CN1936120A - A method for preparing ion exchange fibers by solution electrospinning - Google Patents

Abstract

The invention relates to a method for preparing ion exchange fiber by a solution electrostatic spinning method, belonging to the technical field of chemical fiber material manufacturing methods. Mixing the raw materials and the solvent according to the mass ratio, and stirring to prepare an electrospinning solution; spinning by using an electrostatic spinning device to prepare matrix fibers; treating and functionalizing the matrix fibers to prepare ion exchange fibers; to obtain anion exchange fibers or strong acid type cation exchange fibers such as strong acid type cation exchange fibers, strong alkali or weak alkali anion exchange fibers, carboxylic acid type cation exchange fibers and the like. The matrix fiber of the ion exchange fiber is directly prepared by an electrostatic spinning method, and the matrix fiber is treated and chemically reacted to introduce functional groups to prepare the ion exchange fiber. The ion exchange fiber prepared by the invention has controllable diameter, high exchange capacity and good comprehensive performance; the invention directly prepares the matrix fiber, does not need graft polymerization, simplifies the production steps, saves the production cost, is simple and easy to operate and has good practical prospect.

Description

A method for preparing ion exchange fibers by solution electrospinning

technical field

The invention relates to a method for preparing ion exchange fibers, in particular to a method for ion exchange fibers prepared by electrospinning, and belongs to the technical field of chemical fiber material manufacturing methods.

Background technique

Ion exchange fiber is a kind of special synthetic fiber with ion exchange function. Compared with ion exchange resin, it has outstanding advantages such as large specific surface area, fast exchange and elution speed, and can be used in various application forms such as fiber and its products. Therefore, the use of ion exchange fibers has significant advantages, especially where granular ion exchange resins cannot be used.

In the existing technology of ion exchange fibers and their preparation methods, the commonly used matrix fibers are chemical fibers and synthetic fibers of conventional deniers, with a diameter of tens of microns, and generally grafted styrene by graft polymerization. , and then introduce ion exchange groups through cross-linking and functionalization. For example: Chinese patent ZL 98 1 03455.1 invents a preparation method of ion exchange fibers, using polyolefin fibers to swell with solvent, and then grafting styrene to make anion and cation exchange fibers, the exchange capacity can reach 3-3.5 mmol/g .

Electrospinning is also known as electrostatic fiber manufacturing. The core of this technology is to make the charged polymer solution or melt flow and deform in the electrostatic field, and then condense or solidify after solvent evaporation or melt cooling, so that the fibrous substance. The principle of electrospinning technology is shown in Figure 1. The fine stream of spinning solution flowing out of the capillary hole of the nozzle is accelerated under the action of electrostatic force and split to form a cluster of fine streams. After the solvent evaporates or the melt cools down, it condenses or Solidified into microfilaments, deposited in the form of a non-woven fabric on a stationary or reciprocating or rotating receiving device. The spinning solution is connected to the positive pole of the high-voltage DC generator, and the receiving device is the negative pole and grounded. The conditions of electrospinning are mainly the properties of the spinning solution (viscosity, surface tension and conductivity) and operating conditions (voltage, flow rate of spinning solution, temperature, distance between the nozzle and the receiving device). The diameter of the obtained fiber varies with the processing conditions, and the typical value is 40 nm to 2 μm, which is the most important method for preparing nanofibers at present.

Contents of the invention

The invention provides a method for preparing ion exchange fibers by a solution electrospinning method. The remarkable feature of the present invention is: the matrix fiber of the ion exchange fiber is directly prepared by electrospinning method, the diameter of the matrix fiber is 10nm-10μm, the typical value is 40nm-2μm; the matrix fiber is treated and chemically reacted to introduce functional groups , to prepare ion exchange fibers. The exchange capacity of the ion exchange fiber is high; in the preparation method, the matrix fiber of the ion exchange fiber is directly prepared without graft polymerization, which simplifies the production steps and saves the production cost.

A method for preparing ion-exchange fibers by a solution electrospinning method, the preparation method comprising the following steps:

(1) Preparation of spinning solution

Put the raw material into the solvent (the mass ratio of the raw material to the solvent is 6-30:94-70), and at an appropriate temperature, use magnetic force or mechanical stirring to dissolve into a uniform solution to obtain a spinning solution;

Described raw material is any one of polystyrene, polyacrylonitrile and acrylonitrile copolymer, polyvinylpyrrolidone, polyvinyl alcohol;

Described proper temperature has corresponding relation with raw material as shown in table 1;

The solvent has a corresponding relationship with the raw material as shown in Table 1, and the solvent is any one or more of the solvents corresponding to the raw material.

Table 1

raw material polystyrene Polyacrylonitrile and Acrylonitrile Copolymer Polyvinylpyrrolidone polyvinyl alcohol solvent Tetrahydrofuran, N,N-dimethylformamide, toluene N,N-Dimethylformamide ethanol, water water temperature room temperature 80℃

(2) Preparation of matrix fibers by electrospinning

The spinning solution prepared in step (1) is added to a liquid storage device connected with a spinneret of the electrospinning device; the spinning solution is connected to the positive pole of the power supply, and the negative pole of the power supply is connected to the receiving device; The distance between the head and the receiving device is 5-15cm; turn on the high-voltage power supply, adjust the power supply voltage to 15-25kv, carry out electrospinning, and collect it by the receiving device to obtain the matrix fiber;

The electrospinning device is mainly composed of a liquid storage device connected with a spinneret, a high-voltage power supply, and a receiving device; (accompanying drawing 1)

The spinneret is single hole or multi-hole;

The receiving device adopts a static state, and can also reciprocate or rotate;

The diameter of the matrix fiber is 10 nm to 10 μm, with a typical value of 40 nm to 2 μm;

(3) Cross-linking treatment and functionalization of matrix fibers

The matrix fiber is first cross-linked, and then functionalized by chemical reaction to introduce or/and generate anion or cation functional groups to obtain anion or cation exchange fibers.

The cross-linking treatment is to use a cross-linking agent corresponding to the matrix fiber raw material, and perform cross-linking through a chemical reaction between the cross-linking agent and the matrix fiber;

The functionalization by chemical reaction means that the cross-linked matrix fiber introduces or/and generates anion or cation functional groups through the reaction of the functionalization reagent corresponding to the matrix fiber raw material to obtain anion or cation exchange fibers

See Table 2 for the methods of preparing ion exchange fibers from matrix fibers of various raw materials.

Table 2

Matrix fiber Cross-linking treatment and functionalization method of matrix fiber   Polystyrene matrix fiber 1. Immerse the matrix fiber in the mixed solution prepared by paraformaldehyde: glacial acetic acid: concentrated sulfuric acid according to the mass ratio of 3 ~ 10: 30 ~ 40: 68 ~ 50, so that the matrix fiber is completely submerged, and react at 60 ~ 90 ° C for 4 ~ 5 hours to obtain cross-linked fibers; 2. Soak the cross-linked fibers in sulfonating agent and react at 50-90° C. for 12-3 hours to obtain strongly acidic cation exchange fibers containing sulfonic acid groups, wash with water and air-dry. 3. In the presence of a catalyst, introduce chloromethylated groups into crosslinked fibers, and then react the chloromethylated crosslinked fibers with trimethylamine or ethylenediamine to prepare basic anion exchange fibers.   Polyacrylonitrile and acrylonitrile copolymer matrix fibers 1. Immerse the base fiber in a hydrazine hydrate solution with a mass concentration of 40-60%, and react at 90-120° C. for 5-8 hours to obtain a cross-linked fiber. 2. Immerse the cross-linked fiber in 1M sodium hydroxide solution, react at 70°C for 40 hours, wash with distilled water until neutral, centrifuge and dehydrate, soak in 0.5M hydrochloric acid for 12 hours to obtain carboxylic acid type cation exchange fiber.   Polyvinylpyrrolidone matrix fiber 1. After drying and shaping the matrix fiber in a vacuum oven at 150°C for 4 hours, immerse it in a solution of dibutyl peptide acid/n-hexane with a mass ratio of 40-60/60-40 at room temperature and protected from light. After 30 minutes, anion exchange fibers were obtained.   Polyvinyl alcohol matrix fiber 1. Immerse the matrix fiber in a solution of benzaldehyde, ethanol, deionized water, zinc chloride and sulfuric acid with a mass ratio of 5 to 10/20 to 30/5 to 10/2 to 8/3 to 10. React at ~70°C for 1 to 2 hours to perform cross-linking treatment. 2. Dry the cross-linked fibers in a vacuum oven, and then heat-treat them in an oven at 180-200°C for 1-2 hours; then perform sulfonation treatment with 98% concentrated sulfuric acid for 12-24 hours to obtain strong-acid cation exchange fibers.

The sulfonating agent described in the crosslinking treatment and functionalization method of polystyrene matrix fiber in table 2 is the mixture of concentrated sulfuric acid, sulfuric acid and maleic anhydride with dichloroethane as solvent, chlorosulfonic acid, fuming sulfuric acid , any one of sulfuric acid to chlorosulfonic acid; the catalyst is zinc chloride or tin chloride, and the introduction of chloromethylation groups uses chloromethyl ether with a concentration greater than 50%; to prepare strongly basic anion exchange fibers : Chloromethylated cross-linked fibers react with trimethylamine solution with a concentration of more than 10% at room temperature to 40°C for 24-10 hours; preparation of weakly basic ion exchange fibers: Chloromethylated cross-linked fibers and ethylene glycol Amine solution reaction, ethylenediamine: solvent = 4: 0-8, control the reaction time for 6-48 hours, then separate the ethylenediamine solution, wash with water, and dry. The solvent is water, alcohol compound or halogenated hydrocarbon.

The base fiber of the ion exchange fiber prepared in the present invention is obtained by jet-spinning a charged liquid under the action of an electric field force, and the obtained fiber has a submicron-level different fineness, and the fiber diameter is generally 10nm to 10μm, with a typical value of 40nm ~2μm, in the form of non-woven felt, with the characteristics of small pores, high porosity, high specific surface area, and good comprehensive mechanical properties, it is an ideal matrix fiber for preparing ion exchange fibers. The preparation of strong acid type cation exchange fiber in the present invention is to introduce specific ionic groups into the matrix fiber with submicron-level different deniers by carrying out a series of chemical reactions such as crosslinking and sulfonation on the polystyrene matrix fiber prepared by electrospinning. In order to produce ion exchange fibers. The strong-acid cation exchange fiber prepared by the invention has the advantages of large specific surface area, high exchange capacity, fast exchange speed, short regeneration time, etc., and can be widely used in environmental protection, medicine and health, petrochemical industry, metallurgy, water treatment, chemical adsorption, Resource recovery and other fields.

The present invention provides a method for preparing ion-exchange fibers with high exchange capacity due to the use of electrospinning as the matrix fiber for ion-exchange functionalization:

(1) The fiber diameter of static spinning fiber of the present invention is 10nm～10 μm, typical value is 40nm～2 μm, and thicker fiber endows matrix fiber with good mechanical property in different fineness, and finer fiber provides matrix fiber with large specific surface area, Make the matrix fiber have good comprehensive properties;

(2) The diameter of the matrix fiber of the present invention is controllable, and can be controlled by controlling the concentration of the spinning solution and the spinning process conditions;

(3) The ion exchange fiber prepared by the present invention has the characteristics of high exchange capacity, and the exchange capacity of the strong acid type cation exchange fiber of polystyrene matrix reaches 3.8～5 mmol/g;

(4) The base fiber for preparing the ion exchange fiber in the present invention is directly prepared by electrospinning. Compared with the existing technology of ion exchange fiber and its preparation method, in the existing technology, the matrix fiber often used is chemical fiber and synthetic fiber of conventional denier, its diameter is tens of microns, and generally requires grafting The polymerization method is to graft styrene, and then introduce ion-exchange groups through cross-linking and functionalization. The feature of the present invention is to directly prepare polystyrene matrix fibers. The method is simple, easy to implement, and has broad practical prospects.

Description of drawings

Figure 1 is a schematic diagram of an electrospinning device used in the present invention.

Fig. 2 is a scanning electron micrograph of the polystyrene matrix fiber prepared in Example 2 of the present invention.

Fig. 3 is a scanning electron micrograph of the strong-acid polystyrene matrix ion exchange fiber prepared in Example 2 of the present invention.

Fig. 4 is an infrared spectrogram of the ion exchange fiber with a strong acid polystyrene matrix prepared in Example 2 of the present invention.

Fig. 5 is a scanning electron micrograph of the polyacrylonitrile and acrylonitrile copolymer matrix fibers prepared in Example 7 of the present invention.

Fig. 6 is a scanning electron micrograph of the polyvinylpyrrolidone matrix fiber prepared in Example 10 of the present invention.

Fig. 7 is a scanning electron micrograph of the polyvinyl alcohol matrix fiber prepared in Example 13 of the present invention.

Detailed ways

The present invention will be described in detail below in conjunction with the accompanying drawings and embodiments.

Fig. 1 is a kind of electrospinning device schematic diagram that the present invention adopts, mainly is made of the liquid storage device that is connected with spinneret, high-voltage power supply, receiving device; Spinneret is single hole or multi-hole; Receiver adopts static state, also It can reciprocate or rotate; the high-voltage DC power supply is the product of Tianjin Dongwen High Voltage Power Supply Factory, the model is DW-D303-2AC, and the maximum voltage is 30KV.

Apparently, the examples are for illustrating the present invention rather than limiting the present invention. In the present invention, other polymer materials capable of preparing matrix fibers of ion exchange fibers, corresponding reagents and other electrospinning equipment can also be used.

Example 1:

(1) Preparation of spinning solution: mix raw material polystyrene and solvent tetrahydrofuran in a mass ratio of 8:92, stir and dissolve at room temperature, and prepare an electrospinning solution with a concentration of 8%;

or

Mix the raw material polystyrene and the solvent tetrahydrofuran at a mass ratio of 10:90, stir and dissolve at room temperature to prepare an electrospinning solution with a concentration of 10%;

or

The raw material polystyrene and the solvent tetrahydrofuran were mixed at a mass ratio of 16:84, stirred and dissolved at room temperature, and an electrospinning solution with a concentration of 16 wt% was obtained;

(2) Spinning with an electrospinning device to prepare matrix fibers: the spinning solution prepared in step (1) is added to a liquid storage device connected with a single-hole spinneret of the electrospinning device; Connect to the positive pole of the power supply, connect the negative pole of the power supply to the receiving device, adjust the distance between the spinneret and the receiving device to 10cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to 20KV, carry out electrospinning, and collect it by the static receiving device , to obtain polystyrene matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

(3.1) Immerse the polystyrene matrix fiber obtained in step (2) into a mixture of paraformaldehyde: glacial acetic acid: concentrated sulfuric acid in a mass ratio of 8:35:57, so that the matrix fiber is completely submerged, and react at 80 ° C 4 hours, obtain cross-linked fiber;

(3.2) Immerse the cross-linked fiber described in step (3.1) in a mixture of sulfuric acid and maleic anhydride with ethylene dichloride as a solvent, react at 50°C for 4 hours, then raise the temperature to 80°C for 2 hours, and obtain Strongly acidic cation exchange fibers;

or

(3.2) The cross-linked fiber described in step (3.1) is immersed in 60% chloromethyl ether solution containing 3% zinc chloride as a catalyst, and reacted for 11 hours at 45° C. to obtain the cross-linked fiber of chloromethylation:

(a) in the above-mentioned chloromethylated cross-linked fibers and a trimethylamine solution with a concentration of more than 10%, react at room temperature for 24 hours to prepare strongly basic anion exchange fibers;

(b) The above-mentioned chloromethylated cross-linked fibers were reacted in a solution of ethylenediamine and dichloroethane at a mass ratio of 4:0 for 6 hours, and then the ethylenediamine was separated, washed with water, and dried to prepare weakly alkaline Anion exchange fibers.

Example 2:

(1) Preparation of spinning solution: mix raw material polystyrene and solvent tetrahydrofuran in a mass ratio of 10:90, stir and dissolve at room temperature, and prepare an electrospinning solution with a concentration of 10%;

(2) Spinning with an electrospinning device to prepare matrix fibers: the spinning solution prepared in step (1) is added to a liquid storage device connected with a single-hole spinneret of the electrospinning device; Connect to the positive pole of the power supply, connect the negative pole of the power supply to the receiving device, adjust the distance between the spinneret and the receiving device to 15cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 20KV, and perform electrospinning, and the static receiving device Collect to obtain polystyrene matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

(3.1) Immerse the polystyrene matrix fiber obtained in step (2) into the mixed solution prepared by paraformaldehyde: glacial acetic acid: concentrated sulfuric acid in a mass ratio of 3:40:57, so that the matrix fiber is completely submerged, and react at 60°C 5 hours, obtain cross-linked fiber;

(3.2) Immerse the cross-linked fiber described in step (3.1) in a mixture of sulfuric acid and maleic anhydride with ethylene dichloride as a solvent, and react at 90° C. for 3 hours to obtain a strongly acidic cation exchange fiber.

Example 3

(1) Preparation of spinning solution: mix raw material polystyrene and solvent tetrahydrofuran in a mass ratio of 10:90, stir and dissolve at room temperature, and prepare an electrospinning solution with a concentration of 10%;

(2) Spinning with an electrospinning device to prepare matrix fibers: the prepared spinning solution of step (1) is added to a liquid storage device connected with a three-hole spinneret of the electrospinning device; the spinning solution and The positive pole of the power supply is connected, and the negative pole of the power supply is connected to the receiving device. Adjust the distance between the spinneret and the receiving device to 5cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 25KV, and carry out electrospinning, which is collected by the static receiving device. , to obtain polystyrene matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

(3.1) Immerse the polystyrene matrix fiber obtained in step (2) into a mixture of paraformaldehyde: glacial acetic acid: concentrated sulfuric acid in a mass ratio of 10:22:68, so that the matrix fiber is completely submerged, and react at 90 ° C 4 hours, obtain cross-linked fiber;

(3.2) Immerse the cross-linked fibers described in step (3.1) in a mixture of sulfuric acid and maleic anhydride with dichloroethane as a solvent, and react at 50° C. for 12 hours to obtain strongly acidic cation exchange fibers.

Example 4

(1) Preparation of spinning solution: raw material polystyrene and solvent N, N dimethylformamide were mixed in a mass ratio of 8:92, stirred and dissolved at room temperature, and an electrospinning solution with a concentration of 8% was obtained;

or

The raw material polystyrene and the solvent N, N dimethylformamide are mixed in a mass ratio of 10:90, stirred and dissolved at room temperature, and an electrospinning solution with a concentration of 10% is prepared;

or

Mix the raw material polystyrene and the solvent tetrahydrofuran in a mass ratio of 15:85, stir and dissolve at room temperature, and prepare an electrospinning solution with a concentration of 15%;

(2) Spinning with an electrospinning device to prepare matrix fibers: the spinning solution prepared in step (1) is added to a liquid storage device connected with a single-hole spinneret of the electrospinning device; Connect to the positive pole of the power supply, connect the negative pole of the power supply to the receiving device, adjust the distance between the spinneret and the receiving device to 11cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 20KV, and perform electrospinning, and the static receiving device Collect to obtain polystyrene matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

(3.1) Immerse the polystyrene matrix fiber obtained in step (2) into a mixture of paraformaldehyde: glacial acetic acid: concentrated sulfuric acid in a mass ratio of 8:35:57, so that the matrix fiber is completely submerged, and react at 80 ° C 4 hours, obtain cross-linked fiber;

(3.2) Immerse the cross-linked fiber described in step (3.1) in a mixture of sulfuric acid and maleic anhydride with ethylene dichloride as a solvent, react at 50°C for 4 hours, then raise the temperature to 80°C for 2 hours, and obtain Strongly acidic cation exchange fibers;

or

(3.2) The cross-linked fiber described in step (3.1) is immersed in 50% methyl chloride ether solution containing 4% tin chloride as a catalyst, and reacted for 10 hours at 55° C. to obtain the cross-linked fiber of chloromethylation:

(a) reacting the above-mentioned chloromethylated cross-linked fibers with a trimethylamine solution whose concentration is above 10%, to prepare strongly basic anion exchange fibers;

(b) The above-mentioned chloromethylated cross-linked fibers were reacted in a solution of ethylenediamine and dichloroethane at a mass ratio of 4:8 for 8 hours, and then the ethylenediamine was separated, washed with water, and dried to prepare weakly alkaline Anion exchange fibers.

Example 5

(1) Preparation of spinning solution: mix raw material polystyrene and solvent toluene at a mass ratio of 8:92, stir and dissolve at room temperature, and prepare an electrospinning solution with a concentration of 8%;

or

The raw material polystyrene and the solvent toluene are mixed in a mass ratio of 10:90, stirred and dissolved at room temperature, and an electrospinning solution with a concentration of 10% is prepared;

or

The raw material polystyrene and the solvent toluene are mixed in a mass ratio of 20:80, stirred and dissolved at room temperature, and an electrospinning solution with a concentration of 20% is obtained;

(2) Spinning with an electrospinning device to prepare matrix fibers: the spinning solution prepared in step (1) is added to a liquid storage device connected with a single-hole spinneret of the electrospinning device; Connect to the positive pole of the power supply, connect the negative pole of the power supply to the receiving device, adjust the distance between the spinneret and the receiving device to 11cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 20KV, and perform electrospinning, and the static receiving device Collect to obtain polystyrene matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

(3.1) Immerse the polystyrene matrix fiber obtained in step (2) into a mixture of paraformaldehyde: glacial acetic acid: concentrated sulfuric acid in a mass ratio of 8:35:57, so that the matrix fiber is completely submerged, and react at 80 ° C 4 hours, obtain cross-linked fiber;

(3.2) Immerse the cross-linked fiber described in step (3.1) in a mixture of sulfuric acid and maleic anhydride with ethylene dichloride as a solvent, react at 50°C for 4 hours, then raise the temperature to 80°C for 2 hours, and obtain Strongly acidic cation exchange fibers.

Example 6

(1) Preparation of spinning solution: mix raw material polystyrene and a mixed solvent of N,N dimethylformamide and tetrahydrofuran with a mass ratio of 50/50 at a mass ratio of 8:92, stir and dissolve at room temperature, and prepare A concentration of 8% electrospinning solution was obtained;

or

Mix the raw material polystyrene and the mixed solvent of N,N dimethylformamide and tetrahydrofuran at a mass ratio of 50/50 at a mass ratio of 12:88, stir and dissolve at room temperature, and prepare a 12% electrospun silk solution;

or

Mix the raw material polystyrene and the mixed solvent of N,N dimethylformamide and tetrahydrofuran at a mass ratio of 50/50 at a mass ratio of 16:84, stir and dissolve at room temperature, and prepare a 16% electrospun silk solution;

(2) Spinning with an electrospinning device to prepare matrix fibers: the spinning solution prepared in step (1) is added to a liquid storage device connected with a single-hole spinneret of the electrospinning device; Connect to the positive pole of the power supply, connect the negative pole of the power supply to the receiving device, adjust the distance between the spinneret and the receiving device to 11cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 20KV, and perform electrospinning, and the static receiving device Collect to obtain polystyrene matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

(3.1) Immerse the polystyrene matrix fiber obtained in step (2) into a mixture of paraformaldehyde: glacial acetic acid: concentrated sulfuric acid in a mass ratio of 8:32:50, so that the matrix fiber is completely submerged, and react at 80 ° C 4 hours, obtain cross-linked fiber;

(3.2) Immerse the cross-linked fiber described in step (3.1) in a mixture of sulfuric acid and maleic anhydride with ethylene dichloride as a solvent, react at 50°C for 4 hours, then raise the temperature to 80°C for 2 hours, and obtain Strongly acidic cation exchange fibers.

Example 7

(1) Preparation of spinning solution: the raw material polyacrylonitrile and acrylonitrile copolymer and solvent N, N-dimethylformamide are stirred and dissolved at room temperature in a mass ratio of 6:94 to obtain a concentration of 6%. Electrospinning solution;

or

The raw material polyacrylonitrile and acrylonitrile copolymer and the solvent N, N-dimethylformamide in a mass ratio of 10:90 are stirred and dissolved at room temperature to prepare an electrospinning solution with a concentration of 10%;

or

The raw material polyacrylonitrile and acrylonitrile copolymer and the solvent N, N-dimethylformamide in a mass ratio of 15:85 were stirred and dissolved at room temperature to obtain an electrospinning solution with a concentration of 15%;

(2) Spinning with an electrospinning device to prepare matrix fibers: the spinning solution prepared in step (1) is added to a liquid storage device connected with a single-hole spinneret of the electrospinning device; Connect to the positive pole of the power supply, connect the negative pole of the power supply to the receiving device, adjust the distance between the spinneret and the receiving device to 11cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 20KV, and perform electrospinning, and the static receiving device Collect to obtain polyacrylonitrile and acrylonitrile copolymer matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

(3.1) Immerse the polyacrylonitrile and acrylonitrile copolymer matrix fiber described in step (2) in a hydrazine hydrate solution with a mass concentration of 40%, and react at 90° C. for 8 hours to obtain a crosslinked fiber;

(3.2) Immerse the cross-linked fibers described in step (3.1) in a 1M sodium hydroxide solution, react at 70°C for 40 hours, wash with distilled water until neutral, centrifuge and dehydrate, and soak for 12 hours with 0.5M hydrochloric acid to obtain Carboxylic acid type cation exchange fiber.

Example 8

(1) Preparation of spinning solution: the raw material polyacrylonitrile and acrylonitrile copolymer and solvent N, N-dimethylformamide are in a mass ratio of 10:90, stirred and dissolved at room temperature, and the obtained concentration is 10%. Electrospinning solution;

(2) Spinning with an electrospinning device to prepare matrix fibers: the spinning solution prepared in step (1) is added to a liquid storage device connected with a dual-hole spinneret of the electrospinning device; Connect to the positive pole of the power supply, connect the negative pole of the power supply to the receiving device, adjust the distance between the spinneret and the receiving device to 15cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 25KV, perform electrostatic spinning, and receive by reciprocating motion The device is collected to obtain polyacrylonitrile fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

(3.1) immerse the polyacrylonitrile and acrylonitrile copolymer matrix fiber described in step (2) in a hydrazine hydrate solution with a mass concentration of 60%, and react at 120° C. for 5 hours to obtain a crosslinked fiber;

(3.2) With embodiment 7.

Example 9

(1) Preparation of spinning solution: the raw material polyacrylonitrile and acrylonitrile copolymer and solvent N, N-dimethylformamide are in a mass ratio of 10:90, stirred and dissolved at room temperature, and the obtained concentration is 10%. Electrospinning solution;

(2) Spinning with an electrospinning device to prepare matrix fibers: the prepared spinning solution of step (1) is added to a liquid storage device connected with a three-hole spinneret of the electrospinning device; the spinning solution and The positive pole of the power supply is connected, and the negative pole of the power supply is connected to the receiving device. Adjust the distance between the spinneret and the receiving device to 5cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 15KV, and perform electrospinning. Collect to obtain matrix fibers of polyacrylonitrile and acrylonitrile copolymer;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

(3.1) Immerse the polyacrylonitrile and acrylonitrile copolymer matrix fiber described in step (2) in a hydrazine hydrate solution with a mass concentration of 50%, and react at 110° C. for 6 hours to obtain a crosslinked fiber;

(3.2) With embodiment 7.

Example 10

(1) Preparation of spinning solution: the raw material polyvinylpyrrolidone and the mixed solvent of ethanol and water in a mass ratio of 6:94 are stirred and dissolved at room temperature to prepare an electrospinning solution with a concentration of 6%.

or

The raw material polyvinylpyrrolidone and the mixed solvent of ethanol and water in a mass ratio of 16:84 were stirred and dissolved at room temperature to prepare an electrospinning solution with a concentration of 16%;

or

The raw material polyvinylpyrrolidone and the mixed solvent of ethanol and water in a mass ratio of 30:70 are stirred and dissolved at room temperature to prepare an electrospinning solution with a concentration of 30%;

(2)) Spinning with an electrospinning device to prepare matrix fibers: adding the spinning solution prepared in step (1) to a liquid storage device connected with a single-hole spinneret of the electrospinning device; The liquid is connected to the positive pole of the power supply, and the negative pole of the power supply is connected to the receiving device. Adjust the distance between the spinneret and the receiving device to 11cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 20KV, and carry out electrostatic spinning. The device is collected to obtain polyvinylpyrrolidone matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion-exchange fibers: dry and shape the polyvinylpyrrolidone matrix fibers described in step (2) in a vacuum oven at 150°C for 4 hours, then immerse them in mass The treatment was carried out in a solution of dibutyl peptidic acid/n-hexane with a ratio of 60/40 for 30 minutes to obtain anion exchange fibers.

Example 11

(1) Preparation of spinning solution: the raw material polyvinylpyrrolidone and solvent ethanol are mixed at a mass ratio of 12:88, stirred and dissolved at room temperature, and an electrospinning solution with a concentration of 12% is obtained;

or

The raw material polyvinylpyrrolidone and the solvent ethanol are mixed at a mass ratio of 25:75, stirred and dissolved at room temperature, and an electrospinning solution with a concentration of 25% is obtained;

(2) Spinning with an electrospinning device to prepare matrix fibers: the spinning solution prepared in step (1) is added to a liquid storage device connected with a dual-hole spinneret of the electrospinning device; Connect to the positive pole of the power supply, connect the negative pole of the power supply to the receiving device, adjust the distance between the spinneret and the receiving device to 5cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 15KV, and perform electrospinning, which is received by reciprocating motion The device is collected to obtain polyvinylpyrrolidone matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion-exchange fibers: dry and shape the polyvinylpyrrolidone matrix fibers described in step (2) in a vacuum oven at 150°C for 4 hours, then immerse them in mass The treatment was carried out in a solution of dibutyl peptidic acid/n-hexane with a ratio of 40/60 for 30 minutes to obtain anion exchange fibers.

Example 12

(1) Preparation of spinning solution: the raw material polyvinylpyrrolidone and solvent water are in a mass ratio of 12:88, stirred and dissolved at room temperature, and an electrospinning solution with a concentration of 12% is obtained;

or

The raw material polyvinylpyrrolidone and the solvent water are in a mass ratio of 25:75, stirred and dissolved at room temperature to prepare an electrospinning solution with a concentration of 25%;

(2) Spinning with an electrospinning device to prepare matrix fibers: the prepared spinning solution of step (1) is added to a liquid storage device connected with a three-hole spinneret of the electrospinning device; the spinning solution and The positive pole of the power supply is connected, and the negative pole of the power supply is connected to the receiving device. Adjust the distance between the spinneret and the receiving device to 15cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 25KV, and perform electrostatic spinning. Collect to obtain polyvinylpyrrolidone matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion-exchange fibers: dry and shape the polyvinylpyrrolidone matrix fibers described in step (2) in a vacuum oven at 150°C for 4 hours, then immerse them in mass The treatment was carried out for 30 minutes in a solution of dibutyl peptidic acid/n-hexane with a ratio of 55/45 to obtain anion exchange fibers.

Example 13

(1) Preparation of spinning solution: the raw material polyvinyl alcohol and water are mixed in a mass ratio of 7:93, stirred and dissolved at a temperature of 80° C., and an electrospinning solution with a concentration of 7% is obtained;

or

The raw materials polyvinyl alcohol and water are mixed at a mass ratio of 10:90, stirred and dissolved at a temperature of 80°C, and an electrospinning solution with a concentration of 10% is prepared;

or

The raw material polyvinyl alcohol and water are mixed at a mass ratio of 15:85, stirred and dissolved at a temperature of 80° C., and an electrospinning solution having a concentration of 15% is obtained;

(2) Spinning with an electrospinning device to prepare matrix fibers: the spinning solution prepared in step (1) is added to a liquid storage device connected with a single-hole spinneret of the electrospinning device; Connect to the positive pole of the power supply, connect the negative pole of the power supply to the receiving device, adjust the distance between the spinneret and the receiving device to 11cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 20KV, and perform electrospinning, and the static receiving device Collect to obtain polyvinyl alcohol matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

The matrix fiber is immersed in a solution of benzaldehyde, ethanol, deionized water, zinc chloride and sulfuric acid with a mass ratio of 5/20/5/2/3, and reacted at 50° C. for 2 hours to perform cross-linking treatment. The cross-linked fibers were dried in a vacuum oven until there was no moisture, and then heat-treated in an oven at 180°C for 2 hours; then sulfonated with 98% concentrated sulfuric acid for 12 hours to obtain strong-acid cation exchange fibers.

Example 14

(1) Preparation of spinning solution: the raw materials polyvinyl alcohol and ethanol are mixed in a mass ratio of 7:93, stirred and dissolved at a temperature of 80° C., and an electrospinning solution with a concentration of 7% is obtained;

(2) Spinning with an electrospinning device to prepare matrix fibers: the spinning solution prepared in step (1) is added to a liquid storage device connected with a dual-hole spinneret of the electrospinning device; Connect to the positive pole of the power supply, connect the negative pole of the power supply to the receiving device, adjust the distance between the spinneret and the receiving device to 15cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 25KV, perform electrostatic spinning, and receive by reciprocating motion The device is collected to obtain the polyvinyl alcohol matrix fiber;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

The matrix fiber is immersed in a solution of benzaldehyde, ethanol, deionized water, zinc chloride, and sulfuric acid with a mass ratio of 10/15/10/6/10, reacted at 70° C. for 1 hour, and performs cross-linking treatment. Dry the cross-linked fibers in a vacuum oven until there is no moisture, and then heat-treat in an oven at 200°C for 1 hour; then perform sulfonation treatment with 98% concentrated sulfuric acid for 18 hours to obtain strong-acid cation exchange fibers.

Example 15

(1) Preparation of spinning solution: the mixed solvent of raw materials polyvinyl alcohol, ethanol and water is 7:93 in mass ratio, stirred and dissolved at a temperature of 80° C., and an electrospinning solution with a concentration of 7% is obtained;

(2) Spinning with an electrospinning device to prepare matrix fibers: the prepared spinning solution of step (1) is added to a liquid storage device connected with a three-hole spinneret of the electrospinning device; the spinning solution and The positive pole of the power supply is connected, and the negative pole of the power supply is connected to the receiving device. Adjust the distance between the spinneret and the receiving device to 5cm; turn on the power supply of the high-voltage power supply, adjust the power supply voltage to about 15KV, and perform electrospinning. Collect to obtain polyvinyl alcohol matrix fibers;

(3) Treatment and functionalization of matrix fibers to prepare ion exchange fibers:

The matrix fiber is immersed in a solution of benzaldehyde, ethanol, deionized water, zinc chloride and sulfuric acid with a mass ratio of 6/30/7/8/6, reacted at 60° C. for 2 hours, and performs cross-linking treatment. Dry the cross-linked fibers in a vacuum oven until there is no moisture, and then heat-treat them in an oven at 180°C for 2 hours; then perform sulfonation treatment with 98% concentrated sulfuric acid for 24 hours to obtain strong-acid cation exchange fibers.

Claims (10)

1, a kind of method of preparing ion-exchange fiber by solution electrostatic spinning method is characterized in that, this method may further comprise the steps:

(1) preparation spinning solution: is 8～16: 92～84 with raw material polystyrene and solvent by mass ratio, and stirring and dissolving at room temperature makes concentration and be 8～16% electrospinning silk solution;

Described solvent is oxolane, N, any or multiple in N～dimethyl formamide, the toluene;

(2) use the electrostatic spinning apparatus spinning, the preparation matrix fiber: the prepared spinning solution of step (1) is joined of electrostatic spinning apparatus be connected with in the sump assemblies of spinning head; Spinning solution links to each other with the positive pole of power supply, and the negative pole of power supply links to each other with receiving system, and the distance of regulating between spinning head and the receiving system is 5-15cm; Open the power supply of high voltage source, the adjusting supply voltage is 15-25kv, carries out electrostatic spinning, is collected by receiving system, obtains polystyrene matrix fiber;

(3) processing of matrix fiber and functionalization prepare ion-exchange fibre:

(3.1) the polystyrene matrix fiber that step (2) is obtained immerses paraformaldehyde: glacial acetic acid: the concentrated sulfuric acid is by 3～10: 30～40: 68～50 quality are than in the liquid mixture prepared, make matrix fiber by submergence fully, 60～90 ℃ of reactions 4～5 hours, obtain cross filament;

(3.2) the described cross filament of step (3.1) is immersed in the sulfonating agent,, obtain strong-acid cation exchange fibre 50～90 ℃ of reactions 12～3 hours.

2, the method for a kind of preparing ion-exchange fiber by solution electrostatic spinning method according to claim 1, it is characterized in that described sulfonating agent is the concentrated sulfuric acid, sulfuric acid and maleic anhydride with dichloroethanes any as in the mixture of solvent, chlorosulfonic acid, fuming sulphuric acid, the sulfuric acid～chlorosulfonic acid.

3, a kind of method of preparing ion-exchange fiber by solution electrostatic spinning method is characterized in that, this method may further comprise the steps:

(1) preparation spinning solution: is 8～16: 92～84 with raw material polystyrene and solvent by mass ratio, and stirring and dissolving at room temperature makes concentration and be 8～16% electrospinning silk solution;

Described solvent is oxolane, N, any or multiple in N～dimethyl formamide, the toluene;

(2) use the electrostatic spinning apparatus spinning, the preparation matrix fiber: the prepared spinning solution of step (1) is joined of electrostatic spinning apparatus be connected with in the sump assemblies of spinning head; Spinning solution links to each other with the positive pole of power supply, and the negative pole of power supply links to each other with receiving system, and the distance of regulating between spinning head and the receiving system is 5-15cm; Open the power supply of high voltage source, the adjusting supply voltage is 15-25kv, carries out electrostatic spinning, is collected by receiving system, obtains polystyrene matrix fiber;

(3) processing of matrix fiber and functionalization prepare ion-exchange fibre:

(3.1) the polystyrene matrix fiber that step (2) is obtained immerses paraformaldehyde: glacial acetic acid: the concentrated sulfuric acid is by 3～10: 30～40: 68～50 quality are than in the liquid mixture prepared, make matrix fiber by submergence fully, 60～90 ℃ of reactions 4～5 hours, obtain cross filament;

(3.2) the described cross filament of step (3.1) is immersed the chloromethyl ether solution that contains catalyst, in 45-55 ℃ of reaction 10-11 hour, make the cross filament of chloromethylation, strongly basic anion ion exchange fibre is produced in the reaction 24～10 hours in room temperature～40 ℃ of the cross filament of chloromethylation and trimethylamine solution;

Described catalyst is zinc chloride or butter of tin;

The concentration of described chloromethyl ether solution is greater than 50%.

4, the method for a kind of preparing ion-exchange fiber by solution electrostatic spinning method according to claim 3 is characterized in that, the solvent in the described trimethylamine solution is water, alcohol compound or halogenated hydrocarbon.

5, a kind of method of preparing ion-exchange fiber by solution electrostatic spinning method is characterized in that, this method may further comprise the steps:

(1) preparation spinning solution: is 8～16: 92～84 with raw material polystyrene and solvent by mass ratio, and stirring and dissolving at room temperature makes concentration and be 8～16% electrospinning silk solution;

Described solvent is oxolane, N, any or multiple in N～dimethyl formamide, the toluene;

(2) use the electrostatic spinning apparatus spinning, the preparation matrix fiber: the prepared spinning solution of step (1) is joined of electrostatic spinning apparatus be connected with in the sump assemblies of spinning head; Spinning solution links to each other with the positive pole of power supply, and the negative pole of power supply links to each other with receiving system, and the distance of regulating between spinning head and the receiving system is 5-15cm; Open the power supply of high voltage source, the adjusting supply voltage is 15-25kv, carries out electrostatic spinning, is collected by receiving system, obtains polystyrene matrix fiber;

(3) processing of matrix fiber and functionalization prepare ion-exchange fibre:

(3.1) the polystyrene matrix fiber that step (2) is obtained immerses paraformaldehyde: glacial acetic acid: the concentrated sulfuric acid is by 3～10: 30～40: 68～50 quality are than in the liquid mixture prepared, make matrix fiber by submergence fully, 60～90 ℃ of reactions 4～5 hours, obtain cross filament;

(3.2) the described cross filament of step (3.1) is immersed the chloromethyl ether solution that contains catalyst, in 45-55 ℃ of reaction 10-11 hour, make the cross filament of chloromethylation, the cross filament of chloromethylation and ethylenediamine solution were 40～60 ℃ of reactions 6～48 hours, ethylenediamine: solvent=4: 0～8, isolate ethylenediamine solution then, washing, drying are produced weakly basic anion exchange fibre;

Described catalyst is zinc chloride or butter of tin;

The concentration of described chloromethyl ether solution is greater than 50%.

6, the method for a kind of preparing ion-exchange fiber by solution electrostatic spinning method according to claim 5 is characterized in that, the solvent in the described ethylenediamine solution is water, alcohol compound or halogenated hydrocarbon.

7, a kind of method of preparing ion-exchange fiber by solution electrostatic spinning method is characterized in that, this method may further comprise the steps:

(1) preparation spinning solution: with raw material polyacrylonitrile and acrylonitrile copolymer and solvent N, N～dimethyl formamide is 6～15: 94～85 by mass ratio, and stirring and dissolving at room temperature makes concentration and be 6～15% electrospinning silk solution;

(2) use the electrostatic spinning apparatus spinning, the preparation matrix fiber: the spinning solution of step (1) preparation is joined of electrostatic spinning apparatus be connected with in the sump assemblies of spinning head; Spinning solution links to each other with the positive pole of power supply, and the negative pole of power supply links to each other with receiving system, and the distance of regulating between spinning head and the receiving system is 5-15cm; Open the power supply of high voltage source, the adjusting supply voltage is 15～25kv, carries out electrostatic spinning, is collected by receiving system, obtains polyacrylonitrile and acrylonitrile copolymer matrix fiber;

(3) processing of matrix fiber and functionalization prepare ion-exchange fibre

(3.1) the described polyacrylonitrile of step (2) and acrylonitrile copolymer matrix fiber being immersed mass concentration is 40～60% hydrazine hydrate solution, 90～120 ℃ of reactions 5～8 hours down, obtains cross filament;

(3.2) the described cross filament of step (3.1) is immersed in the sodium hydroxide solution of 1M concentration, reacted 40 hours down at 70 ℃, be washed till neutrality with distilled water, 0.5M salt acid soak 12 hours are used in centrifugal dehydration, obtain carboxylic acid type cation exchange fibre.

8, a kind of method of preparing ion-exchange fiber by solution electrostatic spinning method is characterized in that, this method may further comprise the steps:

(1) preparation spinning solution: is 6～30: 94～70 with material polyethylene pyrrolidones and solvent by mass ratio, and stirring and dissolving at room temperature makes concentration and be 6～30% electrospinning silk solution;

Described solvent is any in ethanol, the water or two kinds;

(2) use the electrostatic spinning apparatus spinning, the preparation matrix fiber: the prepared spinning solution of step (1) is joined of electrostatic spinning apparatus be connected with in the sump assemblies of spinning head; Spinning solution links to each other with the positive pole of power supply, and the negative pole of power supply links to each other with receiving system, and the distance of regulating between spinning head and the receiving system is 5-15cm; Open the power supply of high voltage source, the adjusting supply voltage is 15～25kv, carries out electrostatic spinning, is collected by receiving system, obtains polyvinylpyrrolidone--based body fiber;

(3) processing of matrix fiber and functionalization prepare ion-exchange fibre:

With the described polyvinylpyrrolidone--based body fiber of step (2) at dryness finalization in 150 ℃ the vacuum drying chamber after 4 hours, under room temperature lucifuge condition, the immersion mass ratio is 40～60: 60～40 peptide dibutyl phthalate: handled 30 minutes in the solution of n-hexane, obtain anion-exchange fibre.

9, a kind of method of preparing ion-exchange fiber by solution electrostatic spinning method is characterized in that, this method may further comprise the steps:

(1) preparation spinning solution: is 6～15: 94～85 with material polyethylene alcohol and solvent by mass ratio, and stirring and dissolving under 80 ℃ of temperature makes concentration and be 6～15% electrospinning silk solution;

Described solvent is any or multiple in ethanol, the water;

(2) use the electrostatic spinning apparatus spinning, the preparation matrix fiber: the prepared spinning solution of step (1) is joined of electrostatic spinning apparatus be connected with in the sump assemblies of spinning head; Spinning solution links to each other with the positive pole of power supply, and the negative pole of power supply links to each other with receiving system, and the distance of regulating between spinning head and the receiving system is 5-15cm; Open the power supply of high voltage source, the adjusting supply voltage is 15～25kv, carries out electrostatic spinning, is collected by receiving system, obtains polyvinyl alcohol matrix fiber;

(3) processing of matrix fiber and functionalization prepare ion-exchange fibre:

(3.1) the described polyvinyl alcohol matrix of step (2) fiber being immersed the quality proportioning is 5～10: 20～30: 5～10: 2～8: in the solution of 3～10 benzaldehyde, ethanol, deionized water, zinc chloride, sulfuric acid, reacted 1～2 hour at 50～70 ℃ 3, carry out crosslinking Treatment, obtain cross filament;

(3.2) the described cross filament of step (3.1) is placed vacuum drying oven dry, again 180～200 ℃ of heat treatments 1～2 hour in baking oven; Carry out sulfonation with 98% the concentrated sulfuric acid then and handled 12～24 hours, obtain the strong-acid type cation exchange fiber.

10, according to the method for claim 1 or 3 or 5 or 7 or 8 or 9 described a kind of preparing ion-exchange fiber by solution electrostatic spinning method, it is characterized in that described electrostatic spinning apparatus mainly is made of the sump assemblies that is connected with spinning head, high voltage source, receiving system; Described spinning head is single hole or porous; Described receiving system can be inactive state or reciprocating motion or rotatablely move in any.

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