Hydrophobic elastic fiber as well as preparation method and application thereof

Abstract

The invention relates to the technical field of fiber processing, and discloses a hydrophobic elastic fiber and a preparation method and application thereof. The method comprises the following steps: (1) drying a styrene-ethylene-butylene-styrene block copolymer, and carrying out melt spinning to obtain elastic fibers; in the presence of a solvent, mixing silicon dioxide, a fluorine-containing material, a silane coupling agent and epoxy resin to obtain impregnation liquid; and (2) carrying out impregnation treatment on the elastic fiber in the impregnation liquid to obtain the hydrophobic elastic fiber. The hydrophobic elastic fiber prepared by the method provided by the invention has long-acting super-hydrophobic capacity and excellent mechanical properties, and can be widely applied to the field of textiles.

Description

Technical Field

[0001] The present invention relates to the technical field of fiber processing, and in particular to a hydrophobic elastic fiber and a preparation method and application thereof. Background Art

[0002] Traditional melt-spun fibers have poor elasticity, low elongation and low recovery, which limits their application in some areas. Therefore, elastic fibers, especially styrene-ethylene-butylene-styrene (SEBS)-based elastic fibers, are widely used in medical materials, clothing, filter materials, shape memory materials and other fields. However, conventional SEBS is difficult to spin into elastic fibers with excellent performance due to its large molecular weight and high melt viscosity, which limits its application in the textile field.

[0003] Furthermore, although the elastic fiber spun from SEBS has a certain hydrophobicity due to its rich microstructure, it is insufficient in long-term use or dust and dirt prevention.

[0004] Therefore, preparing a SEBS elastic fiber with long service life and long-term stain resistance and waterproof performance has outstanding economic value and application prospects.

[0005] CN102758269A discloses an elastic fiber, which is characterized in that: the raw material of the elastic fiber is a linear triblock copolymer of styrene-ethylene / butylene-styrene, the styrene content in the block copolymer is greater than 40wt% and less than 60wt%; the elastic recovery rate of the elastic fiber under 100% stretching conditions is greater than 93%, and the elastic recovery rate under 200% stretching conditions is greater than 92%; the elastic fiber provided by the scheme has no hydrophobicity and no anti-fouling effect.

[0006] CN104789124A discloses a method for preparing a super double hydrophobic surface, using an alcohol-water mixed solution as a medium, using an acid or base as a catalyst, an organosilane mixture and nanoparticles undergo a hydrolysis condensation reaction to obtain an organosilane polymer / nanoparticle composite suspension; the organosilane polymer / nanoparticle composite suspension is then sprayed on the substrate surface to form a coating, and then treated by thermal curing to obtain a stable super double hydrophobic surface. This scheme adopts a spraying method, and a thermal curing process is required, which is not conducive to large-scale preparation. Spraying can only be performed for surface modification, and good hydrophobicity modification cannot be achieved for the interior of a fiber with a complex internal network structure. Summary of the invention

[0007] The purpose of the present invention is to solve the problem of insufficient mechanical properties and hydrophobic properties of elastic fibers in the prior art.

[0008] In order to achieve the above object, the first aspect of the present invention provides a method for preparing a hydrophobic elastic fiber, the method comprising:

[0009] (1) drying and melt-spinning the styrene-ethylene-butylene-styrene block copolymer in sequence to obtain the elastic fiber; and

[0010] In the presence of a solvent, silicon dioxide, a fluorine-containing material, a silane coupling agent and an epoxy resin are mixed to obtain an impregnation solution;

[0011] (2) immersing the elastic fiber in the impregnation liquid to obtain the hydrophobic elastic fiber; the conditions of the impregnation treatment include: a temperature of 25-30° C. and a time of 30-90 min;

[0012] Relative to every 100 mL of solvent, the amount of the silicon dioxide is 0.6-1.5 g, the amount of the fluorine-containing material is 1.2-3.2 g, the amount of the silane coupling agent is 0.6-1.5 g, and the amount of the epoxy resin is 0.6-1.5 g;

[0013] The styrene structural unit content of the styrene-ethylene-butylene-styrene block copolymer is 15-30wt%, the Shore A hardness is 50-60, the melt index (230°C, 2.16Kg) is 210-220g / min or the melt index (200°C, 5Kg) is 25-35g / min;

[0014] The fluorine-containing material is selected from at least one of perfluorooctylmethyldichlorosilane, perfluorodecyltriethoxysilane and perfluorodecyltrichlorosilane.

[0015] The second aspect of the present invention provides a hydrophobic elastic fiber prepared by the method described in the first aspect.

[0016] The third aspect of the present invention provides application of the hydrophobic elastic fiber described in the second aspect in the textile field.

[0017] The invention adopts a specific styrene-ethylene-butylene-styrene block copolymer as a raw material to prepare elastic fibers, and the hydrophobic elastic fibers prepared by a specific impregnation treatment have long-lasting super-hydrophobicity and excellent mechanical properties. DETAILED DESCRIPTION

[0018] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0019] As mentioned above, the first aspect of the present invention provides a method for preparing a hydrophobic elastic fiber, characterized in that the method comprises:

[0020] (1) drying and melt-spinning the styrene-ethylene-butylene-styrene block copolymer in sequence to obtain the elastic fiber; and

[0021] In the presence of a solvent, silicon dioxide, a fluorine-containing material, a silane coupling agent and an epoxy resin are mixed to obtain an impregnation solution;

[0022] (2) immersing the elastic fiber in the impregnation liquid to obtain the hydrophobic elastic fiber; the conditions of the impregnation treatment include: a temperature of 25-30° C. and a time of 30-90 min;

[0023] For every 100 mL of solvent, the amount of the silicon dioxide is 0.6-1.5 g, the amount of the fluorine-containing material is 1.2-3.2 g, the amount of the silane coupling agent is 0.6-1.5 g, and the amount of the epoxy resin is 0.6-1.5 g;

[0024] The styrene structural unit content of the styrene-ethylene-butylene-styrene block copolymer is 15-30wt%, the Shore A hardness is 50-60, the melt index (230°C, 2.16Kg) is 210-220g / min or the melt index (200°C, 5Kg) is 25-35g / min;

[0025] The fluorine-containing material is selected from at least one of perfluorooctylmethyldichlorosilane, perfluorodecyltriethoxysilane and perfluorodecyltrichlorosilane.

[0026] Preferably, the epoxy value (eq / 100g) of the epoxy resin is 0.48-0.54, and the inorganic chlorine value (eq / 100g) is ≤1×10 -3 , the viscosity at 40° C. is ≤2500 mPa.S. The inventors found that under this preferred embodiment, the hydrophobic elastic fiber obtained by the present invention has more excellent tensile strength and long-term hydrophobic performance.

[0027] Preferably, before performing step (2), the elastic fiber is washed in acetone, anhydrous ethanol and water respectively in sequence, and the washing time is 4-8 minutes.

[0028] Preferably, the fluorine-containing material is perfluorooctylmethyldichlorosilane. The inventors found that under this preferred embodiment, the hydrophobic elastic fiber obtained by the present invention has more excellent mechanical properties and hydrophobic properties.

[0029] Preferably, for every 100 mL of solvent, the amount of silicon dioxide is 0.8-1.0 g, the amount of fluorine-containing material is 1.5-2.0 g, the amount of silane coupling agent is 0.8-1.0 g, and the amount of epoxy resin is 0.8-1.0 g.

[0030] Preferably, the solvent is an organic solvent.

[0031] More preferably, the solvent is at least one of ethanol, acetonitrile and acetone;

[0032] Preferably, the silane coupling agent is selected from at least one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane and γ-aminopropylmethyldimethoxysilane.

[0033] Preferably, the conditions of the immersion treatment include: a temperature of 25-30° C. and a time of 30-60 min. The inventors found that under this preferred embodiment, the hydrophobic elastic fiber obtained by the present invention has more excellent mechanical properties and hydrophobic properties.

[0034] Preferably, in step (1), the drying conditions include: temperature of 80-100° C. and time of 20-24 h.

[0035] Preferably, the melt spinning step comprises: melt extrusion, melt extrusion, receiving and winding in sequence.

[0036] More preferably, the melt spinning step further comprises: filtering and metering in sequence before melt extrusion.

[0037] It should be noted that, in the present invention, each step of the melt spinning is carried out by a conventional method in the art, which will not be described in detail herein, and those skilled in the art should not interpret this as a limitation to the present invention.

[0038] Preferably, the temperatures of melt extrusion, filtration, metering, and melt extrusion are all 160-175°C; the temperatures of receiving and winding are all 90-100°C, and the speed of winding is 50-200rpm. It should be noted that in the present invention, the temperature of the melt spinning in different areas of the melt spinning machine is different, and the speed of different rollers in the winding process will also be different, so the conditions of the melt spinning are all achieved within the aforementioned range. The present invention will not be repeated here, and those skilled in the art should not be understood as limiting the present invention.

[0039] As mentioned above, the second aspect of the present invention provides a hydrophobic elastic fiber prepared by the method described in the first aspect.

[0040] As mentioned above, the third aspect of the present invention provides the use of the hydrophobic elastic fiber described in the second aspect in the textile field.

[0041] The present invention will be described in detail below by way of examples.

[0042] In the following examples, unless otherwise specified, the experimental instruments, reagents and raw materials involved are all commercially available, and the reagents are all analytically pure products.

[0043] Unless otherwise specified, the ethanol used in the following examples is anhydrous ethanol.

[0044] In the following examples, each part by weight represents 1 g unless otherwise specified.

[0045] raw material

[0046] Styrene-ethylene-butylene-styrene block copolymer: model MD-1648, styrene structural unit content of 20wt%, Shore A hardness of 52, melt index (230℃, 2.16Kg) of 220g / min, purchased from Kraton Corporation of the United States; model YH-505, styrene structural unit content of 20wt%, Shore A hardness of 56, melt index (200℃, 5Kg) of 30g / min, purchased from Sinopec Baling Petrochemical Co., Ltd.; model YH-502, styrene structural unit content of 30wt%, Shore A hardness of 73, purchased from Sinopec Baling Petrochemical Co., Ltd.;

[0047] Epoxy resin I: Epoxy E-51, epoxy value (eq / 100g) is 0.48-0.54, inorganic chlorine value (eq / 100g) ≤1×10 -3 , viscosity at 40°C (mPa.S) ≤ 2500;

[0048] Epoxy resin II: Epoxy E-44, epoxy value (eq / 100g) is 0.41-0.47, inorganic chlorine value (eq / 100g) ≤ 1×10 -3 , the viscosity at 25°C is 6000-10000mPa.S;

[0049] Example 1

[0050] This example is used to illustrate that the elastic fiber of the present invention is prepared according to the formula and process parameters in Table 1 and the method described below.

[0051] Step 1: drying, melt extruding, filtering, metering, melt extruding, receiving and winding the styrene-ethylene-butylene-styrene block copolymer to obtain the elastic fiber; and

[0052] In the presence of a solvent, silicon dioxide, a fluorine-containing material, a silane coupling agent and an epoxy resin are mixed to obtain an impregnation solution;

[0053] The drying conditions are: temperature 40°C, time 6 hours;

[0054] The temperature of melt extrusion, filtration, metering and melt extrusion is 160-175°C, the temperature of receiving and winding is 90-100°C, and the speed of winding is 50-200rpm;

[0055] Step 2: washing the elastic fiber in acetone for 5 min, in anhydrous ethanol for 5 min, and in deionized water for 5 min in sequence;

[0056] Step three: immersing the elastic fiber after ultrasonic cleaning in the immersion liquid to obtain the hydrophobic elastic fiber.

[0057] Unless otherwise specified, the remaining examples were carried out using a process similar to that of Example 1, except that the formulations and process parameters used in each example were different, see Table 1 for details (Note: the parameters not listed in Table 1 are the same as the corresponding parameters in Example 1).

[0058] Table 1

[0059]

[0060] Comparative Example 1

[0061] This comparative example was carried out using a process similar to that of Example 1, except that epoxy resin I was not used in this comparative example.

[0062] The rest are the same as in Example 1.

[0063] The hydrophobic elastic fiber DS1 was prepared.

[0064] Comparative Example 2

[0065] This comparative example was carried out using a process similar to that of Example 1, except that the immersion treatment conditions in this comparative example were: temperature of 25° C. and time of 20 min.

[0066] The rest are the same as in Example 1.

[0067] The hydrophobic elastic fiber DS2 was prepared.

[0068] Comparative Example 3

[0069] This comparative example was carried out using a process similar to that of Example 1, except that the immersion treatment conditions in this comparative example were: temperature of 25° C. and time of 120 min.

[0070] The rest are the same as in Example 1.

[0071] The hydrophobic elastic fiber DS3 was prepared.

[0072] Comparative Example 4

[0073] This comparative example adopts a process similar to that of Example 1, except that in step three, spraying treatment is used in this comparative example instead of the immersion treatment in Example 1; the conditions of the spraying treatment are: the spraying solution is the immersion solution in the example, the spraying pressure is 0.1 MPa, and the spraying distance is 20 cm.

[0074] The rest are the same as in Example 1.

[0075] The hydrophobic elastic fiber DS4 was prepared.

[0076] Comparative Example 5

[0077] This comparative example was carried out in a similar process to that of Example 1, except that an equal mass of YH-503 was used to replace the MD-1648 in Example 1.

[0078] The rest are the same as in Example 1.

[0079] The elastic fiber DS5 was prepared.

[0080] Comparative Example 6

[0081] This comparative example was carried out in a similar process to that of Example 1, except that an equal mass of 1H,1H,2H,2H-perfluorooctyldimethylchlorosilane was used to replace the perfluorooctylmethyldichlorosilane in Example 1.

[0082] The rest are the same as in Example 1.

[0083] Elastic fiber DS6 was prepared.

[0084] Test Case

[0085] The same method was used to test the performance of the hydrophobic elastic fibers prepared in the embodiment and the comparative example, and the results are shown in Table 2.

[0086] 1. The tensile strength and elongation at break of the elastic fiber were measured by a universal material mechanical properties tester (model UTM4104, manufacturer Shenzhen Sansi Zongheng Technology Co., Ltd.);

[0087] 2. Using an optical contact angle meter (model DSA30, manufacturer KRUSS, Germany) to measure the initial water contact angle of the hydrophobic elastic fiber and the water contact angle of the hydrophobic elastic fiber after being placed outdoors for 6 months;

[0088] 3. Use the tape stripping method to verify the wear resistance of the hydrophobic elastic fiber; specifically: use a strong double-sided tape (VHB, 3M600) to adhere to the surface of the material to ensure that there is no gap between the tape and the coating surface, then use a 1Kg weight to roll back and forth on the tape surface 3 times, and finally slowly peel off the tape. After repeating 3 times, test the contact angle data.

[0089] 4. Use a universal material mechanical properties tester (model UTM4104, manufacturer Shenzhen Sansi Zongheng Technology Co., Ltd.) to stretch the sample at a length of 5 cm and a stretching speed of 500 mm / min. The stretching length is 200%, and then the sample is recovered at a speed of 500 mm / min.

[0090] Table 2

[0091]

[0092]

[0093] It can be seen from the results in Table 2 that the elastic fiber obtained by the present invention has excellent hydrophobicity and mechanical properties.

[0094] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing a hydrophobic elastic fiber, It is characterized in that The method includes: (1) drying and melt-spinning a styrene-ethylene-butylene-styrene block copolymer in sequence to obtain an elastic fiber; and In the presence of a solvent, silicon dioxide, a fluorine-containing material, a silane coupling agent and an epoxy resin are mixed to obtain an impregnation solution; (2) immersing the elastic fiber in the impregnation liquid to obtain the hydrophobic elastic fiber; the conditions of the impregnation treatment include: a temperature of 25-30° C. and a time of 30-90 min; Relative to every 100 mL of solvent, the amount of the silicon dioxide is 0.6-1.5 g, the amount of the fluorine-containing material is 1.2-3.2 g, the amount of the silane coupling agent is 0.6-1.5 g, and the amount of the epoxy resin is 0.6-1.5 g; The styrene structural unit content of the styrene-ethylene-butylene-styrene block copolymer is 15-30wt%, the Shore A hardness is 50-60, and the melt index under the conditions of 230°C and 2.16Kg is 210-220g / min, or the melt index under the conditions of 200°C and 5Kg is 25-35g / min; The fluorine-containing material is selected from at least one of perfluorooctylmethyldichlorosilane, perfluorodecyltriethoxysilane and perfluorodecyltrichlorosilane.

2. The method according to claim 1, It is characterized in that The epoxy value of the epoxy resin is 0.48-0.54eq / 100g, and the inorganic chlorine value is ≤1×10 -3 eq / 100g, viscosity at 40°C ≤2500mPa.S.

3. The method according to claim 1 or 2, It is characterized in that The fluorine-containing material is perfluorooctylmethyldichlorosilane.

4. The method according to any one of claims 1 to 3, It is characterized in that Relative to every 100 mL of solvent, the amount of the silicon dioxide is 0.8-1.0 g, the amount of the fluorine-containing material is 1.5-2.0 g, the amount of the silane coupling agent is 0.8-1.0 g, and the amount of the epoxy resin is 0.8-1.0 g.

5. The method according to any one of claims 1 to 4, It is characterized in that The solvent is an organic solvent; preferably at least one of ethanol, acetonitrile and acetone; And / or, the silane coupling agent is selected from at least one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane and γ-aminopropylmethyldimethoxysilane.

6. The method according to any one of claims 1 to 5, It is characterized in that The conditions of the immersion treatment include: a temperature of 25-30° C. and a time of 30-60 min.

7. The method according to any one of claims 1 to 6, It is characterized in that In step (1), the melt spinning step includes: melt extrusion, melt extrusion, receiving and winding in sequence.

8. The method according to any one of claims 7, It is characterized in that In step (1), the temperatures of melt extrusion and melt extrusion are both 160-175°C; the temperatures of receiving and winding are both 90-100°C, and the speed of winding is 50-200rpm.

9. The hydrophobic elastic fiber prepared by the method according to any one of claims 1 to 8.

10. Use of the hydrophobic elastic fiber according to claim 9 in the textile field.

Images