Magnetic response fiber material and its preparation method and application

Abstract

A magnetic response fiber material and a preparation method and an application thereof are provided, which relates to the field of oil-water separation materials. The preparation method includes: mixing a fiber-forming polymer, a primary solvent, a secondary solvent and magnetic nanoparticles to form a uniform spinning solution, where the fiber-forming polymer includes at least one of polyethylene, polypropylene and polymethylpentene; spinning the spinning solution by a spinning process to obtain the magnetic response fiber material. The prepared magnetic response fiber material has the advantages of high oil absorption speed, high oil absorption capacity and high separation efficiency. Magnetic nanoparticles have a high load, which can not only be driven by magnetic force to absorb oil floating on water surface, but also be driven to an underwater oil pollution position to absorb oil, and can be applied to water purification in oil-polluted areas that cannot be reached by manual processing.

Claims

1. A preparation method of a magnetic response fiber material, comprising: step (1), mixing a fiber-forming polymer, a primary solvent, a secondary solvent and magnetic nanoparticles to form a uniform spinning solution, wherein the fiber-forming polymer comprises at least one of polyethylene, polypropylene and polymethylpentene; the primary solvent comprises at least one of aliphatic hydrocarbon and halogenated hydrocarbon; the aliphatic hydrocarbon comprises at least one of n-hexane and butane; the halogenated hydrocarbon comprises at least one of dichloromethane and chloroform; the secondary solvent comprises at least one of alkane, nitrogen and carbon dioxide; the magnetic nanoparticles comprise at least one of iron oxide nanoparticles and nickel oxide nanoparticles; a diameter of the magnetic nanoparticles is in a range of 50-80 nanometers (nm); a mass ratio of the fiber-forming polymer to the magnetic nanoparticles is in a range of (9-10):(1-10); a mass-volume ratio of the fiber-forming polymer to the primary solvent is in a range of (1-2):(6-7) in terms of grams per milliliter (g/mL); and a mass ratio of the fiber-forming polymer to the secondary solvent is (1-2):(7-8); and step (2), spinning the spinning solution by a high-pressure electrospray spinning process to obtain the magnetic response fiber material, wherein conditions of the high-pressure electrospray spinning process comprise: temperature of 200-250 C., pressure of 10-15 megapascals (MPa), and stirring speed of 150-200 revolutions per minute (r/min).

2. The preparation method as claimed in claim 1, wherein the mass ratio of the fiber-forming polymer to the magnetic nanoparticles is 9:(1-9); the mass-volume ratio of the fiber-forming polymer to the primary solvent is 1:(6-7) in terms of g/mL; and the mass ratio of the fiber-forming polymer to the secondary solvent is 1:(7-8), and the secondary solvent is the carbon dioxide.

3. The preparation method as claimed in claim 1, wherein a temperature of the mixing in step (1) is in a range of 200-250 C.

4. The preparation method as claimed in claim 3, wherein the temperature of the mixing in step (1) is 200 C.; and the conditions of the high-pressure electrospray spinning process are as follows: the temperature of 230 C., the pressure of 10-14 MPa, and the stirring speed of 150-200 r/min.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) In order to describe specific embodiments of the disclosure or the technical scheme in the related art more clearly, the attached drawings needed in the description of the specific embodiments or the related art will be briefly introduced below. Apparently, the attached drawings in the following description are some embodiments of the disclosure. For those skilled in related art, other drawings can be obtained based on the attached drawings without creative effort.

(2) FIG. 1 illustrates a schematic structural diagram of high-pressure electrospray spinning equipment used in preparing magnetic response fiber materials in embodiments 1 to 5 of the disclosure.

(3) FIG. 2 illustrates a scanning electron micrograph of morphology of the magnetic response fiber material prepared in the embodiment 5 of the disclosure, magnified by 150 times.

(4) FIG. 3 illustrates a diagram showing a fiber diameter and distribution of the magnetic response fiber material prepared in the embodiment 5 of the disclosure.

(5) FIG. 4 illustrates a photograph showing a contact angle of a water droplet (3 microliters abbreviated as L) in air on a surface of the magnetic response fiber material prepared in the embodiment 5 of the disclosure.

(6) FIG. 5 illustrates a photograph showing a contact angle of an oil droplet (3 L) in air on the surface of the magnetic response fiber material prepared in the embodiment 5 of the disclosure.

(7) FIG. 6 illustrates a diagram showing an absorption rate of the magnetic response fiber material prepared in the embodiment 5 of the disclosure for various oils.

(8) FIG. 7 illustrates a diagram showing a cyclic absorption rate of vacuum pump oil by the magnetic response fiber material prepared in the embodiment 5 of the disclosure.

(9) FIG. 8 illustrates a diagram showing an underwater absorption rate of tetrachloromethane and dichloromethane by the magnetic response fiber material prepared in the embodiment 5 of the disclosure.

(10) FIG. 9 illustrates a magnetic force driving display diagram of the magnetic response fiber material prepared in the embodiment 5 of the disclosure.

DESCRIPTION OF REFERENCE SIGNS

(11) 1autoclave, 2autoclave heating jacket, 3spinneret, 4high-voltage electric valve, 5drive motor, 6agitator, 7pressure relief hole, and 8pressure relief valve.

DETAILED DESCRIPTION OF EMBODIMENTS

(12) The following embodiments are provided for a better understanding of the disclosure, and are not limited to the illustrated embodiments, nor do they limit the content and protection scope of the disclosure. Any product that is the same as or similar to the disclosure obtained by anyone under the inspiration of the disclosure or by combining the disclosure with other features of the related art falls within the protection scope of the disclosure.

(13) The high-pressure electrospray spinning process described in this disclosure is carried out by high-pressure electrospray spinning equipment, and the specific equipment is not limited, and the existing high-pressure electrospray spinning equipment can be selected. The high-pressure electrospray spinning equipment in the embodiments of the disclosure has been disclosed in the Chinese patent document CN105442069A.

(14) As shown in FIG. 1, the high-pressure electrospray spinning equipment includes an autoclave 1, a heating jacket 2, a spinneret 3, a high-voltage electric valve 4, a driving motor 5, an agitator 6, a pressure relief hole 7, and a pressure relief valve 8. The heating jacket 2 is wrapped outside the autoclave 1 to provide heating for the autoclave 1. A lid of the autoclave 1 is provided with the pressure relief hole 7, which is controlled by the pressure relief valve 8. The drive motor 5 drives the agitator 6 to stir the materials in the autoclave 1. The lower surface of the autoclave 1 is directly connected to the spinneret 3 through the high-voltage electric valve 4.

(15) If the specific experimental steps or conditions are not specified in the embodiments, the operation or conditions of the conventional experimental steps described in the literature in the field can be carried out. The raw materials or instruments used are all conventional products available in the market, including but not limited to the raw materials or instruments used in the embodiments of the disclosure.

Embodiment 1

(16) This embodiment provides a magnetic response fiber material, which is prepared according to the following steps. (1) 66 grams (g) of polyethylene, 7.3 g of magnetic Fe.sub.3O.sub.4 nanoparticles with a diameter of 80 nm, and 450 mL of dichloromethane are prepared and placed into the autoclave of the high-pressure electrospray spinning equipment, 0.5 kilograms (kg) of carbon dioxide gas is introduced, then stirred at a speed of 180 r/min, and heated up to 200 C., so that polyethylene can be fully dissolved in dichloromethane to form a uniform spinning solution. (2) The spinning solution is spun at the temperature of 230 C. and the pressure of 10 MPa to obtain the magnetic response fiber material.

(17) The magnetic response fiber material prepared in this embodiment has a crisscrossed distribution with a rough surface, uniformly loaded with magnetic Fe.sub.3O.sub.4 nanoparticles, and an average fiber diameter of 12 micrometers (m).

(18) In air, a contact angle of a water droplet (3 L) on the surface of the magnetic response fiber material prepared in this embodiment 125. In air, a contact angle of an oil droplet (3 L) on the surface of the magnetic response fiber material prepared in this embodiment is 0.

Embodiment 2

(19) This embodiment provides a magnetic response fiber material, and its preparation steps are similar to that of the embodiment 1, except that the dosage of magnetic Fe.sub.3O.sub.4 nanoparticles in the step (1) is 16.5 g, and the spinning pressure in the step (2) is 11 MPa.

(20) The magnetic response fiber material prepared in this embodiment has a crisscrossed distribution with a rough surface, uniformly loaded with magnetic Fe.sub.3O.sub.4 nanoparticles, and an average fiber diameter of 11 m.

(21) In air, the contact angle of the water droplet (3 L) on the surface of the magnetic response fiber material prepared in this embodiment 128. In air, the contact angle of the oil droplet (3 L) on the surface of the magnetic response fiber material prepared in this embodiment is 0.

Embodiment 3

(22) This embodiment provides a magnetic response fiber material, and its preparation steps are similar to that of the embodiment 1, except that the dosage of magnetic Fe.sub.3O.sub.4 nanoparticles in the step (1) is 28.3 g, and the spinning pressure in the step (2) is 12 MPa.

(23) The magnetic response fiber material prepared in this embodiment has a crisscrossed distribution with a rough surface, uniformly loaded with magnetic Fe.sub.3O.sub.4 nanoparticles, and an average fiber diameter of 9 m.

(24) In air, the contact angle of the water droplet (3 L) on the surface of the magnetic response fiber material prepared in this embodiment 135. In air, the contact angle of the oil droplet (3 L) on the surface of the magnetic response fiber material prepared in this embodiment is 0.

Embodiment 4

(25) This embodiment provides a magnetic response fiber material, and its preparation steps are similar to that of the embodiment 1, except that the dosage of magnetic Fe.sub.3O.sub.4 nanoparticles in the step (1) is 44 g, and the spinning pressure in the step (2) is 13 MPa.

(26) The magnetic response fiber material prepared in this embodiment has a crisscrossed distribution with a rough surface, uniformly loaded with magnetic Fe.sub.3O.sub.4 nanoparticles, and an average fiber diameter of 8 m.

(27) In air, the contact angle of the water droplet (3 L) on the surface of the magnetic response fiber material prepared in this embodiment is 139. In air, the contact angle of the oil droplet (3 L) on the surface of the magnetic response fiber material prepared in this embodiment is 0.

Embodiment 5

(28) This embodiment provides a magnetic response fiber material, and its preparation steps are similar to that of the embodiment 1, except that the dosage of magnetic Fe.sub.3O.sub.4 nanoparticles in the step (1) is 66 g, and the spinning pressure in the step (2) is 14 MPa.

(29) As shown in FIG. 2, the scanning electron microscope of the magnetic response fiber material prepared in this embodiment shows that the fiber has a crisscrossed distribution with a rough surface, and is uniformly loaded with magnetic Fe.sub.3O.sub.4 nanoparticles. As shown in FIG. 3, an average diameter of the fiber is 4.5 m.

(30) As shown in FIG. 4, in air, the contact angle of the water droplet (3 L) on the surface of the magnetic response fiber material prepared in this embodiment is 143. As shown in FIG. 5, in air, the contact angle of the oil droplet (3 L) on the surface of the magnetic response fiber material prepared in this embodiment is 0.

Experimental Embodiment

(31) This experimental embodiment aims to verify the oil absorption effect of the magnetic response fiber materials prepared in embodiments 1-5.

(32) 1. Absorption Effect of Magnetic Response Fiber Materials on Different Oils.

(33) Oil (vacuum pump oil, tetrachloromethane, dichloromethane, toluene and n-hexane) into a closed glassware, a certain amount of fiber is taken, the fiber is put in the oil for 1 minute, then the fiber is taken out, and the absorption ratio M (g/g) is calculated according to the following formula:

(34) $\begin{array}{cc}M=\frac{M_1-M_2-M_3}{M_3}100.& \left(1\right)\end{array}$

(35) In the formula, M.sub.1 (g) is the mass of oil in a glass bottle before oil absorption; M.sub.2 (g) is the mass of oil in the glass bottle after oil absorption; and M.sub.3 (g) is the mass of the fiber.

(36) Table 1 Absorption rate (g/g) of the magnetic response fiber materials prepared in the embodiments 1 to 5 for different oils.

(37) TABLE-US-00001 Vacuum Tetrachloro- Dichloro- N- Sample pump oil methane methane Toluene hexane Embodiment 1 71.1 70.2 60.4 50.3 42.5 Embodiment 2 73.4 71.1 61.3 51.6 43.1 Embodiment 3 74.6 72.7 62.5 52.1 40.4 Embodiment 4 75.1 71.6 63.5 53.1 43.1 Embodiment 5 76.2 73.1 64.5 53.2 44.1

(38) As shown in Table 1 and FIG. 6, the magnetic response fiber materials prepared in the embodiments 1-5 have high absorption rate for different oils (vacuum pump oil, tetrachloromethane, dichloromethane, toluene, and n-hexane), among which the absorption rate for the vacuum pump oil in the embodiment 5 is the highest, reaching 76.2 g/g.

(39) 2. Cyclic Performance of the Magnetic Response Fiber Materials

(40) A certain amount of fiber is immersed in vacuum pump oil, taken out with tweezers and weighed. After washing with dichloromethane to remove the residual oil, the next oil adsorption is carried out, the sample is subjected to 10 adsorption-desorption cycles, and the absorption rate of each time is determined to study the recycling performance of the magnetic response fiber materials. The absorption rate is calculated according to the formula (1).

(41) Table 2 Repeated absorption rate (g/g) of vacuum pump oil by magnetic response fiber materials prepared in the embodiments 1 to 5

(42) TABLE-US-00002 Cycle number Sample 1 2 3 4 5 6 7 8 9 10 Embodiment 1 70.9 70.6 70.2 69.8 69.5 69.1 68.6 68.3 68.1 67.6 Embodiment 2 73.3 73.1 72.7 72.2 71.9 71.5 71.2 70.9 70.5 69.8 Embodiment 3 74.7 74.5 74.1 73.6 73.3 72.9 72.6 72.3 71.6 71.1 Embodiment 4 75.1 74.9 74.6 74.1 73.7 73.3 72.9 72.5 71.9 71.4 Embodiment 5 76.2 76.1 75.8 75.3 74.9 74.6 74.3 73.9 73.6 73.1

(43) As shown in Table 2 and FIG. 7, the oil absorption rate of the magnetic response fiber materials prepared in the embodiments 1 to 5 is not significantly reduced after being recycled for 10 times, and the 10.sup.th oil absorption of the embodiment 5 is 96% of the first oil absorption, indicating that the fiber material still has a high oil-water separation capacity after 10 times of repeated oil absorption-desorption.

(44) 3. Underwater Oil Absorption Effect of Magnetic Response Fiber Materials

(45) 40 mL of water and 40 mL of oil (tetrachloromethane and dichloromethane) are placed in a glass bottle a, a certain amount of fiber is placed in the oil, and the fiber is taken out after 1 minute, and the taken-out fiber is placed in a closed glass bottle b. The liquid in the glass bottle b is poured into a separating funnel to separate the liquid, and the weight of water absorbed by the fiber is obtained. The underwater oil absorption is calculated according to the following formula:

(46) $\begin{array}{cc}M=\frac{M_1-M_2-M_3-M_4}{M_2}100.& \left(2\right)\end{array}$

(47) In the formula, M.sub.1 (g) is the mass of oil in glass bottle a before oil absorption; M.sub.2 (g) is the mass of the fiber; M.sub.3 (g) is the mass of oil in glass bottle a after oil absorption; M.sub.4 (g) is the weight of water absorbed by the fiber.

(48) Table 3 Underwater oil absorption rate (g/g) of the magnetic response fiber materials prepared in the embodiments 1 to 5.

(49) TABLE-US-00003 Samples Tetrachloromethane Dichloromethane Embodiment 1 62.1 48.2 Embodiment 2 63.4 49.1 Embodiment 3 64.9 50.5 Embodiment 4 63.5 50.2 Embodiment 5 65.3 52.7

(50) As shown in Table 3 and FIG. 8, the magnetic response fiber materials prepared in the embodiments 1-5 still have high oil absorption for tetrachloromethane and dichloromethane under water.

(51) 4. Magnetic Driving Effect of Magnetic Response Fiber Materials

(52) In order to characterize the oil adsorption effect of fiber magnetic drive, two kinds of special-shaped pipes are used, and vacuum pump oil and dichloromethane (Sudan III staining) are dripped at different positions of the pipes to simulate the underwater oil pollution, and then the fiber is driven to absorb oil under the guidance of magnetic force.

(53) As shown in FIG. 9, the magnetic response fiber material prepared in the embodiment 5 has good magnetic response performance and good driving ability, and can move flexibly in various special-shaped pipes to efficiently complete the oil removal operation.

(54) Apparently, the above embodiments are merely examples for clarity of illustration and are not limiting of the embodiments. For those skilled in the art, other changes or modifications in different forms can be made on the basis of the above description. An exhaustive list of all embodiments is not required and is not exhaustive. The obvious changes or modifications caused by this are still within the scope of protection created by the disclosure.