阅读说明：本技术 一种尼龙多孔纤维膜及其制备方法、双向拉伸尼龙多孔纤维膜及其制备方法 (Nylon porous fiber membrane and preparation method thereof, and biaxially oriented nylon porous fiber membrane and preparation method thereof ) 是由 贾露 刘运锦 陈曦 林新土 李智尧 郑伟 牟青英 于 2019-11-08 设计创作，主要内容包括：本发明涉及薄膜材料技术领域,特别涉及一种尼龙多孔纤维膜及其制备方法、双向拉伸尼龙多孔纤维膜及其制备方法,其中,所述尼龙多孔纤维膜为核壳结构,其中,壳层为尼龙,核层为碳纤；通过静电方式的方法制备了微纳米尼龙多孔纤维膜,后经过多次的热轧和双向拉伸、定型制得尼龙多孔纤维膜。本发明制得的双向拉伸尼龙多孔纤维膜具有很好的耐温性、高的比表面积和孔隙率以及良好的力学性能,可广泛应用于包装材料、过滤膜、隔膜等领域。(The invention relates to the technical field of film materials, in particular to a nylon porous fiber membrane and a preparation method thereof, and a biaxially oriented nylon porous fiber membrane and a preparation method thereof, wherein the nylon porous fiber membrane is of a core-shell structure, a shell layer is made of nylon, and a core layer is made of carbon fibers; the method comprises the steps of preparing a micro-nano nylon porous fiber membrane by an electrostatic method, and then performing hot rolling, biaxial stretching and shaping for multiple times to obtain the nylon porous fiber membrane. The biaxially oriented nylon porous fiber membrane prepared by the invention has good temperature resistance, high specific surface area and porosity and good mechanical property, and can be widely applied to the fields of packaging materials, filtering membranes, diaphragms and the like.)

1. A nylon porous fiber membrane is characterized in that: the nylon porous fiber membrane is of a core-shell structure, wherein a shell layer is made of nylon, and a core layer is made of carbon fiber.

2. The nylon porous fiber membrane of claim 1, wherein: the melting point of the nylon is 200-260 ℃.

3. The nylon porous fiber membrane of claim 2, wherein: the nylon is one or more of nylon 6, nylon 66, nylon 6/66 and nylon 11.

4. A method for preparing a nylon porous fiber membrane according to any one of claims 1 to 3, comprising the steps of:

① preparing shell solution:

adding nylon into formic acid, and stirring at the temperature of 50-80 ℃ to obtain a nylon spinning solution;

② preparation of core layer solution:

adding carbon fibers into a weak acid solvent, and performing ultrasonic dispersion to obtain a dispersion liquid;

③ preparation of Nylon porous fiber Membrane:

and (3) respectively placing the nylon spinning solution prepared in the step ① and the dispersion solution prepared in the step ② in the outer layer and the inner layer of an injection pump, and performing coaxial electrostatic spinning at room temperature to obtain the nylon porous fiber membrane.

5. The method for preparing a nylon porous fiber membrane according to claim 4, characterized in that: the weak acid solvent is acetic acid.

6. A preparation method of a biaxially oriented nylon porous fiber membrane is characterized by comprising the following steps: the method comprises the following steps:

s100, placing the nylon porous fiber membrane at 10-60 MPa and 50-60 ℃ for primary hot rolling, then performing primary biaxial stretching at 120-140 ℃, and then placing at 140-160 ℃ for heat setting to obtain a primary biaxial stretching nylon porous fiber membrane;

s200, placing the primary biaxially oriented nylon porous fiber membrane obtained in the step S100 at a temperature of 80-100 ℃ under 5-30 MPa for secondary hot rolling, then performing secondary biaxially oriented stretching at a temperature of 130-150 ℃, and then placing at a temperature of 140-170 ℃ for heat setting to obtain a secondary biaxially oriented nylon porous fiber membrane;

s300, placing the secondary biaxially-oriented nylon porous fiber membrane obtained in the step S200 at 5-30 MPa and 90-120 ℃ for three times of hot rolling to obtain a tertiary biaxially-oriented nylon porous fiber membrane;

s400, placing the three-time biaxially-oriented nylon porous fiber membrane obtained in the step S300 at a temperature of 160-180 ℃ for heat setting to obtain a biaxially-oriented nylon porous fiber membrane;

the nylon porous fiber membrane is prepared by the nylon porous fiber membrane of claim 1 or the preparation method of the nylon porous fiber membrane of claim 3.

7. A biaxially oriented nylon porous fiber membrane produced by the method for producing a biaxially oriented nylon porous fiber membrane according to claim 6.

Technical Field

The invention relates to the technical field of thin film materials, in particular to a nylon porous fiber membrane and a preparation method thereof, and a biaxially oriented nylon porous fiber membrane and a preparation method thereof.

Background

The electrostatic spinning technology is that under the action of a high-voltage electric field, polymer solution is sprayed and spun, and in the operation process, a solvent is volatilized and finally solidified on a collecting plate to form fibers. The diameter of the fiber obtained by the electrostatic spinning technology is submicron, the obtained material has the characteristics of large specific surface area, high porosity and the like, and has the advantages of controllable multistage coarse structure, fiber diameter, stacking density, capability of being communicated to form a fiber network and the like, so that the material attracts high attention of people and is widely applied to the fields of catalysis, adsorption, environment, energy, food, medicine and the like. However, since the non-oriented fiber film obtained by electrospinning is generally formed by random overlapping between fibers, strong force is not applied between the filaments, and the strength of the obtained fiber film is not sufficient, which limits the range of use thereof.

Nylon films have been widely used in the field of packaging technology in recent years due to their excellent puncture resistance, solvent resistance, heat and cold resistance, oil resistance, and good tensile strength and tensile strength. The hot rolling and the biaxial stretching are combined, so that the properties of the film such as strength, toughness and the like can be obviously improved.

In the existing preparation technology of the biaxially oriented polyamide film, a nylon fiber porous film with high specific surface area, high temperature resistance, high porosity and excellent mechanical properties cannot be obtained.

The preparation method of the biaxially oriented nylon fiber porous membrane is characterized in that the preparation method comprises the steps of carrying out hot rolling and biaxial orientation on a nylon melt-blown or spun-bonded fiber net for multiple times, and finally carrying out heat setting to obtain the nylon fiber porous membrane, wherein the preparation method is characterized in that the preparation method is 201610315619.0, and the preparation date is 2016, 08 and 10 days; however, the nylon fiber porous film prepared by the scheme still has insufficient mechanical properties such as temperature resistance, porosity, tensile strength and the like.

Disclosure of Invention

In order to solve the defects of the existing biaxially oriented polyamide film in the background technology in the aspects of temperature resistance, porosity, tensile strength and other mechanical properties, the invention provides a nylon porous fiber film which is of a core-shell structure, wherein a shell layer is made of nylon, and a core layer is made of carbon fibers.

On the basis of the scheme, the melting point of the nylon is 200-260 ℃.

On the basis of the scheme, further, the nylon is one or more of nylon 6, nylon 66, nylon 6/66 and nylon 11.

The invention provides a preparation method of a nylon porous fiber membrane, which comprises the following steps:

① preparing shell solution:

adding nylon into formic acid, and stirring at the temperature of 50-80 ℃ to obtain a nylon spinning solution, wherein the nylon spinning solution is preferably prepared into a uniform nylon spinning solution with the concentration of 10-25 wt%;

② preparation of core layer solution:

adding carbon fibers into a weak acid solvent, and performing ultrasonic dispersion to obtain a dispersion liquid, wherein the dispersion liquid is preferably a uniform dispersion liquid with the concentration of 1-3 wt%;

③ preparation of Nylon porous fiber Membrane:

respectively placing the nylon spinning solution prepared in the step ① and the dispersion solution prepared in the step ② in the outer layer and the inner layer of an injection pump, and performing coaxial electrostatic spinning at room temperature to obtain a nylon porous fiber membrane;

the nylon porous fiber membrane has a three-dimensional net structure, and the thickness of the prepared nylon porous fiber membrane can be controlled by controlling the spinning time and the rotating speed of the collecting roller;

wherein the voltage is preferably 15-30 kV, the distance between the needle head and the collecting roller is preferably 15-20 cm, the diameter of the outer-layer needle head is preferably 0.5-0.7 mm, the diameter of the inner-layer needle head is preferably 0.3mm, the advancing speed of the outer layer is preferably 0.5-1 mL/h, the advancing speed of the inner layer is preferably 0.1-0.3 mL/h, and the humidity is preferably 25-35%.

On the basis of the scheme, further, the weak acid solvent is acetic acid.

The invention provides a preparation method of a biaxially oriented nylon porous fiber membrane, which comprises the following steps:

s100, placing the nylon porous fiber membrane at 10-60 MPa and 50-60 ℃ for primary hot rolling, wherein the primary hot rolling time is preferably 1-10S, then performing primary biaxial stretching at 120-140 ℃, and then placing at 140-160 ℃ for heat setting to obtain a primary biaxial stretching nylon porous fiber membrane;

wherein the initial stretching delay time is preferably 3s, the stretching completion delay time is preferably 3s, the heat setting time is preferably 60s, the retraction speed is preferably 1mm/s, and the stretching multiplying power is preferably 2.0 x 2.0-3.0 x 3.0;

s200, placing the primary biaxially oriented nylon porous fiber membrane obtained in the step S100 at 5-30 MPa and 80-100 ℃ for secondary hot rolling, wherein the secondary hot rolling time is preferably 1-10S, then performing secondary biaxial orientation at 130-150 ℃, and then placing at 140-170 ℃ for heat setting to obtain a secondary biaxially oriented nylon porous fiber membrane;

wherein the initial stretching delay time is preferably 3s, the stretching completion delay time is preferably 3s, the heat setting time is preferably 60s, the retraction speed is preferably 1mm/s, and the stretching magnification is preferably 1.0 multiplied by 1.0-2.0 multiplied by 2.0;

s300, placing the secondary biaxially-oriented nylon porous fiber membrane obtained in the step S200 at a temperature of between 90 and 120 ℃ under 5 to 30MPa for three times of hot rolling, wherein the time for the three times of hot rolling is preferably 1 to 5S, so as to obtain a tertiary biaxially-oriented nylon porous fiber membrane;

s400, placing the three-time biaxially-oriented nylon porous fiber membrane obtained in the step S300 at a temperature of 160-180 ℃ for heat setting to obtain a biaxially-oriented nylon porous fiber membrane;

the nylon porous fiber membrane is prepared by the nylon porous fiber membrane or the preparation method of the nylon porous fiber membrane.

The invention provides a biaxially oriented nylon porous fiber membrane prepared by the preparation method of the biaxially oriented nylon porous fiber membrane.

Compared with the prior art, the nylon porous fiber membrane and the preparation method thereof provided by the invention have the following technical principles and beneficial effects:

(1) by adopting the electrostatic spinning technology, the nylon porous fiber membrane with controllable diameter and thickness and high specific surface area and porosity is prepared more simply and conveniently;

(2) the hot rolling and biaxial tension technology are combined, so that the temperature resistance and the mechanical property of the electrostatic spinning film are improved;

(3) the heat resistance and the mechanical property of the film material are favorably improved by adding the carbon fibers, and in order to further improve the film property, the specific preparation process is adopted to effectively avoid the problem that the film property is influenced due to agglomeration and uneven dispersion of the carbon fibers in the spinning process.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention also provides the following embodiments: