POLYURETHANE NANOFIBER WATERPROOF MOISTURE-PERMEABLE FILM, PREPARATION METHOD THEREOF AND APPLICATION THEREOF

Abstract

The present invention provides a polyurethane nanofiber waterproof moisture-permeable film, a preparation method thereof and application thereof. The polyurethane nanofiber waterproof moisture-permeable film is prepared from two kinds of isothiocyanate and two kinds of polyethylene glycol as raw materials, and the polyurethane nanofiber waterproof moisture-permeable film has good water pressure resistance, tensile property, and moisture permeability. In addition, the polyurethane nanofiber waterproof moisture-permeable film is prepared by adopting an electrostatic spinning method, is low in cost, simple to operate and high in production efficiency, and has a good application prospect in the fields of clothing, medical treatment, electronic appliances, and the like.

Claims

1. A polyurethane nanofiber waterproof moisture-permeable film, wherein the polyurethane nanofiber waterproof moisture-permeable film is prepared from the following raw materials: isothiocyanate I with a functionality of 2, isothiocyanate II with a functionality of 3, polyethylene glycol I with a functionality of 2 and polyethylene glycol II with a functionality of 3.

2. The polyurethane nanofiber waterproof moisture-permeable film according to claim 1, wherein the isothiocyanate I has the following structure: ##STR00011## wherein m is a positive integer of 1 to 3.

3. The polyurethane nanofiber waterproof moisture-permeable film according to claim 1, wherein the isothiocyanate II has the following structure: ##STR00012##

4. The polyurethane nanofiber waterproof moisture-permeable film according to claim 1, wherein the polyethylene glycol I is any one of PEG 400, PEG 800, PEG 1000, PEG 2000, PEG 4000, PEG 6000, PEG 8000 or PEG 10000.

5. The polyurethane nanofiber waterproof moisture-permeable film according to claim 1, wherein the polyethylene glycol II has the following structure: ##STR00013## wherein n is an integer of 6 to 12.

6. A preparation method of the polyurethane nanofiber waterproof moisture-permeable film according to claim 1, comprising the following steps: (1) mixing isothiocyanate I, isothiocyanate II, polyethylene glycol I, and polyethylene glycol II, to dissolve in a solvent; (2) adding a catalyst, heating up to perform reflux reaction, and collecting a product after the reaction ends; and (3) performing electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film.

7. The preparation method of the polyurethane nanofiber waterproof moisture-permeable film according to claim 6, wherein a molar ratio of the isothiocyanate I, isothiocyanate II, polyethylene glycol I, and polyethylene glycol II in the step (1) is (8-16) to (1-1.5) to (8.4-24) to (1.05-3); and the solvent is selected from any one or a mixture of tetrahydrofuran, N, N-dimethylformamide, toluene or dimethyl sulfoxide.

8. The preparation method of the polyurethane nanofiber waterproof moisture-permeable film according to claim 6, wherein the catalyst in step (2) is selected from any one or a mixture of N, N-dimethylethanolamine, trimethylamine, triethylamine, dimethylethanolamine or N-methylmorpholine; and a reaction temperature is 45-55? C.

9. The preparation method of the polyurethane nanofiber waterproof moisture-permeable film according to claim 6, wherein electrospinning conditions in step (3) are as follows: A voltage is 10-90 kV, a receiving distance is 10-50 cm, a liquid supply velocity is 0.1-10 mL/h, a temperature of an spinning environment is 20-35? C., and a relative humidity is 50-95%.

10. An application of the polyurethane nanofiber waterproof moisture-permeable film according to claim 1 in fields of clothing, medical treatment, electronic appliances, and the like.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0036] FIG. 1 is a DSC spectrum of a polyurethane nanofiber waterproof moisture-permeable film prepared in Embodiment 1.

DETAILED DESCRIPTION OF EMBODIMENTS

[0037] The present invention will be described below in combination with specific embodiments. It should be noted that the following embodiments are examples of the present invention, and are only used to illustrate the present invention, not to limit the present invention. Other combinations and various modifications within the concept of the present invention can be made without departing from the spirit or scope of the present invention.

[0038] In the following embodiments, the compounds used and related reagents can be purchased from the market. Polyethylene glycol raw materials can be purchased from Dow, Bayer, Shandong Wanhua and Bluestar Dongda.

Preparation of isothiocyanate I-1

[0039] A preparation method includes the following steps.

[0040] Add 18.2 g of diaminodiphenyl into a reactor including 600 ml of tetrahydrofuran, start stirring, add 67.2 g of triethylenediamine, maintain a temperature at 25? C., dropwise add 44.16 g of carbon disulfide slowly, slowly separate out a light yellow solid after the dropwise addition, stop reaction after 2 hours, filter to obtain a light yellow solid, and wash a filter cake 3 times with 150 ml of n-hexane.

[0041] Add the filter cake obtained in step (1) into 1000 ml of tetrahydrofuran, control a temperature of the system at 5? C., dropwise add 195 g of triphosgene dissolved in tetrahydrofuran, heat up to 50? C. within 2 hours after the dropwise addition for reaction, and maintain the reaction for 2 hours.

[0042] Purify the light yellow solid obtained by the reaction by many times of n-hexane beating, to obtain a product which is isothiocyanate I-1 (a yield is 62%), where an HNMR analysis result with deuterated chloroform as solvent 1 shows that ?7.3-7.5 is a characteristic peak of hydrogen on biphenyl, and the product has a molecular weight of 270 according to an LCMS test.

##STR00006##

Preparation of isothiocyanate 1-2

[0043] A preparation method includes the following steps.

[0044] Add 10.8 g of p-phenylenediamine into a reactor including 600 ml of tetrahydrofuran, start stirring, add 66.09 g of triethylenediamine, maintain a temperature at 25? C., dropwise add 53.3 g of carbon disulfide slowly, slowly separate out a light yellow solid after the dropwise addition, stop reaction after 2 hours, filter to obtain a light yellow solid, and wash a filter cake 3 times with 150 ml of n-hexane.

[0045] Add the filter cake obtained in step (1) into 1000 ml of tetrahydrofuran, control a temperature of the system at 5? C., dropwise add 195 g of triphosgene dissolved in tetrahydrofuran, heat up to 50? C. within 2 hours after the dropwise addition for reaction, and maintain the reaction for 2 hours.

[0046] Purify the light yellow solid obtained by the reaction by many times of n-hexane beating, to obtain a product which is isothiocyanate I-2 (a yield is 58%), where an HNMR analysis result with deuterated chloroform as solvent 1 shows that ?7.3 is a characteristic peak of hydrogen on benzene, and the product has a molecular weight of 194 according to an LCMS test.

##STR00007##

Preparation of isothiocyanate II-1

[0047] A preparation method includes the following steps.

[0048] Add 13.3 g of compound 1 into a reactor including 600 ml of tetrahydrofuran, start stirring, add 67.3 g of triethylenediamine, maintain a temperature at 25? C., dropwise add 39.74 g of carbon disulfide slowly, slowly separate out a light yellow solid after the dropwise addition, stop reaction after 2 hours, filter to obtain a light yellow solid, and wash a filter cake 3 times with 150 ml of n-hexane.

[0049] Add the filter cake obtained in step (1) into 1000 ml of tetrahydrofuran, control a temperature of the system at 5? C., dropwise add 195 g of triphosgene dissolved in tetrahydrofuran, heat up to 50? C. within 2 hours after the dropwise addition for reaction, and maintain the reaction for 2 hours.

[0050] Purify the light yellow solid obtained by the reaction by many times of n-hexane beating, to obtain a final product which is isothiocyanate I-1 (a yield is 53%), where an HNMR analysis result with deuterated chloroform as a solvent 1 shows that ?7.3 is a characteristic peak of hydrogen on benzene, and the product has a molecular weight of 251 according to an LCMS test.

##STR00008##

Preparation of isothiocyanate II-2

[0051] A preparation method includes the following steps.

[0052] Add 28.9 g of compound 2 into a reactor including 600 ml of tetrahydrofuran, start stirring, add 100.8 g of triethylenediamine, maintain a temperature at 25? C., dropwise add 66.24 g of carbon disulfide slowly, slowly separate out a light yellow solid after the dropwise addition, stop reaction after 2 hours, filter to obtain a light yellow solid, and wash a filter cake 3 times with 150 ml of n-hexane.

[0053] Add the filter cake obtained in step (1) into 1000 ml of tetrahydrofuran, control a temperature of the system at 5? C., dropwise add 296 g of triphosgene dissolved in tetrahydrofuran, heat up to 50? C. within 2 hours after the dropwise addition for reaction, and maintain the reaction for 2 hours.

[0054] Purify the light yellow solid obtained by the reaction by many times of n-hexane beating, to obtain a final product which is isothiocyanate II-2 (a yield is 49%), where an HNMR analysis result with deuterated chloroform as a solvent 1 shows that ?7.1-7.2 is a characteristic peak of hydrogen on benzene, and the product has a molecular weight of 417 according to an LCMS test.

##STR00009##

Preparation of isothiocyanate II-3

[0055] A preparation method includes the following steps.

[0056] Add 13.3 g of compound 1 into a reactor including 600 ml of tetrahydrofuran, start stirring, add 67.3 g of triethylenediamine, maintain a temperature at 25? C., dropwise add 39.74 g of carbon disulfide slowly, slowly separate out a light yellow solid after the dropwise addition, stop reaction after 2 hours, filter to obtain a light yellow solid, and wash a filter cake 3 times with 150 ml of n-hexane.

[0057] Add the filter cake obtained in step (1) into 1000 ml of tetrahydrofuran, control a temperature of the system at 5? C., dropwise add 195 g of triphosgene dissolved in tetrahydrofuran, heat up to 50? C. within 2 hours after the dropwise addition for reaction, and maintain the reaction for 2 hours.

[0058] Purify the light yellow solid obtained by the reaction by many times of n-hexane beating, to obtain a final product which is isothiocyanate II (a yield is 65%), where an HNMR analysis result with deuterated chloroform as a solvent 1 shows that ?7.1, ?7.5, and ?7.7 are characteristic peaks of hydrogen on benzene, and the product has a molecular weight of 479 according to an LCMS test.

##STR00010##

Embodiment 1

[0059] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps.

[0060] Add 4 mol of isothiocyanate I-1, 0.3 mol of isothiocyanate II-1, 4.2 mol of PEG 400, and 0.53 mol of polyethylene glycol II with a relative molecular weight of 1000 into a tetrahydrofuran solution.

[0061] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0062] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 20? C., a relative humidity is 50%, a voltage is 10 kV, a receiving distance is 10 cm, and a liquid supply speed is 0.1 mL/h.

Embodiment 2

[0063] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps.

[0064] Add 4 mol of isothiocyanate I-1, 0.29 mol of isothiocyanate II-2, 5mo1 of PEG 800, and 0.56 mol of polyethylene glycol II with a relative molecular weight of 1000 into a tetrahydrofuran solution.

[0065] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0066] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 25? C., a relative humidity is 60%, a voltage is 20 kV, a receiving distance is 15 cm, and a liquid supply speed is 0.5 mL/h.

Embodiment 3

[0067] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps.

[0068] Add 4 mol of isothiocyanate I, 0.27 mol of isothiocyanate II-3, 4.4 mol of PEG 1000, and 0.55 mol of polyethylene glycol II with a relative molecular weight of 1000 into a tetrahydrofuran solution.

[0069] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0070] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 28? C., a relative humidity is 70%, a voltage is 30 kV, a receiving distance is 20 cm, and a liquid supply speed is 1 mL/h.

Embodiment 4

[0071] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps.

[0072] Add 4 mol of isothiocyanate I-2, 0.44 mol of isothiocyanate II-1, 4.8 mol of PEG 2000, and 0.53 mol of polyethylene glycol II with a relative molecular weight of 1500 into a tetrahydrofuran solution.

[0073] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0074] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 30? C., a relative humidity is 75%, a voltage is 40 kV, a receiving distance is 25 cm, and a liquid supply speed is 2 mL/h.

Embodiment 5

[0075] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps.

[0076] Add 4 mol of isothiocyanate I-2, 0.4 mol of isothiocyanate II-2, 5.2 mol of PEG 4000, and 0.52 mol of polyethylene glycol II with a relative molecular weight of 2000 into a tetrahydrofuran solution

[0077] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0078] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 33? C., a relative humidity is 80%, a voltage is 50 kV, a receiving distance is 30 cm, and a liquid supply speed is 3 mL/h.

Embodiment 6

[0079] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps:

[0080] Add 4 mol of isothiocyanate I-2, 0.25 mol of isothiocyanate II-3, 5.6 mol of PEG 6000, and 0.35 mol of polyethylene glycol II with a relative molecular weight of 1000 into a tetrahydrofuran solution.

[0081] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0082] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 35? C., a relative humidity is 85%, a voltage is 60 kV, a receiving distance is 35 cm, and a liquid supply speed is 4 mL/h.

Embodiment 7

[0083] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps.

[0084] Add 4 mol of isothiocyanate I-1, 0.26 mol of isothiocyanate II-2, 5.2 mol of PEG 8000, and 0.36 mol of polyethylene glycol II with a relative molecular weight of 1500 into a tetrahydrofuran solution.

[0085] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0086] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 22? C., a relative humidity is 90%, a voltage is 70 kV, a receiving distance is 40 cm, and a liquid supply speed is 5 mL/h.

Embodiment 8

[0087] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps:

[0088] Add 4 mol of isothiocyanate I-1, 0.31 mol of isothiocyanate II-3, 4.8 mol of PEG 10000, and 0.37 mol of polyethylene glycol II with a relative molecular weight of 2000 into a tetrahydrofuran solution.

[0089] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0090] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 28? C., a relative humidity is 95%, a voltage is 80 kV, a receiving distance is 45 cm, and a liquid supply speed is 6 mL/h.

Embodiment 9

[0091] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps.

[0092] Add 4 mol of isothiocyanate I-2, 0.33 mol of isothiocyanate II-1, 4.6 mol of PEG 400, and 0.38 mol of polyethylene glycol II with a relative molecular weight of 1000 into a tetrahydrofuran solution.

[0093] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0094] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 30? C., a relative humidity is 70%, a voltage is 90 kV, a receiving distance is 50 cm, and a liquid supply speed is 8 mL/h.

Embodiment 10

[0095] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps.

[0096] Add 4 mol of isothiocyanate I-2, 0.36 mol of isothiocyanate II-2, 4.4 mol of PEG 800, and 0.4 mol of polyethylene glycol II with a relative molecular weight of 2000 into a tetrahydrofuran solution.

[0097] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0098] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 35? C., a relative humidity is 65%, a voltage is 30 kV, a receiving distance is 35 cm, and a liquid supply speed is 10 mL/h.

Comparative Example 1

[0099] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps.

[0100] Add 0.3 mol of isothiocyanate II-1, 4.2 mol of PEG 400, and 0.53 mol of polyethylene glycol II with a relative molecular weight of 1000 into a tetrahydrofuran solution.

[0101] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0102] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 20? C., a relative humidity is 50%, a voltage is 10 kV, a receiving distance is 10 cm, and a liquid supply speed is 0.1 mL/h.

Comparative Example 2

[0103] A preparation method of a polyurethane nanofiber waterproof moisture-permeable film includes the specific steps following steps.

[0104] Add 4 mol of isothiocyanate I-1, 5 mol of PEG 800, and 0.56 mol of polyethylene glycol II with a relative molecular weight of 1000 into a tetrahydrofuran solution.

[0105] Add 0.01 mol of N, N-dimethylethanolamine, heat up to 50? C. to perform reflux reaction, and collect a product after the reaction ends.

[0106] Perform electrospinning on the product to prepare the polyurethane nanofiber waterproof moisture-permeable film, where during spinning, a temperature is controlled to 25? C., a relative humidity is 60%, a voltage is 20 kV, a receiving distance is 15 cm, and a liquid supply speed is 0.5 mL/h.

[0107] The waterproof moisture-permeable film prepared in the Embodiments and Comparative Examples is tested, and the test items included moisture permeability, water pressure resistance, tensile strength, elongation at break and differential scanning calorimetry. The moisture permeability is tested with reference to standard ASTM E96-1995 BW. The water pressure resistance is tested with reference to JIS L1092B standard. The tensile strength and elongation at break are tested with reference to standard ASTM D-412, and the results are shown in the table below.

TABLE-US-00001 TABLE 1 Related index test results of a waterproof and moisture-permeable film in Embodiments and Comparative Examples Moisture Water pressure Breaking Elongation Serial permeability resistance strength at break number (g/(m.sup.2 .Math. d)) (mmH.sub.2O) (MPa) (%) Comparative 9529 11563 38.6 400 Example 1 Comparative 9931 11498 37.5 468 Example 2 Embodiment 17865 16295 48.6 765 1 Embodiment 16547 15987 47.2 784 2 Embodiment 17856 16234 48.3 870 3 Embodiment 18210 15863 46.9 941 4 Embodiment 14854 16398 44.5 912 5 Embodiment 15210 16478 45.6 956 6 Embodiment 17596 16385 48.9 1081 7 Embodiment 18410 16888 48.7 945 8 Embodiment 16987 16289 45.6 845 9 Embodiment 17583 16301 44.1 811 10

[0108] It can be learned from the comparison of Comparative Example 1, Comparative Example 2 and embodiment 1, that the polyurethane waterproof moisture-permeable film in Embodiment 1 has higher moisture permeability, water pressure resistance, elongation at break and breaking strength, and has better performance. Based on the comparison of the Comparative Examples and Embodiments, it can be learned that the polyurethane nanofiber waterproof moisture-permeable film provided in the present invention has good water pressure resistance, and tensile performance. The polyurethane nanofiber waterproof moisture-permeable film provided in the present invention is prepared using isothiocyanate as a raw material. The biphenyl structure contained in isothiocyanate can show a liquid crystal state (as shown in FIG. 1) at a specific temperature. There are more micropore structures, an atomic radius of S is larger, and there are larger pore diameters in the structure, so that a gas transmission rate can be increased and moisture permeability is excellent. In addition, the polyurethane nanofiber waterproof moisture-permeable film provided in the present invention is prepared by adopting an electrostatic spinning method, is low in cost, simple to operate and high in production efficiency, and has a good application prospect in the fields of clothing, medical treatment, electronic appliances, and the like.

[0109] The above embodiments are only to illustrate the technical concepts and characteristics of the present invention, and their purpose is to let those familiar with the technology understand the content of the present invention and implement them, and cannot limit the scope of protection of the present invention. All equivalent changes or modifications shall be fall within the protection scope of the present invention.