阅读说明：本技术 一种金属有机框架化合物修饰涤棉织物导电材料的制法 (Preparation method of metal organic framework compound modified polyester-cotton fabric conductive material ) 是由 王潮霞 韩玮屹 原韵 冯宏 吴怡 李泽钊 殷允杰 王博 于 2020-06-12 设计创作，主要内容包括：本发明公开了一种金属有机框架化合物修饰涤棉织物导电材料的制法,包括以下步骤：(1)将涤棉织物基材在施加张力的条件下浸渍于碱性溶剂中使棉织物纤维溶胀并羧基化,后洗涤、干燥；(2)将金属盐溶液和有机配体溶液加入到步骤(1)得到的织物中,后洗涤并在溶剂中激活后干燥；(3)将步骤(2)得到的织物浸渍于碱性溶液中,得到所述金属有机框架化合物修饰涤棉织物导电材料。本发明的方法简单、条件温和,能够制备出弹性好且耐拉伸的金属有机框架化合物修饰涤棉织物柔性导电材料。(The invention discloses a preparation method of a metal organic framework compound modified polyester-cotton fabric conductive material, which comprises the following steps: (1) soaking a polyester cotton fabric base material in an alkaline solvent under the condition of applying tension to swell and carboxylate cotton fabric fibers, and then washing and drying; (2) adding a metal salt solution and an organic ligand solution into the fabric obtained in the step (1), washing, activating in a solvent and drying; (3) and (3) soaking the fabric obtained in the step (2) in an alkaline solution to obtain the metal organic framework compound modified polyester-cotton fabric conductive material. The method is simple and mild in condition, and the metal organic framework compound modified polyester-cotton fabric flexible conductive material with good elasticity and stretch resistance can be prepared.)

1. A method for preparing a metal organic framework compound modified polyester-cotton fabric conductive material is characterized by comprising the following steps:

(1) soaking a polyester-cotton fabric base material in a mixed solvent of an alkaline agent A for swelling the polyester-cotton fabric and an alkaline agent B for providing negative charge sites under the condition of applying tension, and then washing and drying;

(2) and (2) adding a metal salt solution and an organic ligand solution into the fabric obtained in the step (1), washing, activating in a solvent, and drying to obtain the metal organic framework compound modified polyester-cotton fabric conductive material.

2. The method for preparing the metal organic framework compound modified polyester-cotton fabric conductive material according to claim 1, wherein the metal organic framework compound modified polyester-cotton fabric conductive material obtained in the step (2) is immersed in an alkaline solution to obtain an etched metal organic framework compound modified polyester-cotton fabric conductive material.

3. The method for preparing the metal organic framework compound modified polyester-cotton fabric conductive material according to claim 1, wherein in the step (1), the alkaline solvent A is sodium hydroxide or potassium hydroxide; the alkaline solvent B is a mixed solution of sodium chloroacetate and disodium ethylene diamine tetraacetate.

4. The method for preparing the metal organic framework compound modified polyester-cotton fabric conductive material as claimed in claim 3, wherein the mass ratio of the alkaline solvent A, the sodium chloroacetate solution and the disodium ethylene diamine tetraacetate is 240-320: 699-932: 34-168.

5. The preparation method of the metal organic framework compound modified polyester-cotton fabric conductive material according to claim 1, wherein in the step (1), the component ratio of polyester to cotton in the polyester-cotton fabric is 50:50-20: 80.

6. The method for preparing the metal organic framework compound modified polyester-cotton fabric conductive material according to claim 2, wherein the concentration of the alkaline solution is 6-8 mol/L.

7. The method for preparing the metal organic framework compound modified polyester-cotton fabric conductive material according to claim 1, wherein in the step (1), the tension is 20-50N.

8. The method for preparing the metal-organic framework compound modified polyester-cotton fabric conductive material according to claim 1, wherein in the step (2), the metal salt is copper trifluoroacetylacetonate, copper oxalate or copper acetate; the organic ligand is 2,3,6,7,10, 11-hexahydro triphenylene.

9. The method for preparing the metal-organic framework compound modified polyester-cotton fabric conductive material according to claim 1, wherein in the step (2), the solvent of the metal salt and the organic ligand is water: NMP or DMF is 1:1 to 10: 1.

10. The preparation method of the metal organic framework compound modified polyester-cotton fabric conductive material according to claim 1, wherein in the step (2), the concentration of the metal salt solution is 0.02-0.06 mol/L; the concentration of the organic ligand solution is 0.01-0.03 mol/L.

Technical Field

The invention relates to a method for preparing a fabric conductive material, in particular to a method for preparing a metal organic framework compound modified polyester-cotton fabric flexible conductive material.

Background

Compared with the common rigid conductive material, the flexible conductive material has the advantages of softness and flexibility, and is widely concerned by people. The flexible conductive material has wide application prospect in wearable equipment. The metal organic framework compound (MOF) is a porous and high-surface-area solid material consisting of organic ligands and metal ion/cluster centers, and has good electric signal transmission and storage functions.

Patent 201711067706.X uses polyimide as a fabric substrate, and MOFs of ZIF-8 type, MIL88D type, MIL100-101 type or IRMOF1-18 type are grafted on the surface by radiation to obtain a metal organic framework fabric.

Disclosure of Invention

The purpose of the invention is as follows: the invention aims to provide a method for preparing a metal organic framework compound modified polyester-cotton fabric flexible conductive material, which is simple in method and mild in condition.

The technical scheme is as follows: the invention relates to a method for preparing a metal organic framework compound modified polyester-cotton fabric conductive material, which comprises the following steps:

(1) soaking a polyester-cotton fabric base material in a mixed solvent of an alkaline agent A for swelling the polyester-cotton fabric and an alkaline agent B for providing negative charge sites under the condition of applying tension, and then washing and drying;

(2) and (2) adding a metal salt solution and an organic ligand solution into the fabric obtained in the step (1), washing, activating in a solvent, and drying to obtain the metal organic framework compound modified polyester-cotton fabric conductive material.

The polyester-cotton fabric with the surface modified with the metal-organic framework compound is an original plane fabric, the positions and the flexibility of fibers and yarns are basically unchanged, but the fabric is obviously insufficient in elasticity. In order to improve the elasticity and the mechanical property, the metal organic framework compound modified polyester-cotton fabric conductive material obtained in the step (2) is soaked in an alkaline solution to obtain an etched metal organic framework compound modified polyester-cotton fabric conductive material. The concentration of the alkaline solution is 6-8 mol/L. Preferably, the mixture is soaked in alkaline solution for 5-15min at 20-30 deg.C, wherein the alkaline solution may be sodium hydroxide or potassium hydroxide, or other alkaline solvent.

In order to effectively expand the polyester-cotton fabric substrate, on one hand, the flattened fabric substrate is changed into an oval shape, and on the other hand, more MOF (metal organic framework) binding sites are formed on the fabric substrate, and the alkaline solvent A is sodium hydroxide or potassium hydroxide; the alkaline solvent B is a mixed solution of sodium chloroacetate and disodium ethylene diamine tetraacetate.

In order to balance the degree of cellulose swelling and loosening and the number of provided binding sites, in the step (1), the mass ratio of the alkaline solvent A, the sodium chloroacetate solution and the disodium ethylene diamine tetraacetate is 240-320: 699-932: 34-168. If the amount of the alkali solvent A is too low, the conductivity will be deteriorated, and the strength will be increased, while if the amount of the sodium chloroacetate solution and disodium ethylenediaminetetraacetate is too low, the conductivity will be deteriorated. Therefore, the proportion range of the three components is kept in the range of the application, and the effect is better.

In order to balance the elasticity and the stretch resistance of the fabric, in the step (1), the component ratio of the polyester fiber to the cotton fiber in the polyester-cotton fabric is 50:50-20: 80.

In order to obtain a better stretching condition and enable the elongation state of the polyester-cotton fabric to be better, in the step (1), the tension is 20-50N.

In order to obtain a metal organic framework compound which has good adaptability with polyester-cotton fabrics and better grafting effect, in the step (2), the metal salt comprises copper trifluoroacetylacetonate, copper oxalate or copper acetate; the organic ligand is 2,3,6,7,10, 11-hexahydro triphenylene.

In order to make the metal salt and the organic ligand better dissolve, the solvent of the metal salt and the organic ligand is water, NMP or DMF, and the ratio of water: NMP or DMF is 1:1 to 10: 1; the concentration of the metal salt solution is 0.02-0.06 mol/L; the concentration of the organic ligand solution is 0.01-0.03 mol/L.

Under the condition of applying a certain tension, the polyester-cotton fabric is soaked in the mixed solution of sodium hydroxide, sodium chloroacetate and disodium ethylene diamine tetraacetate to make the cellulose expand and become loose, so that the hygroscopicity of the fiber is increased, more carboxyl groups are conveniently formed on the cotton fiber, the quantity of negative charges on the surface of the cotton fiber is increased, the quantity of the negative charges on the surface of the cellulose is increased by about 30%, and the Cu are formed on the polyester-cotton fabric²⁺The binding force of the MOF and the fabric substrate is enhanced by the sites connected by the coordination bonds of the plasma metal ions. The MOF has the characteristics of porosity and high surface area, and can be combined with the polyester-cotton fabric, so that the flexibility and the air permeability of the polyester-cotton fabric can be maintained while the conductivity of the polyester-cotton fabric is endowed. In the process, the surface of the polyester fiber has no sites, so that the metal organic framework compound cannot be deposited on the surface, and the conductive material can fall off after cleaning.

The polyester-cotton fabric with the surface modified with the metal-organic framework compound is an original plane fabric, the positions and the flexibility of fibers and yarns are basically unchanged, but the fabric is obviously insufficient in elasticity. And continuously putting the planar metal organic framework compound modified polyester-cotton fabric flexible conductive material in an alkaline solution, wherein no tension is applied to the fiber material. The cotton fiber is subjected to alkali shrinkage under the condition of concentrated alkali, and meanwhile, the polyester fiber is partially etched and stripped under the condition of concentrated alkali. The whole conductive fabric shrinks in size and increases in thickness as a result of the action of the concentrated alkali. The contracted fabric cotton component has certain elasticity, and the size can be lengthened after stretching; the terylene component is still distributed among the cotton components, maintains the original position and is embedded among the conductive cotton components by the insulation of the terylene component, so that the conductive material on the surface of the cotton can not be stacked or unfolded when the fabric is stretched and contracted, the conductive stability of the conductive fabric is maintained, meanwhile, the terylene component can still endow the conductive fabric with mechanical property, and the condition that the cotton component is broken due to overlarge tension can be avoided.

Has the advantages that: compared with the prior art, the invention has the following beneficial effects: (1) the method comprises the steps of treating the polyester-cotton fabric under the condition of applying a certain tension to enable cotton fibers to expand and become loose, soaking the primarily obtained polyester-cotton fabric modified by the metal organic framework compound in an alkaline solvent, and preparing the metal organic framework compound modified polyester-cotton fabric flexible conductive material with strong MOF (metal organic framework) and polyester-cotton fabric bonding force, elasticity and tensile resistance without harsh conditions and complicated steps; (2) the material has good elasticity and stretch resistance, the conductivity is kept stable under different stress conditions, and the signal stability of the material in wearable application is enhanced; (3) the cotton/polyester fabric obtained by knitting or weaving is used as a base material and has good flexibility and air permeability. The MOF material has a porous structure and a high surface area, and the MOF-polyester cotton fabric flexible conductive material endows the polyester cotton fabric with conductivity while keeping the flexibility and the air permeability of the polyester cotton fabric; (4) the fabric has very good potential application value in the fields of wearable electronic equipment, human body signal detection equipment and the like, and the polyester-cotton fabric is used as a base material, so that the fabric is low in cost, easy to process and good in application performance.

Detailed Description

The present invention is described in further detail below.