membrane was prepared by electrospinning using a mixed solvent of N,N-dimethylacetamide and acetone, in which urethane-based functional reagents, spinning aids and polyurethane were made.

[0011] The mass ratio of urethane-based functional reagent to polyurethane is (0.1-0.5):(9.5-9.9).

[0012] Furthermore, the volume ratio of N,N-dimethylacetamide to acetone is 4:6-10.

[0013] Furthermore, the spinning aid is lithium chloride.

[0014] Furthermore, during the electrospinning process, the receiving distance is 20-25 cm.

[0015] Furthermore, the thickness of the multifunctional nanofiber waterproof and breathable membrane is 30-50 μm.

[0016] Furthermore, the multifunctional nanofiber waterproof and breathable membrane has antibacterial properties.

[0017] An application of a multifunctional nanofiber waterproof and breathable membrane, wherein the multifunctional nanofiber waterproof and breathable membrane is used as a functional layer for sports products such as windproof jackets, mountaineering clothes, and diving suits.

[0018] The beneficial effects of this invention are as follows:

[0019] Based on the mechanisms of urethane reaction, Vilsmeier-Haack reaction and Schiff base reaction, urethane functional reagents were prepared using dodecyl isocyanate, N,N-dihydroxyethylaniline and polyhexamethylene guanidine hydrochloride as raw materials.

[0020] A spinning solution was prepared by combining urethane-based functional reagents and polyurethane, and a multifunctional nanofiber waterproof and breathable membrane was prepared by electrospinning technology.

[0021] Experimental tests show that the multifunctional nanofiber waterproof and breathable membrane prepared by this invention has excellent waterproof and breathable properties, and its antibacterial rate reaches 99.6%. Detailed Implementation

[0022] Experimental Example 1:

[0023] The preparation of urethane-based functional reagents includes the following steps:

[0024] 4.2 g of dodecyl isocyanate and 1.8 g of N,N-dihydroxyethylaniline were added to 100 mL of anhydrous toluene. After stirring and mixing thoroughly, nitrogen gas was introduced, and 0.1 g of dibutyltin dilaurate was added. The temperature was raised to 80 °C and reacted for 1 h. After heating was stopped and the mixture was cooled to room temperature, toluene was removed by vacuum distillation to obtain phenylalkyl long-chain terminal urethane monomer.

[0025] The chemical reaction formula for phenylalkyl long-chain terminal urethane monomers is as follows:

[0026]

[0027] In an ice bath at 0°C, 2.5 g of phosphorus oxychloride was added to 10 mL of N,N-dimethylformamide and stirred for 2 h. Then, 20 mL of N,N-dimethylformamide containing 5.9 g of phenylalkyl long-chain terminal urethane monomer was added and mixed thoroughly. The reaction system was then heated to 90°C and stirred for 4 h. After cooling, the mixture was added to 200 mL of ice water containing 6 g of sodium carbonate and stirred for 12 h. The product was then collected by filtration to obtain aldehyde-modified alkyl long-chain terminal urethane monomer.

[0028] The chemical reaction formula for aldehyde-modified alkyl long-chain terminal urethane monomers is as follows:

[0029]

[0030] The 1H NMR characterization results of the aldehyde-modified alkyl long-chain capped urethane monomer are as follows: 1 H NMR (400MHz, DMSO-D6, δ, ppm): 0.84-0.93 (t, 6H), 1.2-1.37 (m, 36H), 1.43-1.51 (m, 4H), 2.94-2.99 (m, 4H), 3.81-3.85(t, 4H), 4.23-4.27(t, 4H), 5.79-5.82(t, 2H), 6.94-6.97(d, 2H), 7.52-7.54(d, 2H), 9.93(S, 1H);

[0031] Nitrogen gas was introduced, and 2.1 g of polyhexamethylene guanidine hydrochloride (Mn = 2100 g / mol) was added to 20 mL of dimethyl sulfoxide. The mixture was sonicated for 0.5 h, and then 0.64 g of aldehyde-modified alkyl long-chain terminal urethane monomer was added. After stirring evenly, 0.25 mL of triethylamine was added, and the mixture was reacted for 2 h. The dimethyl sulfoxide was removed by vacuum distillation, and the mixture was washed with deionized water and dried to obtain the urethane functional reagent.

[0032] Example 1:

[0033] A method for preparing a multifunctional nanofiber waterproof and breathable membrane includes the following steps:

[0034] Step 1: Prepare a mixed solvent of N,N-dimethylacetamide and acetone at a volume ratio of 2:3. Add polyurethane (BASF, purchased from Shanghai Jingjian Plastics Co., Ltd.) and urethane-based functional reagent (prepared in Example 1) to the mixed solvent to prepare a 10wt% polyurethane-urethane-based functional reagent solution. Add 0.01wt% lithium chloride of the total solution mass. Stir magnetically at 300 r / min for 12 h at room temperature to obtain a uniform spinning solution. The mass ratio of polyurethane to urethane-based functional reagent is 9.6:0.3.

[0035] Step 2: Take the prepared spinning solution and place it on the electrospinning device to start spinning. Under the conditions of 25℃ and 25% relative humidity, set the voltage to 25.5kV, the receiving distance to 22cm, the receiving roller speed to 150r / min, and spin for 8 hours. After spinning is completed, dry it at 80℃ for 4 hours to obtain a multifunctional nanofiber waterproof and breathable membrane with a thickness of 40μm, which is denoted as membrane 1.

[0036] Example 2:

[0037] The application of the multifunctional nanofiber waterproof and breathable membrane prepared in Example 1 is as follows:

[0038] Copolyamide (model DR805PA, purchased from Shanghai Dongrui New Material Co., Ltd.) was used as a hot melt adhesive to laminate polyester fabric and film 1 using a dispensing process. The dispensing time was 0.005s, the dispensing distance was 5mm, the dispensing pressure was 0.38MPa, the melt temperature was 220℃, and the glue dot density was controlled at 50 dots / cm². 2 The cross-sectional area of ​​the adhesive dot is 0.6 mm. 2 .

[0039] Comparative Example 1:

[0040] A method for preparing a multifunctional nanofiber waterproof and breathable membrane includes the following steps:

[0041] Step 1: Prepare a mixed solvent of N,N-dimethylacetamide and acetone at a volume ratio of 2:3. Add polyurethane (BASF, purchased from Shanghai Jingjian Plastics Co., Ltd.) to the mixed solvent to prepare a 10wt% polyurethane solution. Add 0.01wt% lithium chloride of the total mass of the solution. Stir magnetically at 300r / min for 12h at room temperature to obtain a uniform spinning solution.

[0042] Step 2: Take the prepared spinning solution and place it on the electrospinning device to start spinning. Under the conditions of 25℃ and 25% relative humidity, set the voltage to 25.5kV, the receiving distance to 22cm, the receiving roller speed to 150r / min, and spin for 8 hours. After spinning is completed, dry it at 80℃ for 4 hours to obtain a multifunctional nanofiber waterproof and breathable membrane with a thickness of 40μm, which is denoted as membrane 3.

[0043] Performance testing:

[0044] (1) Contact angle test: The water contact angle of membranes 1, 2 and 3 prepared in Example 1 and Comparative Examples 1-2 was measured using an OCA20 Dataphysics contact angle meter. The single circle tangent method was adopted. The volume of deionized water was 5 μL. Fifteen different points were selected on the membrane for measurement, and the average value was recorded.

[0045] (2) Water pressure resistance test: According to the method in AATCC 127-2003 "Water resistance hydrostatic pressure test", membranes 1, 2 and 3 were tested using a YG812C water pressure tester. The membranes were laid on the test ring, and the pressure was increased at a rate of 5 kPa / min. The test area was 100 cm². 2 When the third water droplet appears on the membrane surface, record the hydrostatic pressure value in the instrument;

[0046] (3) Moisture permeability test: The moisture permeability of membranes 1, 2 and 3 was measured using a YG601 water vapor transmission rate tester. Three test points were selected at different locations on the membranes, and 33cm sections were cut. 2 For a circular sample, fix the circular sample in a sample cup, place it in a moisture permeation chamber, set the humidity in the moisture permeation chamber to 90%RH and the temperature to 37℃, cycle the operation 3 times, read the moisture permeation rate, and record the average value.

[0047] The test results are shown in Table 1:

[0048] Table 1 - Test Results

[0049]

[0050] As shown in Table 1, the multifunctional nanofiber waterproof and breathable membrane prepared in Example 1 of the present invention has excellent waterproof and breathable properties. In contrast, Comparative Example 1 only used polyurethane to prepare the nanofiber waterproof and breathable membrane without adding urethane-based functional reagents, resulting in poor waterproof performance.

[0051] According to GB / T 20944.3-2008 standard, the antibacterial rate of membrane 1 was tested, with Staphylococcus aureus selected as the test species. The antibacterial rate was recorded as shown in Table 2.

[0052] Table 2 - Results of Antibacterial Rate Test

[0053] Membrane 1 99.6

[0054] As shown in Table 2, the multifunctional nanofiber waterproof and breathable membrane prepared in Example 1 of the present invention has excellent antibacterial properties.

[0055] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a multifunctional nanofiber waterproof and breathable membrane, characterized in that, Includes the following steps: Dodecyl isocyanate and N,N-dihydroxyethylaniline were added to anhydrous toluene and stirred thoroughly until homogeneous. Dibutyltin dilaurate was then added, and the temperature was raised to 80°C. The reaction was carried out for 1 hour to obtain a phenyl-alkyl long-chain end-capped urethane monomer. The chemical structural formula of the phenylalkyl long-chain terminal urethane monomer is as follows: ； Based on the Vilsmeier-Haack reaction mechanism, an aldehyde functional group is introduced onto the phenyl functional group in the phenylated alkyl long-chain capped urethane monomer to obtain an aldehyde-modified alkyl long-chain capped urethane monomer. Based on the Schiff base reaction mechanism, aldehyde-modified alkyl long-chain end-capped urethane monomers are grafted onto polyhexamethylene guanidine hydrochloride to obtain urethane functional reagents. A multifunctional nanofiber waterproof and breathable membrane was prepared by electrospinning using a mixed solvent of N,N-dimethylacetamide and acetone, in which urethane-based functional reagents, spinning aids and polyurethane were made. The mass ratio of urethane-based functional reagent to polyurethane is (0.1-0.5):(9.5-9.9).

2. The method for preparing a multifunctional nanofiber waterproof and breathable membrane according to claim 1, characterized in that, The volume ratio of N,N-dimethylacetamide to acetone is 4:6-10.

3. The method for preparing a multifunctional nanofiber waterproof and breathable membrane according to claim 1, characterized in that, The spinning aid is lithium chloride.

4. The method for preparing a multifunctional nanofiber waterproof and breathable membrane according to claim 1, characterized in that, During electrospinning, the receiving distance is 20-25cm.

5. The method for preparing a multifunctional nanofiber waterproof and breathable membrane according to claim 1, characterized in that, The thickness of the multifunctional nanofiber waterproof and breathable membrane is 30-50 μm.

6. A multifunctional nanofiber waterproof and breathable membrane prepared by the method described in claim 1, characterized in that, The multifunctional nanofiber waterproof and breathable membrane has antibacterial properties.

7. An application of the multifunctional nanofiber waterproof and breathable membrane according to claim 6, characterized in that, The multifunctional nanofiber waterproof and breathable membrane is used as a functional layer in sports products such as windbreakers, mountaineering clothes, and diving suits.

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