WO2021142933A1 - 导电丝素材料及其制备方法和应用 - Google Patents

导电丝素材料及其制备方法和应用 Download PDF

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WO2021142933A1
WO2021142933A1 PCT/CN2020/080876 CN2020080876W WO2021142933A1 WO 2021142933 A1 WO2021142933 A1 WO 2021142933A1 CN 2020080876 W CN2020080876 W CN 2020080876W WO 2021142933 A1 WO2021142933 A1 WO 2021142933A1
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silk fibroin
aqueous solution
preparation
fibroin material
conductive
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PCT/CN2020/080876
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English (en)
French (fr)
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邢铁玲
赵俊涛
卢神州
王义容
卢书晴
陈国强
林楚楚
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南通纺织丝绸产业技术研究院
苏州大学
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Priority to US17/265,689 priority Critical patent/US11845843B2/en
Publication of WO2021142933A1 publication Critical patent/WO2021142933A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/14—Chemical modification with acids, their salts or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2481/02—Polythioethers; Polythioether-ethers

Definitions

  • the invention relates to a conductive material, in particular to a conductive silk fibroin material and a preparation method and application thereof.
  • Silk fibroin can be used as a material for biomedical applications because it has excellent biocompatibility, high surface-to-mass ratio, good mechanical properties and good forming ability, as well as good biocompatibility and slow biodegradability , Has great application potential.
  • the newly developed conductive polymers Compared with traditional conductive materials (inorganic semiconductor materials, metal materials), the newly developed conductive polymers have the characteristics of both polymer materials and conductive materials, and have better biocompatibility and flexibility.
  • the use of conductive polymers for silk The conductive modification of prime protein materials has attracted the attention of many scholars.
  • conductive silk fibroin film As a new type of functional material, conductive silk fibroin film has unique physical and chemical properties, and has a certain degree of intelligence because it can respond to specific external stimuli. Conductive silk fibroin film has potential application prospects in functional memory, sensors, electronic devices and other fields.
  • polypyrrole As the most widely studied conductive polymer, polypyrrole has been widely used in the modification of silk fibroin, including the modification of silk fibers and fabrics, and the in-situ oxidative polymerization of regenerated silk fibroin materials (Sun Donghao. Polypyrrole /Silk fibroin conductive composites preparation and characteristics[J].Silk,2009(04):22-25.) and electrochemical polymerization (Nie Ming,Huang Feng,Wang Zhengao,Fu Rumin,Ning Chengyun.Polypyrrole/ The electrochemical synthesis of polydopamine and its effect on the corrosion resistance of aluminum alloy[J]. Journal of Composite Materials, 2019,36(10):2364-2370) and other different polymerization methods.
  • polyaniline as a conductive polymer has also been reported in the modification of wool, polyester and silk fibroin, including in-situ oxidative polymerization of polyester, wool and other fabrics and silk fibroin (Li Xiaoru. Wet spinning Silk fibroin/polyaniline conductive flexible filament[J].Journal of Textile Science and Engineering,2019,36(01):120-124+170.) and electrochemical polymerization (Zhang Yue. Electrochemistry of polyaniline nanofibers Rapid synthesis and application research[D]. Wuhan University of Technology, 2014)
  • Poly3,4-ethylenedioxythiophene is a new type of conductive polymer, which belongs to a kind of polythiophene. Due to its unique epoxy structure, it has higher conductivity and better stability.
  • the physical coating and impregnation method is currently reported (Wang Dafeng, Study on the preparation and performance of conductive silk by adsorption polymerization [D]. Soochow University, 2010; Wang Dafeng, Xing Tieling, Chen Guoqiang. Preparation of 3,4-ethylenedioxythiophene modified silk and its electrical conductivity[J].Dyeing Auxiliaries,2010,27(07):13-15).
  • the purpose of the present invention is to provide a conductive silk fibroin material and its preparation method and application.
  • the present invention adopts an in-situ chemical modification method to make 3,4-ethylenedioxythiophene under the action of manganese dioxide.
  • In situ polymerization on the surface of the silk fibroin material, the prepared conductive silk fibroin material has good conductivity and biocompatibility.
  • the preparation method of conductive silk fibroin material of the present invention includes the following steps:
  • insoluble silk fibroin material the silk fibroin aqueous solution and small molecule monoalcohol are mixed and formed to obtain a three-dimensional and water-insoluble silk fibroin material.
  • the silk fibroin aqueous solution the silk fibroin The concentration of protein is 30-70mg/mL, the molecular weight of silk fibroin is 8000-14000 Da, and the mass ratio of silk fibroin to small molecule monoalcohol is 100-1000:1;
  • step (3) Surface oxidation of silk fibroin material:
  • the silk fibroin material treated in step (2) is immersed in 0.1-1mol/L (preferably 0.3-0.6mol/L) potassium permanganate aqueous solution at 15-30°C In the process, the silk fibroin material after surface oxidation is obtained after treatment for less than 10 minutes;
  • the small molecule monohydric alcohol is one or more of methanol, ethanol and propanol.
  • the silk fibroin aqueous solution contains high molecular weight silk fibroin, and the preparation method thereof includes the following steps:
  • step (1) it is poured into a mold and molded at room temperature. Because silk fibroin has a certain degree of plasticity, it will not be limited to a certain macroscopic shape. It can be molded into any shape in theory by changing the shape of the molding die.
  • the strong base is sodium hydroxide and/or potassium hydroxide.
  • step (2) the pH value of the aqueous solution of the weak reducing acid and/or the weak reducing acid salt is 4-6.
  • the weak reducing acid is sulfurous acid and/or formic acid; the weak reducing acid salt is sodium bisulfite and/or potassium bisulfite.
  • the peroxide is one or more of ammonium persulfate, sodium perborate, potassium perborate, sodium persulfate and potassium persulfate, and the concentration of the aqueous peroxide solution is 0.1-0.5 mol/L.
  • step (4) the concentration of 3,4-ethylenedioxythiophene is 0.1-0.5 mol/L.
  • step (1) the three-dimensional and water-insoluble silk fibroin material is in the shape of a flat film, and the conductive silk fibroin material produced in step (4) is also in the shape of a flat film.
  • step (4) the reaction is carried out for 1-10 h under shaking conditions.
  • step (4) after the reaction is completed, it further includes the steps of ultrasonically cleaning the obtained conductive silk fibroin material in deionized water for 1-5 minutes, and drying at room temperature for more than 24 hours.
  • the present invention also provides a conductive silk fibroin material prepared by the above preparation method, comprising a three-dimensional and water-insoluble silk fibroin material and a conductive layer grafted on the surface of the silk fibroin material.
  • the conductive layer includes poly 3 , 4-Ethylenedioxythiophene, the surface resistance of the conductive silk fibroin material is 100 ohms-5000 ohms.
  • the conductive silk fibroin material is in the shape of a flat film.
  • the invention also discloses the application of the conductive silk fibroin material prepared by the above method as a flexible electronic device.
  • the flexible electronic device is used to detect human blood sugar level and heartbeat.
  • the preparation principle of the conductive silk fibroin material is as follows:
  • the acid salt quickly removes alkaline substances such as sodium hydroxide on the surface of the silk fibroin membrane and forms a reducing surface.
  • strong alkali activation is to destroy the surface crystalline layer of the silk fibroin membrane, so that the reducing groups such as surface amino groups and hydroxyl groups are exposed on the silk fibroin membrane surface.
  • the potassium permanganate is treated with potassium permanganate solution so that the potassium permanganate can oxidize the reducing groups such as amino groups and hydroxyl groups on the surface of the silk fibroin membrane.
  • the potassium permanganate is reduced to manganese dioxide.
  • Manganese dioxide binds to the surface of the silk fibroin film to form nano-catalytic particles.
  • surface catalytic oxidation grafting was carried out on the surface of silk fibroin membrane.
  • the oxidized silk fibroin film is placed in an aqueous solution of 3,4-ethylenedioxythiophene.
  • the present invention has at least the following advantages:
  • Both silk fibroin and poly3.4-ethylenedioxythiophene have good biocompatibility, and silk fibroin itself can be degraded.
  • 3,4-ethylenedioxythiophene is The surface of the three-dimensional silk fibroin material is polymerized in situ, so that the composite material has good conductivity.
  • the conductive silk fibroin material of the present invention is relatively soft and has good biocompatibility and good electrical conductivity, it is a good flexible biological conductive material and can be used as a material for measuring human blood sugar and heartbeat.
  • Figure 1 is a scanning electron micrograph of the silk fibroin membrane of the present invention before and after treatment.
  • insoluble silk fibroin film refers to "water-insoluble silk fibroin film”.
  • the degummed silk was dissolved in a 9.3mol/L lithium bromide solution at 65 ⁇ 2°C at a bath ratio of 15:100. After the solution obtained by the dissolution is sufficiently cooled, it is dialyzed against deionized water with a cellulose dialysis membrane (8000-14000 Da) for 3 days to obtain an aqueous solution of high molecular weight silk fibroin.
  • the silk fibroin membrane after the surface treatment is immersed in a 0.5mol/L potassium permanganate aqueous solution at room temperature for 1 minute.
  • the oxidized silk fibroin film was immersed in an aqueous solution of ammonium persulfate with a concentration of 0.2 mol/L, 3,4-ethylenedioxythiophene was added to make the concentration reach 0.3 mol/L, and the reaction was shaken at 25° C. for 6 hours.
  • the silk fibroin membrane was taken out, rinsed with deionized water, and then vibrated for 2 minutes in an ultrasonic cleaner, and dried at room temperature for more than 24 hours to obtain a conductive silk fibroin membrane with a resistance of 3800 ohms.
  • the degummed silk was dissolved in a 9.3mol/L lithium bromide solution at 65 ⁇ 2°C at a bath ratio of 15:100. After the solution obtained by the dissolution is sufficiently cooled, it is dialyzed against deionized water with a cellulose dialysis membrane (8000-14000 Da) for 3 days to obtain an aqueous solution of high molecular weight silk fibroin.
  • the silk fibroin membrane after the surface treatment is immersed in a 0.5mol/L potassium permanganate aqueous solution at room temperature for 1 minute.
  • the oxidized silk fibroin film was immersed in an aqueous solution of ammonium persulfate with a concentration of 0.2 mol/L, 3,4-ethylenedioxythiophene was added to make the concentration reach 0.3 mol/L, and the reaction was shaken at 25° C. for 6 hours.
  • the silk fibroin membrane was taken out, rinsed with deionized water, and then vibrated for 2 minutes in an ultrasonic cleaner, and dried at room temperature for more than 24 hours to obtain a conductive silk fibroin membrane with a resistance of 3500 ohms.
  • the degummed silk was dissolved in a 9.3mol/L lithium bromide solution at 65 ⁇ 2°C at a bath ratio of 15:100. After the solution obtained by the dissolution is sufficiently cooled, it is dialyzed against deionized water with a cellulose dialysis membrane (8000-14000 Da) for 3 days to obtain an aqueous solution of high molecular weight silk fibroin.
  • the silk fibroin membrane after the surface treatment is immersed in a 0.4mol/L potassium permanganate aqueous solution at room temperature for 1 minute.
  • the oxidized silk fibroin film was immersed in a potassium persulfate aqueous solution with a concentration of 0.2 mol/L, 3,4-ethylenedioxythiophene was added to make the concentration reach 0.2 mol/L, and the reaction was shaken at 25° C. for 3 hours.
  • the silk fibroin membrane was taken out, rinsed with deionized water, and then vibrated for 2 minutes in an ultrasonic cleaner, and dried at room temperature for more than 24 hours to obtain a conductive silk fibroin membrane with a resistance of 3000 ohms.
  • the degummed silk was dissolved in a 9.3mol/L lithium bromide solution at 65 ⁇ 2°C at a bath ratio of 15:100. After the solution obtained by the dissolution is sufficiently cooled, it is dialyzed against deionized water with a cellulose dialysis membrane (8000-14000 Da) for 3 days to obtain an aqueous solution of high molecular weight silk fibroin.
  • the silk fibroin film after surface treatment is immersed in a 0.6mol/L potassium permanganate aqueous solution at room temperature for 1 minute.
  • the oxidized silk fibroin film was immersed in an aqueous solution of ammonium persulfate with a concentration of 0.2 mol/L, 3,4-ethylenedioxythiophene was added to make the concentration reach 0.3 mol/L, and the reaction was shaken at 25°C for 3 hours.
  • the silk fibroin membrane was taken out, rinsed with deionized water, and then vibrated for 2 minutes in an ultrasonic cleaner, and dried at room temperature for more than 24 hours to obtain a conductive silk fibroin membrane with a resistance of 4300 ohms.
  • the degummed silk was dissolved in a 9.3mol/L lithium bromide solution at 65 ⁇ 2°C at a bath ratio of 15:100. After the solution obtained by the dissolution is sufficiently cooled, it is dialyzed against deionized water with a cellulose dialysis membrane (8000-14000 Da) for 3 days to obtain an aqueous solution of high molecular weight silk fibroin.
  • the silk fibroin membrane after the surface treatment is immersed in a 0.5mol/L potassium permanganate aqueous solution at room temperature for 1 minute.
  • the oxidized silk fibroin film was immersed in an aqueous solution of ammonium persulfate with a concentration of 0.2 mol/L, 3,4-ethylenedioxythiophene was added to make the concentration reach 0.3 mol/L, and the reaction was shaken at 25°C for 3 hours.
  • the silk fibroin membrane was taken out, rinsed with deionized water, and then vibrated for 2 minutes in an ultrasonic cleaner, and dried at room temperature for more than 24 hours to obtain a conductive silk fibroin membrane with a resistance of 3500 ohms.
  • the degummed silk was dissolved in a 9.3mol/L lithium bromide solution at 65 ⁇ 2°C at a bath ratio of 15:100. After the solution obtained by the dissolution is sufficiently cooled, it is dialyzed against deionized water with a cellulose dialysis membrane (8000-14000 Da) for 3 days to obtain an aqueous solution of high molecular weight silk fibroin.
  • the silk fibroin membrane after the surface treatment is immersed in a 0.2mol/L potassium permanganate aqueous solution at room temperature for 1 minute.
  • the oxidized silk fibroin film was immersed in an aqueous sodium persulfate solution with a concentration of 0.2 mol/L, 3,4-ethylenedioxythiophene was added to make the concentration reach 0.3 mol/L, and the reaction was shaken at 25°C for 3 hours.
  • the silk fibroin membrane was taken out, rinsed with deionized water, and then vibrated for 2 minutes in an ultrasonic cleaner, and then taken out and dried at room temperature for more than 24 hours to obtain a conductive silk fibroin membrane with a resistance of 9800 ohms.
  • the degummed silk was dissolved in a 9.3mol/L lithium bromide solution at 65 ⁇ 2°C at a bath ratio of 15:100. After the solution obtained by the dissolution is sufficiently cooled, it is dialyzed against deionized water with a cellulose dialysis membrane (8000-14000 Da) for 3 days to obtain an aqueous solution of high molecular weight silk fibroin.
  • the silk fibroin membrane after the surface treatment is immersed in a 0.5mol/L potassium permanganate aqueous solution at room temperature for 45 seconds.
  • the oxidized silk fibroin film was immersed in a sodium perborate aqueous solution with a concentration of 0.2 mol/L, 3,4-ethylenedioxythiophene was added to make the concentration reach 0.3 mol/L, and the reaction was shaken at 25°C for 3 hours.
  • the silk fibroin membrane was taken out, rinsed with deionized water first, and then vibrated for 2 minutes in an ultrasonic cleaner, and dried at room temperature for more than 24 hours to obtain a conductive silk fibroin membrane with a resistance of 1500 ohms.
  • the degummed silk was dissolved in a 9.3mol/L lithium bromide solution at 65 ⁇ 2°C at a bath ratio of 15:100. After the solution obtained by the dissolution is sufficiently cooled, it is dialyzed against deionized water with a cellulose dialysis membrane (8000-14000 Da) for 3 days to obtain an aqueous solution of high molecular weight silk fibroin.
  • the silk fibroin membrane after the surface treatment is immersed in a 1mol/L potassium permanganate aqueous solution at room temperature for 30 seconds.
  • the oxidized silk fibroin film was immersed in an aqueous solution of ammonium persulfate with a concentration of 0.2 mol/L, 3,4-ethylenedioxythiophene was added to make the concentration reach 0.3 mol/L, and the reaction was shaken at 25°C for 3 hours.
  • the silk fibroin membrane was taken out, rinsed with deionized water, and then vibrated for 2 minutes in an ultrasonic cleaner, and dried at room temperature for more than 24 hours to obtain a conductive silk fibroin membrane with a resistance of 720 ohms.
  • the degummed silk was dissolved in a 9.3mol/L lithium bromide solution at 65 ⁇ 2°C at a bath ratio of 15:100. After the solution obtained by the dissolution is sufficiently cooled, it is dialyzed against deionized water with a cellulose dialysis membrane (8000-14000 Da) for 3 days to obtain an aqueous solution of high molecular weight silk fibroin.
  • the silk fibroin membrane after the surface treatment is immersed in a 0.8mol/L potassium permanganate aqueous solution at room temperature for 30 seconds.
  • the oxidized silk fibroin film was immersed in a potassium perborate aqueous solution with a concentration of 0.2 mol/L, 3,4-ethylenedioxythiophene was added to make the concentration reach 0.3 mol/L, and the reaction was shaken at 25° C. for 4 hours.
  • the silk fibroin membrane was taken out, rinsed with deionized water, and then vibrated for 2 minutes in an ultrasonic cleaner, and dried at room temperature for more than 24 hours to obtain a conductive silk fibroin membrane with a resistance of 4200 ohms.
  • the degummed silk was dissolved in a 9.3mol/L lithium bromide solution at 65 ⁇ 2°C at a bath ratio of 15:100. After the solution obtained by the dissolution is sufficiently cooled, it is dialyzed against deionized water with a cellulose dialysis membrane (8000-14000 Da) for 3 days to obtain an aqueous solution of high molecular weight silk fibroin.
  • the silk fibroin membrane after the surface treatment is immersed in a 1mol/L potassium permanganate aqueous solution at room temperature for 30 seconds.
  • the oxidized silk fibroin film was immersed in an aqueous solution of ammonium persulfate with a concentration of 0.2 mol/L, 3,4-ethylenedioxythiophene was added to make the concentration reach 0.2 mol/L, and the reaction was shaken at 25° C. for 5 hours.
  • the silk fibroin membrane was taken out, rinsed with deionized water, and then vibrated for 2 minutes in an ultrasonic cleaner, and then taken out and dried at room temperature for more than 24 hours to obtain a conductive silk fibroin membrane with a resistance of 1200 ohms.
  • Example Square resistance Example one 3800 ohm
  • Example two 3500 ohm Example three 3000 ohm
  • Example four 4300 ohm Example five 3500 ohm
  • Example Six 9800 ohm Example Seven 1500 ohm
  • Example 9 4200 ohm Example ten 1200 ohm
  • Figure 1 is a scanning electron micrograph of the silk fibroin film in Example 1 of the present invention before and after the treatment.
  • Figure 1a is the smooth surface before the treatment;
  • Figure 1b is the 3,4-ethylenedioxythiophene treatment after the surface is deposited.
  • a conductive layer is provided.

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Abstract

一种导电丝素材料的制备方法，制备方法包括以下步骤：(1)高分子量丝素蛋白溶液的制备；(2)不溶性丝素蛋白材料的制备；(3)丝素蛋白材料的表面处理；(4)丝素蛋白材料的氧化；(5)3，4-乙烯二氧噻吩在接枝改性后的丝素蛋白材料表面进行原位氧化聚合。

Description

导电丝素材料及其制备方法和应用 技术领域
本发明涉及导电材料，尤其涉及一种导电丝素材料及其制备方法和应用。
背景技术
丝素蛋白可以作为生物医学应用的材料，因为它具有优异的生物相容性，高表面质量比，良好的机械性能以及较好的成形能力，以及良好的生物相容性和缓慢的生物降解性，具有很大的应用潜力。
相较于传统导电材料(无机半导体材料、金属材料)，新兴发展的导电高聚物兼具高分子材料和导电材料的特点，具有更佳生物相容性及柔性，使用导电高聚物对丝素蛋白材料进行导电改性吸引了很多学者的关注。
导电丝素膜作为一类新颖的功能材料，具有独特的物理化学性质，因能对外部的特定刺激产生响应而具有一定的智能性。导电丝素膜在功能性记忆，传感器，电子器械等领域具有潜在的应用前景。
聚吡咯作为研究最为广泛的导电高分子，已有大量应用于丝素蛋白的改性工作，包括对真丝纤维、面料的改性以及对再生丝素蛋白材料的原位氧化聚合(孙东豪.聚吡咯/丝素导电复合材料的制备及特性[J].丝绸,2009(04):22-25.)及电化学聚合(聂铭,黄丰,王珍高,付如民,宁成云.聚吡咯/聚多巴胺的电化学合成及其对铝合金耐蚀性的影响[J].复合材料学报,2019,36(10):2364-2370)等不同聚合方法的改性。
采用聚苯胺作为导电高分子的，用在羊毛、涤纶以及丝素蛋白改性工作中同样已有报道，包括对涤纶、羊毛等织物以及对丝素蛋白的原位氧化聚合(李晓茹.湿法纺制丝素蛋白/聚苯胺导电柔性长丝[J].纺织科学与工程学报,2019,36(01):120-124+170.)以及电化学聚合(张悦.聚苯胺纳米纤维的电化学快速合成与应用研究[D].武汉理工大学,2014)
聚3,4-乙烯二氧噻吩是一种新型的导电高分子，属于聚噻吩的一种，由于其自身独特的环氧结构使其拥有较高电导率的同时拥有比较好的稳定性，关于对聚3,4-乙烯二氧噻吩与蚕丝等织物的复合，目前报道的主要是物理涂浸法(汪大峰，吸附聚合法制备导电真丝及其性能研究[D].苏州大学,2010；汪大峰,邢铁玲,陈国强.3,4-乙烯二氧噻吩改性真丝的制备及其导电性能的研究[J].印染助剂,2010,27(07):13-15)。但是，目前尚未见到有关于聚3,4-乙烯二氧噻吩系列导电高聚物对丝素蛋白进行原位化学导电聚合改性的工艺方法。
发明内容
为解决上述技术问题，本发明的目的是提供一种导电丝素材料及其制备方法和应用，本发明采用原位化学改性法，使3,4-乙烯二氧噻吩在二氧化锰的作用下在丝素蛋白材料表面原位聚合，所制备的导电丝素材料具有良好的导电性和生物相容性。
本发明的一种导电丝素材料的制备方法，包括以下步骤：
(1)不溶性丝素蛋白材料的制备：将丝素蛋白水溶液与小分子一元醇混匀后成型，得到三维立体状且不溶于水的丝素蛋白材料，其中，丝素蛋白水溶液中，丝素蛋白的浓度为30-70mg/mL，丝素蛋白的分子量为8000-14000Da，丝素蛋白与小分子一元醇的质量比为100-1000:1；
(2)丝素蛋白材料的表面处理：将丝素蛋白材料浸入pH＞14的强碱水溶液中，处理0.1-5秒后取出，再浸入0.1-1mol/L的还原性弱酸和/或还原性弱酸盐的水溶液中处理1-10分钟；
(3)丝素蛋白材料的表面氧化：将经步骤(2)处理后的丝素蛋白材料于15-30℃浸入0.1-1mol/L(优选为0.3-0.6mol/L)高锰酸钾水溶液中，处理10分钟以下，得到表面氧化后的丝素蛋白材料；
(4)丝素蛋白材料表面的原位氧化聚合：将表面氧化后的丝素蛋白材料浸入过氧化物水溶液中，然后向其中加入3,4-乙烯二氧噻吩并在20-30℃下反应，以使得3,4-乙烯二氧噻吩在丝素蛋白材料表面发生聚合，反应完全后得到导电丝素材料。
进一步地，在步骤(1)中，小分子一元醇为甲醇、乙醇和丙醇中的一种或几种。
进一步地，在步骤(1)中，丝素蛋白水溶液中含有高分子了的丝素蛋白，其制备方法包括以下步骤：
将新鲜蚕茧取出蚕蛹后，以1：100的浴比加入pH＝9-9.5的NaHCO 3/Na 2CO 3缓冲溶液中，在微沸状态下处理30min后洗净后，再重复上述操作3次；然后洗净烘干，得到脱胶蚕丝。将脱胶蚕丝以浴比为15：100加入65±2℃的9.3mol/L溴化锂水溶液中溶解。溶解获得的溶液充分冷却后，用纤维素透析膜(8000-14000Da)在去离子水中透析3天获得丝素蛋白水溶液。
进一步地，在步骤(1)中，在模具中浇注成型，并在室温下成型。由于丝素蛋白具有一定的可塑能力，不会局限于某种宏观的形状，改变成型模具的形状，理论上能够成型为任何形状。
进一步地，在步骤(2)中，强碱为氢氧化钠和/或氢氧化钾。
进一步地，在步骤(2)中，还原性弱酸和/或还原性弱酸盐的水溶液的pH值为4-6。
进一步地，在步骤(2)中，还原性弱酸为亚硫酸和/或甲酸；还原性弱酸盐为亚硫酸氢钠和/或亚硫酸氢钾。
进一步地，在步骤(4)中，过氧化物为过硫酸铵、过硼酸钠、过硼酸钾、过硫酸钠和过硫酸钾中的一种或几种，过氧化物水溶液浓度为0.1-0.5mol/L。
进一步地，在步骤(4)中，3,4-乙烯二氧噻吩的浓度为0.1-0.5mol/L。
进一步地，在步骤(1)中，三维立体状且不溶于水的丝素蛋白材料呈平面膜状，步骤(4)所制成的导电丝素材料同样呈平面膜状。
进一步地，在步骤(4)中，在振荡条件下反应1-10h。
进一步地，在步骤(4)中，反应完全后还包括将得到的导电丝素材料在去离子水中超声清洗1-5分钟，并在室温下干燥24h以上的步骤。
本发明还提供了一种采用上述制备方法所制备的导电丝素材料，包括三维立体状且不溶于水的丝素蛋白材料及接枝于丝素蛋白材料表面的导电层，导电层包括聚3,4-乙烯二氧噻吩，导电丝素材料的表面方阻为100欧姆-5000欧姆。
进一步地，导电丝素材料呈平面膜状。
本发明还公开了上述方法制备的导电丝素材料作为柔性电子器件的应用。
进一步地，该柔性电子器件用于检测人体血糖水平和心跳。
本发明中，以膜状的导电丝素材料为例，导电丝素材料的制备原理如下：
将少量一元醇与丝素蛋白溶液共混塑化而形成的不溶于水的丝素蛋白膜，并将丝素蛋白膜用强碱溶液进行活化处理，然后浸入还原性弱酸和/或还原性弱酸盐中快速去除丝素蛋白膜表面的氢氧化钠等碱性物质，并形成还原性的表面。强碱活化的目的是为了破坏丝素蛋白膜表面结晶层，使得表面氨基、羟基等还原性基团暴露在丝素蛋白膜表面。然后用高锰酸钾溶液处理，使得高锰酸钾能够氧化丝素蛋白膜表面氨基、羟基等还原性基团，在此过程中，高锰酸钾被还原成二氧化锰。二氧化锰结合在丝素蛋白膜的表面，形成纳米催化颗粒。随后在丝素蛋白膜表面进行表面催化氧化接枝。将氧化后的丝素蛋白膜置于3,4-乙烯二氧噻吩的水溶液中，由于3.4-乙烯二氧噻吩在过氧化物氧化剂的作用下失去电子，形成阳离子自由基，而丝素蛋白膜中的肽键(-CO-NH-)的氧和氮原子具有部分负电荷，因此基于静电力作用游离的3,4-乙烯二氧噻吩单体阳离子会被带负电荷的丝素蛋白膜大分子吸引而聚集在材料表面，进而在丝素蛋白膜表面通过静电力结合的单体阳离子作为活性种，在丝素蛋白膜表面的二氧化锰的催化作用下引发原位聚合，最终氧化聚合形成聚3.4-乙烯二氧噻吩，形成导电层。
借由上述方案，本发明至少具有以下优点：
丝素蛋白与聚3.4-乙烯二氧噻吩均具有良好的生物相容性，且丝素蛋白本身就能够降解，通过二氧化锰的原位催化聚合反应，将3,4-乙烯二氧噻吩在三维立体状的丝素蛋白材料表面进行原位聚合，使得复合后的材料具备良好的导电性。
由于本发明导电丝素材料较为柔软又具有很好的生物相容性及良好的导电性能，因此是很好的柔性生物导电材料，可用作测量人体血糖和心跳的材料。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
图1是本发明丝素蛋白膜在处理前后的扫描电镜图。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
如无特殊说明，本发明中，“不溶性的丝素蛋白膜”均指的是“不溶于水的丝素蛋白膜”。
实施例一
丝素蛋白膜的制备过程：新鲜蚕茧取出蚕蛹后，以1:100的浴比加入pH＝9-9.5的NaHCO 3/Na 2CO 3缓冲溶液中，加热，调节溶液状态为微沸，处理30min后用去离子水洗涤干净，再重复上述操作3次；充分洗净后，将蚕丝扯开铺平，放入60℃烘箱中烘干。脱胶后的蚕丝以浴比为15：100加入65±2℃的9.3mol/L溴化锂溶液中溶解。溶解获得的溶液充分冷却后，用纤维素透析膜(8000-14000Da)在去离子水中透析3天获得高分子量丝素蛋白水溶液。
调节高分子量丝素蛋白水溶液浓度为50毫克/毫升，向其中加入乙醇，其中乙醇与丝素蛋白的质量比为1:100，混合均匀，将得到的混合液浇注到模具中，室温下成膜，获得不溶性的丝素蛋白膜。
将不溶性的丝素蛋白膜浸入氢氧化钠水溶液中，其浓度为5摩尔/升，处理1秒后取出，再将丝素蛋白膜浸入0.5摩尔/升的亚硫酸氢钠水溶液中，处理3分钟，取出用去离子水漂洗3次。
将经过表面处理后的丝素蛋白膜，于常温下浸入0.5mol/L高锰酸钾水溶液中，处理1分钟。将表面氧化后的丝素蛋白膜浸入过硫酸铵水溶液中，其浓度为0.2摩尔/升，加入3,4-乙烯二氧噻吩，使浓度达到0.3mol/L，在25℃下振荡反应6h。反应结束取出丝素蛋白膜，先用 去离子水冲洗，然后再超声波清洗仪中振动清洗2分钟，取出在室温下干燥24h以上，得到导电丝素蛋白膜，其电阻为3800欧姆。
实施例二
丝素蛋白膜的制备过程：新鲜蚕茧取出蚕蛹后，以1：100的浴比加入pH＝9-9.5的NaHCO 3/Na 2CO 3缓冲溶液中，加热，调节溶液状态为微沸，处理30min后用去离子水洗涤干净，再重复上述操作3次；充分洗净后，将蚕丝扯开铺平，放入60℃烘箱中烘干。脱胶后的蚕丝以浴比为15：100加入65±2℃的9.3mol/L溴化锂溶液中溶解。溶解获得的溶液充分冷却后，用纤维素透析膜(8000-14000Da)在去离子水中透析3天获得高分子量丝素蛋白水溶液。
调节高分子量丝素蛋白水溶液浓度为50毫克/毫升，向其中加入甲醇，其中甲醇与丝素蛋白的质量比为1:500，混合均匀，将得到的混合液浇注到模具中，室温下成膜，获得不溶性的丝素蛋白膜。
将不溶性的丝素蛋白膜浸入氢氧化钠水溶液中，其浓度为6摩尔/升，处理2秒后取出，再将丝素蛋白膜浸入0.5摩尔/升的亚硫酸氢钠水溶液中，处理3分钟，取出用去离子水漂洗3次。
将经过表面处理后的丝素蛋白膜，于常温下浸入0.5mol/L高锰酸钾水溶液中，处理1分钟。将表面氧化后的丝素蛋白膜浸入过硫酸铵水溶液中，其浓度为0.2摩尔/升，加入3,4-乙烯二氧噻吩，使浓度达到0.3mol/L，在25℃下振荡反应6h。反应结束取出丝素蛋白膜，先用去离子水冲洗，然后再超声波清洗仪中振动清洗2分钟，取出在室温下干燥24h以上，得到导电丝素蛋白膜，其电阻为3500欧姆。
实施例三
丝素蛋白膜的制备过程：新鲜蚕茧取出蚕蛹后，以1：100的浴比加入pH＝9-9.5的NaHCO 3/Na 2CO 3缓冲溶液中，加热，调节溶液状态为微沸，处理30min后用去离子水洗涤干净，再重复上述操作3次；充分洗净后，将蚕丝扯开铺平，放入60℃烘箱中烘干。脱胶后的蚕丝以浴比为15：100加入65±2℃的9.3mol/L溴化锂溶液中溶解。溶解获得的溶液充分冷却后，用纤维素透析膜(8000-14000Da)在去离子水中透析3天获得高分子量丝素蛋白水溶液。
调节高分子量丝素蛋白水溶液浓度为50毫克/毫升，向其中加入甲醇，其中甲醇与丝素 蛋白的质量比为1:600，混合均匀，将得到的混合液浇注到模具中，室温下成膜，获得不溶性的丝素蛋白膜。
将不溶性的丝素蛋白膜浸入氢氧化钠水溶液中，其浓度为5摩尔/升，处理1秒后取出，再将丝素蛋白膜浸入0.5摩尔/升的亚硫酸氢钠水溶液中，处理3分钟，取出用去离子水漂洗3次。
将经过表面处理后的丝素蛋白膜，于常温下浸入0.4mol/L高锰酸钾水溶液中，处理1分钟。将表面氧化后的丝素蛋白膜浸入过硫酸钾水溶液中，其浓度为0.2摩尔/升，加入3,4-乙烯二氧噻吩，使浓度达到0.2mol/L，在25℃下振荡反应3h。反应结束取出丝素蛋白膜，先用去离子水冲洗，然后再超声波清洗仪中振动清洗2分钟，取出在室温下干燥24h以上，得到导电丝素蛋白膜，其电阻为3000欧姆。
实施例四
丝素蛋白膜的制备过程：新鲜蚕茧取出蚕蛹后，以1：100的浴比加入pH＝9-9.5的NaHCO 3/Na 2CO 3缓冲溶液中，加热，调节溶液状态为微沸，处理30min后用去离子水洗涤干净，再重复上述操作3次；充分洗净后，将蚕丝扯开铺平，放入60℃烘箱中烘干。脱胶后的蚕丝以浴比为15：100加入65±2℃的9.3mol/L溴化锂溶液中溶解。溶解获得的溶液充分冷却后，用纤维素透析膜(8000-14000Da)在去离子水中透析3天获得高分子量丝素蛋白水溶液。
调节高分子量丝素蛋白水溶液浓度为30毫克/毫升，向其中加入丙醇，其中丙醇与丝素蛋白的质量比为1:100，混合均匀，将得到的混合液浇注到模具中，室温下成膜，获得不溶性的丝素蛋白膜。
将不溶性的丝素蛋白膜浸入氢氧化钠水溶液中，其浓度为5摩尔/升，处理2秒后取出，再将丝素蛋白膜浸入0.1摩尔/升的甲酸水溶液中，处理3分钟，取出用去离子水漂洗3次。
将经过表面处理后的丝素蛋白膜，于常温下浸入0.6mol/L高锰酸钾水溶液中，处理1分钟。将表面氧化后的丝素蛋白膜浸入过硫酸铵水溶液中，其浓度为0.2摩尔/升，加入3,4-乙烯二氧噻吩，使浓度达到0.3mol/L，在25℃下振荡反应3h。反应结束取出丝素蛋白膜，先用去离子水冲洗，然后再超声波清洗仪中振动清洗2分钟，取出在室温下干燥24h以上，得到导电丝素蛋白膜，其电阻为4300欧姆。
实施例五
丝素蛋白膜的制备过程：新鲜蚕茧取出蚕蛹后，以1：100的浴比加入pH＝9-9.5的NaHCO 3/Na 2CO 3缓冲溶液中，加热，调节溶液状态为微沸，处理30min后用去离子水洗涤干 净，再重复上述操作3次；充分洗净后，将蚕丝扯开铺平，放入60℃烘箱中烘干。脱胶后的蚕丝以浴比为15：100加入65±2℃的9.3mol/L溴化锂溶液中溶解。溶解获得的溶液充分冷却后，用纤维素透析膜(8000-14000Da)在去离子水中透析3天获得高分子量丝素蛋白水溶液。
调节高分子量丝素蛋白水溶液浓度为60毫克/毫升，向其中加入甲醇，其中甲醇与丝素蛋白的质量比为1:1000，混合均匀，将得到的混合液浇注到模具中，室温下成膜，获得不溶性的丝素蛋白膜。
将不溶性的丝素蛋白膜浸入氢氧化钠水溶液中，其浓度为5摩尔/升，处理1秒后取出，再将丝素蛋白膜浸入1摩尔/升的亚硫酸氢钠水溶液中，处理3分钟，取出用去离子水漂洗3次。
将经过表面处理后的丝素蛋白膜，于常温下浸入0.5mol/L高锰酸钾水溶液中，处理1分钟。将表面氧化后的丝素蛋白膜浸入过硫酸铵水溶液中，其浓度为0.2摩尔/升，加入3,4-乙烯二氧噻吩，使浓度达到0.3mol/L，在25℃下振荡反应3h。反应结束取出丝素蛋白膜，先用去离子水冲洗，然后再超声波清洗仪中振动清洗2分钟，取出在室温下干燥24h以上，得到导电丝素蛋白膜，其电阻为3500欧姆。
实施例六
丝素蛋白膜的制备过程：新鲜蚕茧取出蚕蛹后，以1：100的浴比加入pH＝9-9.5的NaHCO 3/Na 2CO 3缓冲溶液中，加热，调节溶液状态为微沸，处理30min后用去离子水洗涤干净，再重复上述操作3次；充分洗净后，将蚕丝扯开铺平，放入60℃烘箱中烘干。脱胶后的蚕丝以浴比为15：100加入65±2℃的9.3mol/L溴化锂溶液中溶解。溶解获得的溶液充分冷却后，用纤维素透析膜(8000-14000Da)在去离子水中透析3天获得高分子量丝素蛋白水溶液。
调节高分子量丝素蛋白水溶液浓度为30毫克/毫升，向其中加入异丙醇，其中异丙醇与丝素蛋白的质量比为1:100，混合均匀，将得到的混合液浇注到模具中，室温下成膜，获得不溶性的丝素蛋白膜。
将不溶性的丝素蛋白膜浸入氢氧化钠水溶液中，其浓度为5摩尔/升，处理0.5秒后取出，再将丝素蛋白膜浸入1摩尔/升的亚硫酸氢钠水溶液中，处理4分钟，取出用去离子水漂洗3次。
将经过表面处理后的丝素蛋白膜，于常温下浸入0.2mol/L高锰酸钾水溶液中，处理1分钟。将表面氧化后的丝素蛋白膜浸入过硫酸钠水溶液中，其浓度为0.2摩尔/升，加入3,4-乙 烯二氧噻吩，使浓度达到0.3mol/L，在25℃下振荡反应3h。反应结束取出丝素蛋白膜，先用去离子水冲洗，然后再超声波清洗仪中振动清洗2分钟，取出在室温下干燥24h以上，得到导电丝素蛋白膜，其电阻为9800欧姆。
实施例七
丝素蛋白膜的制备过程：新鲜蚕茧取出蚕蛹后，以1：100的浴比加入pH＝9-9.5的NaHCO 3/Na 2CO 3缓冲溶液中，加热，调节溶液状态为微沸，处理30min后用去离子水洗涤干净，再重复上述操作3次；充分洗净后，将蚕丝扯开铺平，放入60℃烘箱中烘干。脱胶后的蚕丝以浴比为15：100加入65±2℃的9.3mol/L溴化锂溶液中溶解。溶解获得的溶液充分冷却后，用纤维素透析膜(8000-14000Da)在去离子水中透析3天获得高分子量丝素蛋白水溶液。
调节高分子量丝素蛋白水溶液浓度为40毫克/毫升，向其中加入甲醇，其中甲醇与丝素蛋白的质量比为1:800，混合均匀，将得到的混合液浇注到模具中，室温下成膜，获得不溶性的丝素蛋白膜。
将不溶性的丝素蛋白膜浸入氢氧化钠水溶液中，其浓度为5摩尔/升，处理3秒后取出，再将丝素蛋白膜浸入0.7摩尔/升的亚硫酸氢钠水溶液中，处理4分钟，取出用去离子水漂洗3次。
将经过表面处理后的丝素蛋白膜，于常温下浸入0.5mol/L高锰酸钾水溶液中，处理45秒钟。将表面氧化后的丝素蛋白膜浸入过硼酸钠水溶液中，其浓度为0.2摩尔/升，加入3,4-乙烯二氧噻吩，使浓度达到0.3mol/L，在25℃下振荡反应3h。反应结束取出丝素蛋白膜，先用去离子水冲洗，然后再超声波清洗仪中振动清洗2分钟，取出在室温下干燥24h以上，得到导电丝素蛋白膜，其电阻为1500欧姆。
实施例八
丝素蛋白膜的制备过程：新鲜蚕茧取出蚕蛹后，以1：100的浴比加入pH＝9-9.5的NaHCO 3/Na 2CO 3缓冲溶液中，加热，调节溶液状态为微沸，处理30min后用去离子水洗涤干净，再重复上述操作3次；充分洗净后，将蚕丝扯开铺平，放入60℃烘箱中烘干。脱胶后的蚕丝以浴比为15：100加入65±2℃的9.3mol/L溴化锂溶液中溶解。溶解获得的溶液充分冷却后，用纤维素透析膜(8000-14000Da)在去离子水中透析3天获得高分子量丝素蛋白水溶液。
调节高分子量丝素蛋白水溶液浓度为45毫克/毫升，向其中加入甲醇，其中甲醇与丝素蛋白的质量比为1:900，混合均匀，将得到的混合液浇注到模具中，室温下成膜，获得不溶性 的丝素蛋白膜。
将不溶性的丝素蛋白膜浸入氢氧化钠水溶液中，其浓度为5摩尔/升，处理1秒后取出，再将丝素蛋白膜浸入1摩尔/升的亚硫酸水溶液中，处理3分钟，取出用去离子水漂洗3次。
将经过表面处理后的丝素蛋白膜，于常温下浸入1mol/L高锰酸钾水溶液中，处理30秒钟。将表面氧化后的丝素蛋白膜浸入过硫酸铵水溶液中，其浓度为0.2摩尔/升，加入3,4-乙烯二氧噻吩，使浓度达到0.3mol/L，在25℃下振荡反应3h。反应结束取出丝素蛋白膜，先用去离子水冲洗，然后再超声波清洗仪中振动清洗2分钟，取出在室温下干燥24h以上，得到导电丝素蛋白膜，其电阻为720欧姆。
实施例九
丝素蛋白膜的制备过程：新鲜蚕茧取出蚕蛹后，以1：100的浴比加入pH＝9-9.5的NaHCO 3/Na 2CO 3缓冲溶液中，加热，调节溶液状态为微沸，处理30min后用去离子水洗涤干净，再重复上述操作3次；充分洗净后，将蚕丝扯开铺平，放入60℃烘箱中烘干。脱胶后的蚕丝以浴比为15：100加入65±2℃的9.3mol/L溴化锂溶液中溶解。溶解获得的溶液充分冷却后，用纤维素透析膜(8000-14000Da)在去离子水中透析3天获得高分子量丝素蛋白水溶液。
调节高分子量丝素蛋白水溶液浓度为50毫克/毫升，向其中加入甲醇，其中甲醇与丝素蛋白的质量比为1:700，混合均匀，将得到的混合液浇注到模具中，室温下成膜，获得不溶性的丝素蛋白膜。
将不溶性的丝素蛋白膜浸入氢氧化钠水溶液中，其浓度为4摩尔/升，处理4秒后取出，再将丝素蛋白膜浸入0.85摩尔/升的亚硫酸氢钾水溶液中，处理4分钟，取出用去离子水漂洗3次。
将经过表面处理后的丝素蛋白膜，于常温下浸入0.8mol/L高锰酸钾水溶液中，处理30秒钟。将表面氧化后的丝素蛋白膜浸入过硼酸钾水溶液中，其浓度为0.2摩尔/升，加入3,4-乙烯二氧噻吩，使浓度达到0.3mol/L，在25℃下振荡反应4h。反应结束取出丝素蛋白膜，先用去离子水冲洗，然后再超声波清洗仪中振动清洗2分钟，取出在室温下干燥24h以上，得到导电丝素蛋白膜，其电阻为4200欧姆。
实施例十
丝素蛋白膜的制备过程：新鲜蚕茧取出蚕蛹后，以1：100的浴比加入pH＝9-9.5的NaHCO 3/Na 2CO 3缓冲溶液中，加热，调节溶液状态为微沸，处理30min后用去离子水洗涤干净，再重复上述操作3次；充分洗净后，将蚕丝扯开铺平，放入60℃烘箱中烘干。脱胶后的 蚕丝以浴比为15：100加入65±2℃的9.3mol/L溴化锂溶液中溶解。溶解获得的溶液充分冷却后，用纤维素透析膜(8000-14000Da)在去离子水中透析3天获得高分子量丝素蛋白水溶液。
调节高分子量丝素蛋白水溶液浓度为35毫克/毫升，向其中加入甲醇，其中乙醇与丝素蛋白的质量比为1:300，混合均匀，将得到的混合液浇注到模具中，室温下成膜，获得不溶性的丝素蛋白膜。
将不溶性的丝素蛋白膜浸入氢氧化钠水溶液中，其浓度为7摩尔/升，处理0.5秒后取出，再将丝素蛋白膜浸入1摩尔/升的亚硫酸氢钾水溶液中，处理3分钟，取出用去离子水漂洗3次。
将经过表面处理后的丝素蛋白膜，于常温下浸入1mol/L高锰酸钾水溶液中，处理30秒钟。将表面氧化后的丝素蛋白膜浸入过硫酸铵水溶液中，其浓度为0.2摩尔/升，加入3,4-乙烯二氧噻吩，使浓度达到0.2mol/L，在25℃下振荡反应5h。反应结束取出丝素蛋白膜，先用去离子水冲洗，然后再超声波清洗仪中振动清洗2分钟，取出在室温下干燥24h以上，得到导电丝素蛋白膜，其电阻为1200欧姆。
以上各实施例中所制备的导电丝素蛋白膜的方阻汇总结果见表一。
表一 不同导电丝素蛋白膜的方阻
实施例 方阻
实施例一 3800欧姆
实施例二 3500欧姆
实施例三 3000欧姆
实施例四 4300欧姆
实施例五 3500欧姆
实施例六 9800欧姆
实施例七 1500欧姆
实施例八 720欧姆
实施例九 4200欧姆
实施例十 1200欧姆
图1是本发明实施例1中丝素蛋白膜在处理前后的扫描电镜图，图1a为处理前，其表面光滑；图1b为使用3,4-乙烯二氧噻吩处理后，其表面沉积了一层导电层。
以上仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的 普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。

Claims (10)

  1. 一种导电丝素材料的制备方法，其特征在于，包括以下步骤：
    (1)将丝素蛋白水溶液与小分子一元醇混匀后成型，得到三维立体状且不溶于水的丝素蛋白材料，其中，所述丝素蛋白水溶液中，丝素蛋白的浓度为30-70mg/mL，丝素蛋白的分子量为8000-14000Da，丝素蛋白与小分子一元醇的质量比为100-1000:1；
    (2)将所述丝素蛋白材料浸入pH＞14的强碱水溶液中，处理0.1-5秒后取出，再浸入0.1-1mol/L的还原性弱酸和/或还原性弱酸盐的水溶液中处理1-10分钟；
    (3)将经步骤(2)处理后的丝素蛋白材料于15-30℃下浸入0.1-1mol/L高锰酸钾水溶液中，处理10分钟以下，得到表面氧化后的丝素蛋白材料；
    (4)将表面氧化后的丝素蛋白材料浸入过氧化物水溶液中，然后向其中加入3,4-乙烯二氧噻吩并在20-30℃下反应，以使得3,4-乙烯二氧噻吩在丝素蛋白材料表面发生聚合，反应完全后得到所述导电丝素材料。
  2. 根据权利要求1所述的制备方法，其特征在于：在步骤(1)中，所述小分子一元醇为甲醇、乙醇和丙醇中的一种或几种。
  3. 根据权利要求1所述的制备方法，其特征在于：在步骤(2)中，强碱为氢氧化钠和/或氢氧化钾。
  4. 根据权利要求1所述的制备方法，其特征在于：在步骤(2)中，所述还原性弱酸或还原性弱酸盐的水溶液的pH值为4-6。
  5. 根据权利要求1所述的制备方法，其特征在于：在步骤(2)中，还原性弱酸为亚硫酸和/或甲酸；还原性弱酸盐为亚硫酸氢钠和/或亚硫酸氢钾。
  6. 根据权利要求1所述的制备方法，其特征在于：在步骤(4)中，过氧化物为过硫酸铵、过硼酸钠、过硼酸钾、过硫酸钠和过硫酸钾中的一种或几种，所述过氧化物水溶液浓度为0.1-0.5mol/L。
  7. 根据权利要求1所述的制备方法，其特征在于：在步骤(4)中，所述3,4-乙烯二氧噻吩的浓度为0.1-0.5mol/L。
  8. 根据权利要求1所述的制备方法，其特征在于：在步骤(1)中，所述三维立体状且不溶于水的丝素蛋白材料呈平面膜状。
  9. 一种权利要求1-8中任一项所述的制备方法所制备的导电丝素材料，其特征在于，包括三维立体状且不溶于水的丝素蛋白材料及接枝于丝素蛋白材料表面的导电层，所述导电层包括聚3,4-乙烯二氧噻吩，所述导电丝素材料的表面方阻为100欧姆-5000欧姆。
  10. 权利要求9所述的导电丝素材料作为柔性电子器件的应用。
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