CN104313872A - Preparation method of graphene/polyaniline covalent binding conductive fabric - Google Patents

Abstract

The invention discloses a method for preparing a graphene/polyaniline covalently bonded flexible conductive fabric, which belongs to the technical field of textile chemistry. In the present invention, the reaction product of graphene oxide or its derivatives and p-phenylenediamine is firstly applied to the fabric and then reduced, and then the above-mentioned fabric is made to absorb aniline monomer, and then the aniline monomer is polymerized in situ on the fabric to form polyaniline And form a covalent bond with graphene. The method obtains a conductive layer covalently combined with graphene and polyaniline on the surface of the fabric, improves the stability of the conductive layer, and obtains a conductive fabric with excellent effect. This method is applicable to common fabrics such as cotton, wool, silk and other natural fibers, polyester, nylon, acrylic and other synthetic fibers, as well as the conductive finishing of blended or interwoven fabrics of the above fabrics. The prepared functional fabrics can be used in medical care, smart sensors, Mobile power generation, military and other fields.

Description

A preparation method of graphene/polyaniline covalently bonded flexible conductive fabric

technical field

The invention belongs to the technical field of textile chemistry, and relates to a method for self-preparing flexible conductive fabrics by covalently combining graphene or its derivatives and high molecular conductive polymers.

Background technique

As a functional fabric, conductive fabric has broad application prospects in flexible electronic devices, smart materials, new solar cells and other fields. Blending and coating are the earliest methods to develop conductive textile materials. These two methods are simple to process and uniformly conductive. However, the flexibility of the finished fabric is not enough, especially the conductive fabric prepared by the coating method, which encounters strong pull during wearing. Stretching or folding can crack the coating. Therefore, the conductive finishing method of forming a flexible film on the surface of the fabric with graphene and polymerizing the surface of the fabric with a polymer conductive polymer has attracted people's attention.

Graphene exists in the form of a single-layer honeycomb multi-hexagonal structure. Because the carbon atoms are connected by stable covalent bonds, graphene has super conductivity. However, the pure graphene conductive fabric must be uniformly covered with a sufficient amount of graphene before the fabric has better conductivity and uniformity of conductivity; the pure polyaniline conductive fabric also has poor heat resistance and stability. , conductivity is not a strong issue. The present invention first prepares a homogeneous solution system of graphene oxide or its derivatives, the purpose is to prevent the aggregation of graphene in the subsequent reaction process; then add p-phenylenediamine to make it covalently react with graphene oxide, and then fabric Immerse the aqueous solution of p-phenylenediamine-grafted graphene oxide or its derivatives to make the fabric fully absorb p-phenylenediamine-grafted graphene oxide or its derivatives, then dry and reduce; finally use in-situ polymerization on the fabric Aniline or its derivatives are used to prepare flexible conductive fabrics covalently bonded with graphene and polyaniline. Due to the covalent bond formed between graphene and polyaniline, the resulting fabric has good washability and high conductivity.

Contents of the invention

The purpose of the present invention is to apply the graphene and its derivatives and high molecular conductive polymer to the fabric by self-assembly method, so that the fabric can obtain high electrical conductivity.

The present invention adopts following technical scheme:

1 Use p-phenylenediamine to graft graphene oxide, then impregnate and reduce the fabric, and covalently bond with polymer conductive polymer monomers to prepare washable graphene/polyaniline covalently bonded flexible conductive fabrics.

2. The p-phenylenediamine grafted graphene oxide adopts the following process steps:

(1) Add 0.01 to 0.5 parts by mass of anionic surfactant and 0.05 to 0.4 parts by mass of sulfuric acid to 0.05 to 1 part by mass of graphene oxide or its derivatives, at 20 to 60°C, 300-1000W power Ultrasonic reaction for 0.5-2 hours to obtain a uniform mixed solution of graphene oxide or its derivatives and anionic surfactant;

(2) Add 0.1 to 2 parts by mass of p-phenylenediamine and 0.01 to 1 part by mass of thionyl chloride into the solution obtained in (1), and react at 40 to 80°C for 1 to 6 hours under the protection of nitrogen, Obtain p-phenylenediamine grafted graphene oxide or derivatives thereof;

The graphene oxide or its derivatives are at least one of graphene oxide, carboxylated graphene oxide, and sulfonated graphene oxide;

The anionic surfactant is alkyl sulfonate, alkylbenzene sulfonate, alkyl carboxylate, alkylbenzene carboxylate, alkyl naphthalene sulfonate, alkyl naphthalene carboxylate, alkyl anthracene At least one of quinone sulfonate and alkyl anthraquinone carboxylate.

3. The fabric impregnation and reduction treatment adopts the following process steps:

The fabric is immersed in the solution obtained by grafting graphene oxide or its derivatives with p-phenylenediamine, the immersion temperature is 20-50°C, the immersion time is 0.5-2h, and then the fabric is dried at 50-80°C for 0.5-5h, and then The dried fabric is reduced in a reducing agent solution of 1-10g/L, the reduction temperature is 50-100°C, the reduction time is 0.5-6h, and finally washed with water and dried to obtain the graft-reduced graphene oxide covered with p-phenylenediamine or fabrics of its derivatives;

The reducing agent is at least one of sodium dithionite, sodium bisulfite, glucose, chitosan, vitamin C, hydrazine hydrate, and sodium borohydride.

4. The covalent combination with the high molecular conductive polymer monomer adopts the following process steps:

Immerse the obtained fabric into a solution containing 0.02-1mol/L high molecular conductive polymer monomer and 0.02-1mol/L acid solution, the immersion temperature is 0-40°C, the immersion time is 0.5-24h, and then the initiator is added to make the polymer single Bulk polymerization into high-molecular conductive polymers to obtain graphene/polyaniline covalently bonded flexible conductive fabrics;

The high molecular conductive polymer monomer is at least one of aniline, p-aminobenzenesulfonic acid and m-aminobenzenesulfonic acid.

The beneficial effects of the present invention are: the graphene and the high-resolution conductive polymer are applied to the surface of the fabric in a covalently bonded manner. The technical scheme of the present invention is simple and easy to operate. There is no special requirement for the equipment, and conventional dyeing and finishing equipment can be used. Large-scale production has broad application prospects.

Detailed ways

The present invention will be further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

Example 1

A kind of preparation method of graphene/polyaniline covalently combining flexible conductive fabric, its process is as follows:

(1) Prepare a uniform mixed solution of graphene oxide and anionic surfactant: add 0.2 mass parts of anionic surfactant and 0.1 mass part of sulfuric acid into the graphene oxide of 0.4 mass parts, at 40 ℃, 800W Ultrasonic reaction under power for 1h, to obtain a uniform mixed solution of graphene oxide or its derivatives and anionic surfactant;

(2) p-Phenylenediamine grafted graphene oxide or its derivatives: 0.12 parts by mass of p-phenylenediamine and 0.06 parts by mass of thionyl chloride were added to the solution obtained in (1), at 50 ° C under nitrogen Reaction 4h under the protection of p-phenylenediamine grafted graphene oxide or its derivatives;

(3) Preparation of fabrics grafted with p-phenylenediamine-reduced graphene oxide: immerse the fabrics in the solution obtained in (2), the immersion temperature is 30°C, the immersion time is 1h, then the fabrics are dried at 60°C for 3h, and then The dried fabric was reduced in a 5g/L sodium dithionite solution, the reduction temperature was 90°C, the reduction time was 0.5h, and finally washed and dried to obtain a fabric covered with p-phenylenediamine grafted reduced graphene oxide;

(4) Preparation of graphene/polyaniline covalently bonded conductive fabric: immerse the fabric obtained in (3) into a solution containing 0.2mol/L aniline and 1mol/L hydrochloric acid, the immersion temperature is 20°C, the immersion time is 12h, and then 0.2 The mol/L initiator ammonium persulfate in situ polymerized aniline into polyaniline to obtain graphene/polyaniline covalently bonded flexible conductive fabric with good washability and conductivity.

Example 2

A kind of preparation method of graphene/polyaniline covalently combining flexible conductive fabric, its process is as follows:

(1) prepare the homogeneous mixed solution of carboxylated graphene oxide and anionic surfactant: the anionic surfactant of 0.1 mass part, the sulfuric acid of 0.2 mass part, join in the carboxylated graphene oxide of 0.3 mass part, in Ultrasonic reaction at 30°C and 500W power for 2 hours to obtain a uniform mixed solution of carboxylated graphene oxide or its derivatives and anionic surfactant;

(2) p-Phenylenediamine grafted with carboxylated graphene oxide: add 0.08 parts by mass of p-phenylenediamine and 0.04 parts by mass of thionyl chloride to the solution obtained in (1), and place it under the protection of nitrogen at 70 ° C. After reacting for 3h, p-phenylenediamine grafted carboxylated graphene oxide or its derivatives are obtained;

(3) Preparation of the fabric of carboxylated graphene oxide grafted with p-phenylenediamine: immerse the fabric in the solution obtained in (2), the immersion temperature is 20°C, the immersion time is 1.5h, and then the fabric is dried at 60°C for 3h , and then reducing the dried fabric in 4g/L hydrazine hydrate solution, the reduction temperature is 80°C, the reduction time is 2h, and finally washed and dried to obtain a fabric covered with p-phenylenediamine grafted and reduced carboxylated graphene oxide;

(4) Preparation of graphene/polyaniline covalently bonded conductive fabric: immerse the fabric obtained in (3) into a solution containing 0.5mol/L aniline and 1mol/L hydrochloric acid, the immersion temperature is 30°C, the immersion time is 6h, and then add 0.5 The mol/L initiator ammonium persulfate in situ polymerized aniline into polyaniline to obtain graphene/polyaniline covalently bonded flexible conductive fabric with good washability and conductivity.

Example 3

A kind of preparation method of graphene/polyaniline covalently combining flexible conductive fabric, its process is as follows:

(1) Prepare a uniform mixed solution of sulfonated graphene oxide and anionic surfactant: the anionic surfactant of 0.15 mass parts, the sulfuric acid of 0.15 mass parts, join the sulfonated graphite oxide of 0.4 mass part ene, ultrasonic reaction at 40°C and 800W power for 1.5h, to obtain a uniform mixed solution of sulfonated graphene oxide or its derivatives and anionic surfactant;

(2) p-Phenylenediamine grafted sulfonated graphene oxide: 0.13 parts by mass of p-phenylenediamine and 0.06 parts by mass of thionyl chloride were added to the solution obtained in (1), at 60 ° C under nitrogen Reaction for 8h under the protection of p-phenylenediamine grafted sulfonated graphene oxide or derivatives thereof;

(3) Preparation of the fabric of sulfonated graphene oxide grafted with p-phenylenediamine: immerse the fabric into the solution obtained in (2), the immersion temperature is 250°C, the immersion time is 2.5h, and then the fabric is dried at 50°C Dry for 6 hours, then reduce the dried fabric in 6g/L sodium dithionite solution, the reduction temperature is 90°C, the reduction time is 0.5h, and finally washed with water and dried to obtain the covered p-phenylenediamine graft reduction sulfonation Fabrics of graphene oxide or its derivatives;

(4) Preparation of graphene/polyaniline covalently bonded conductive fabric: immerse the fabric obtained in (3) into a solution containing 0.35mol/L aniline and 1mol/L hydrochloric acid, the immersion temperature is 10°C, the immersion time is 18h, and then 0.35 The mol/L initiator ammonium persulfate in situ polymerized aniline into polyaniline to obtain graphene/polyaniline covalently bonded flexible conductive fabric with good washability and conductivity.

Example 4

A kind of preparation method of graphene/polyaniline covalently combining flexible conductive fabric, its process is as follows:

(1) Prepare a uniform mixed solution of graphene oxide and anionic surfactant: add 0.12 parts by mass of anionic surfactant and 0.05 parts by mass of sulfuric acid into graphene oxide of 0.5 parts by mass, at 20°C, 600W Ultrasonic reaction under power for 2 hours to obtain a uniform mixed solution of sulfonated graphene oxide or its derivatives and anionic surfactant;

(2) p-Phenylenediamine grafted graphene oxide: add 0.15 parts by mass of p-phenylenediamine and 0.08 parts by mass of thionyl chloride to the solution obtained in (1), and react at 40°C under the protection of nitrogen 12h, obtain p-phenylenediamine grafted graphene oxide or derivatives thereof;

(1) Preparation of fabrics grafted with p-phenylenediamine-reduced graphene oxide: immerse the fabrics in the solution obtained in (2), the immersion temperature is 20°C, the immersion time is 1h, then the fabrics are dried at 70°C for 2h, and then The dried fabric is reduced in 4g/L hydrazine hydrate solution, the reduction temperature is 95°C, the reduction time is 1h, and finally washed and dried to obtain a fabric covered with p-phenylenediamine grafted reduced graphene oxide or its derivatives;

(4) Preparation of graphene/polyaniline covalently bonded conductive fabric: immerse the fabric obtained in (3) into a solution containing 0.15mol/L aniline and 1mol/L hydrochloric acid, the immersion temperature is 20°C, the immersion time is 8h, and then add 0.15 The mol/L initiator ammonium persulfate in situ polymerized aniline into polyaniline to obtain graphene/polyaniline covalently bonded flexible conductive fabric with good washability and conductivity.

Implementation effect of the present invention

After the fabrics were treated in Examples 1-4, the following tests were carried out, and the test results are shown in Table 1.

The surface resistance of the fabric was measured on a SZT-2A four-probe tester (Suzhou Tongchuang Electronics Co., Ltd.).

It can be seen from Table 1 that the resistance value of the finished fabric decreased significantly. It can be seen that the technical solution provided by the present invention can endow the polyester-cotton fabric with excellent electrical conductivity.

Table 1 Test results of implementing fabrics

Claims (4)

1. the preparation method of a graphene/polyaniline covalent bond compliant conductive fabric, it is characterized in that adopting p-phenylenediamine (PPD) grafted graphene oxide, then to textile impregnation and reduction treatment, and with conductive polymer polymer monomer covalent bond, prepare washable graphene/polyaniline covalent bond compliant conductive fabric.

2., as right wants the preparation method of a kind of graphene/polyaniline covalent bond compliant conductive fabric as described in 1, it is characterized in that described p-phenylenediamine (PPD) grafted graphene oxide adopts following processing step:

(1) by the anion surfactant of 0.01 ~ 0.5 parts by mass, the sulfuric acid of 0.05 ~ 0.4 parts by mass, join in the graphene oxide or derivatives thereof of 0.05 ~ 1 parts by mass, at 20 ~ 60 DEG C, ultrasonic reaction 0.5 ~ 2h under 300-1000W power, obtain the homogeneous mixture solotion of graphene oxide or derivatives thereof and anion surfactant;

(2) by the p-phenylenediamine (PPD) of 0.1 ~ 2 parts by mass, the thionyl chloride of 0.01 ~ 1 parts by mass, adds in the solution of (1) gained, and under 40 ~ 80 DEG C of protections at nitrogen, reaction 1 ~ 6h, obtains p-phenylenediamine (PPD) grafted graphene oxide or derivatives thereof;

Described graphene oxide or derivatives thereof is at least one in graphene oxide, carboxylated graphene oxide, sulfonic group graphene oxide;

Described anion surfactant is at least one in alkylsulfonate, alkylbenzenesulfonate, alkyl carboxylate, alkylbenzene carboxylates, alkylnaphthalene sulfonate, Fluhyzon carboxylate, alkyl-anthraquinone sulfonate, alkyl-anthraquinone carboxylate.

3., as right wants the preparation method of a kind of graphene/polyaniline covalent bond compliant conductive fabric as described in 1, it is characterized in that described textile impregnation and reduction treatment adopt following processing step:

By textile impregnation in the solution of p-phenylenediamine (PPD) grafted graphene oxide or derivatives thereof gained, dipping temperature 20 ~ 50 DEG C, dip time 0.5 ~ 2h, again by fabric in 50 ~ 80 DEG C of drying 0.5 ~ 5h, then oven dry fabric is reduced in the reductant solution of 1 ~ 10g/L, reduction temperature 50 ~ 100 DEG C, recovery time 0.5 ~ 6h, finally wash, dry, obtain the fabric covering p-phenylenediamine (PPD) grafting redox graphene or derivatives thereof;

Described reductant is at least one in sodium dithionite, sodium hydrogensulfite, glucose, shitosan, vitamin C, hydrazine hydrate, sodium borohydride.

4., as right wants the preparation method of a kind of graphene/polyaniline covalent bond compliant conductive fabric as described in 1, it is characterized in that described and conductive polymer polymer monomer covalent bond adopts following processing step:

By the textile impregnation of gained to containing in 0.02 ~ 1mol/L conductive polymer polymer monomer and 0.02 ~ 1mol/L acid solution, dipping temperature 0 ~ 40 DEG C, dip time 0.5 ~ 24h, then adding initator makes polymer monomer aggregate into conductive polymer polymer, obtains graphene/polyaniline covalent bond compliant conductive fabric;

Described conductive polymer polymer monomer is at least one in aniline, sulfanilic acid, metanilic acid.