CN105603761B - A sensitive and scalable method for preparing polyaniline fibers Humidity - Google Patents

A sensitive and scalable method for preparing polyaniline fibers Humidity Download PDF

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CN105603761B
CN105603761B CN 201610058509 CN201610058509A CN105603761B CN 105603761 B CN105603761 B CN 105603761B CN 201610058509 CN201610058509 CN 201610058509 CN 201610058509 A CN201610058509 A CN 201610058509A CN 105603761 B CN105603761 B CN 105603761B
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fibers
conductive
polyaniline
fiber
acid
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CN105603761A (en )
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韩文鹏
龙云泽
张君诚
闫旭
赵惠
高志远
巩凡
于桂凤
贺晓晓
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青岛大学
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Abstract

本发明公开了一种湿度敏感可伸缩聚苯胺导电纤维及其制备方法,该纤维包括模板纤维和包覆于模板纤维上的质子酸掺杂聚苯胺导电层,所述模板纤维为氨纶包芯棉纱,所述氨纶包芯棉纱以氨纶为内线,弯曲缠绕在氨纶内线上的棉纱线包裹内线,质子酸掺杂聚苯胺形成的导电层均匀包覆在棉纱线上。 The present invention discloses a moisture-sensitive and scalable method for preparing polyaniline fibers, the fibers comprising fibers and coated on the template template protonic acid doped polyaniline fibers conductive layer, the template is a spandex core yarn fibers the spandex core yarn is a spandex inside curved cotton yarn wound spandex package inside the line, protonic acid doped polyaniline conductive layer is formed uniformly coated yarn line. 该纤维具有优越的拉伸弯曲性能,其导电率在纤维拉伸弯曲状态下仍可保持相对稳定,变化幅度很小;此外,该导电纤维对湿度感应灵敏,其导电率随湿度变化明显,且制备方法简单,成本较低,适宜大批量生产,可用于制备柔性导线和柔性湿敏传感器。 The fibers have excellent tensile flexural properties, its conductivity can be maintained at a relatively stable state fiber drawing is bent, the magnitude of change is small; in addition, the conductive fibers sensitive to humidity sensor, its conductivity changes significantly with humidity, and preparation method is simple, low cost, suitable for mass production, can be used to prepare a flexible conductor and a flexible moisture sensor.

Description

一种湿度敏感可伸缩聚苯胺导电纤维及其制备方法 A sensitive and scalable method for preparing polyaniline fibers Humidity

技术领域 FIELD

[0001] 本发明涉及一种湿度敏感可伸缩聚苯胺导电纤维及其制备方法,属于导电材料制备领域。 [0001] The present invention relates to a moisture-sensitive and scalable method for preparing polyaniline fibers, which belongs to the field of preparation of a conductive material.

背景技术 Background technique

[0002] 随着科技发展水平的不断提高,近年来人们对可穿戴设备的需求不断增加,美国苹果公司、韩国三星公司等世界知名企业都相继进入这一领域,开发出了相关产品。 [0002] With the increasing level of technology development in recent years for wearable devices increasing demand, the US Apple, Samsung and other world-renowned companies have entered the field, the development of related products. 传感器作为当代电子设备的重要部分,如何制备不同类型和用途的可穿戴传感器元器件也成了当代科技研究的一个热点,其相关领域涉及材料开发、制造工艺技术革新等领域。 Sensor as an important part of contemporary electronic devices, how to prepare and use various types of wearable sensor components has become a research hotspot of modern technology, the related art which relates to the field of materials development, manufacturing technology innovation like.

[0003] 聚苯胺作为一种研究广泛的导电聚合物材料,具有多样化的结构、独特的掺杂机理、优异的物化结构、良好的稳定性和廉价易得、合成简单等优点,因而被认为是最有希望在实际中得到应用的导电聚合物材料之一。 [0003] As a widely studies of polyaniline conductive polymer material, having a variety of structures, unique doping mechanism, excellent physical and chemical structure, good stability and readily available and inexpensive, and simple synthesis, which is considered one of the most promising is to give a conductive polymer material is applied in practice. 得益于聚苯胺材料独特的电化学性质,近年来关于聚苯胺传感器的报道层出不穷,包括化学、生物、湿度等不同类型的传感器,但能够应用于可穿戴设备的可伸缩柔性传感器始终未见报道。 Thanks to the unique electrochemical properties of the material polyaniline, polyaniline in recent years, reports on the endless sensors, including different types of chemical, biological, and humidity sensors, but can be applied to a wearable device scalable flexible sensor always been reported . 目前制备复合材料是科研工作者获得具备可伸缩性质聚苯胺材料的主要方法,该方法利用具备可伸缩性质的材料为基本材料, 在制备过程中掺杂聚苯胺,最终复合得到既具备可伸缩性又能够导电的复合材料,中国专利(专利公开号:CN103243563A)公开了一种聚苯胺/聚乳酸复合导电纤维的制备方法,制备工艺简单,纤维导电性能优良;中国专利(专利公开号:CN103255634)公开了一种聚丙烯腈/ 聚苯胺复合微纳米导电纤维的制备方法,该发明所使用的聚乙二醇是一种用途广泛的水溶性高分子,对环境没有污染且成本低廉。 Currently the main method of making a composite comprising the scalable nature of the material scientists polyaniline obtained using the method comprising the scalable nature of the material as the basic material, doped polyaniline during the manufacturing process, to obtain the final composite includes both scalability and an electrically conductive composite material, Chinese Patent (Patent Publication No: CN103243563A) discloses a polyaniline / PLA composite conductive fiber preparation, simple preparation process, high conductivity fibers; Chinese Patent (Patent Publication number: CN103255634) discloses a polyacrylonitrile / polyaniline composite micro-nano preparing conductive fibers used in this invention, the polyethylene glycol is a widely used water-soluble polymer, no environmental pollution and low cost. 但是这两种方法制备的导电纤维并不具备可伸缩性。 However, the two conductive fiber prepared by the method does not have scalability. 中国专利(专利公开号:CN102692288A)公布了一种柔性力敏传感器的制备方法,该发明制成纳米结构导电聚苯胺同轴有序纤维的柔性力敏传感器,其导电聚苯胺柔性纤维力学性能好,不易破碎,灵敏度高,响应时间短,但是纤维拉伸程度有限(仅为原长的4%),并且制备方法相对复杂。 Chinese Patent (Patent Publication No: CN102692288A) published a method for preparing a flexible force-sensitive sensor, made of the electrically conducting polyaniline nanostructures invention orderly fiber coaxial flexible force sensor, conductive polyaniline which good mechanical properties of flexible fibers , easily broken, high sensitivity, short response time, but the limited extent of fiber drawing (only 4% of the original length), and the preparation is relatively complicated. 同时,现有方法制备的材料导电性随着本身形变的增加会有明显的降低, 并不适宜用来制备具有可穿戴性质的柔性传感器。 Meanwhile, the conductive material is prepared by a conventional method increases as the deformation per se will be significantly reduced, the flexible sensor is not suitable for preparing a wearable property.

发明内容 SUMMARY

[0004] 本发明的目的在于克服现有技术的不足,提供一种湿度敏感可伸缩聚苯胺导电纤维及其制备方法,该纤维具有优越的拉伸弯曲性能,其导电率在纤维拉伸弯曲状态下仍可保持相对稳定,变化幅度很小,此外,该导电纤维对湿度感应灵敏,其导电率随湿度变化明显,且制备方法简单,成本较低,适宜大批量生产,可用于制备柔性导线和柔性湿敏传感器。 [0004] The object of the present invention is to overcome the disadvantages of the prior art, there is provided a moisture-sensitive and scalable method for preparing polyaniline fibers, which fibers have excellent tensile flexural properties, its conductivity in the fiber drawing bent state under still remained relatively stable, the variation width is small, moreover, the conductive fibers sensitive to humidity sensor, its conductivity changes significantly with humidity, and the preparation method is simple, low cost, suitable for mass production, and can be used to prepare flexible conductor The flexible moisture sensor.

[0005] 为了实现上述目的,本发明提供的技术方案如下: [0005] To achieve the above object, the present invention provides the following technical solution:

[0006] —种湿度敏感可伸缩聚苯胺导电纤维的制备方法,包括以下步骤: [0006] - humidity sensitive species scalable method for preparing polyaniline fibers, comprising the steps of:

[0007] (1)配制反应液:质子酸溶于去离子水配制成质子酸溶液记为溶液1,氧化剂和苯胺共同加入去离子水中搅拌得乳浊液状的聚苯胺反应液记为溶液2; [0007] (1) Preparation of the reaction solution: a proton acid was dissolved in deionized water formulated as a solution the protic acid solution is designated 1, the aniline and the oxidizing agent in deionized water was added together with stirring to give an emulsion of the liquid reaction solution was referred to as polyaniline solution 2;

[0008] (2)模板纤维表面原位聚合导电层:将氨纶包芯棉纱作为模板纤维拉伸缠绕在镂空支架上,将缠绕有模板纤维的镂空支架浸入装有溶液2的容器中,再向溶液2中逐滴加入溶液1,待步骤(1)配制的溶液1完全加入溶液2后将容器密封放置于冷藏箱中,静置待聚苯胺导电层完全包覆模板纤维表面,形成导电纤维; [0008] (2) in-situ polymerization of the conductive fiber surface template layer: the spandex core yarn is wound as a template in the hollow fiber drawing frame, template wound hollow fiber scaffold was immersed in a vessel containing a solution of 2, again the solution was added dropwise a solution of 2-by-1 until the step (1) was prepared 1 2 after complete addition solution was sealed vessel placed in a refrigerator and allowed to stand until completely coated fiber polyaniline conductive layer surface of the template, forming a conductive fiber;

[0009] (3)清洗纤维:将步骤(2)所得的缠有导电纤维从镂空支架从步骤(2)的混合液体中取出,把导电纤维从镂空支架上取下,用去离子水反复冲洗所得纤维; [0009] (3) washing the fibers: the step (2) is wound with electrically conductive fibers obtained from the mixed liquid withdrawn from the hollow holder step (2), the conductive fibers removed from the hollow holder, repeatedly washed with deionized water The resulting fiber;

[0010] (4)干燥纤维:干燥步骤⑶清洗干净的导电纤维即得湿度敏感可伸缩聚苯胺导电纤维。 [0010] (4) drying the fiber: the step of drying the cleaned ⑶ conductive fibers to obtain moisture-sensitive fibers may be telescopically polyaniline.

[0011] 作为模板纤维的氨纶包芯棉纱,由氨纶内线和弯曲缠绕在氨纶内线上的棉纱线组成,氨纶包芯棉纱拉伸时,其内线拉伸,而包裹在内线上的棉纱线仅由弯曲状被拉直,棉纱线的总长不发生变化,将模板纤维以拉伸的形式缠绕在镂空支架上,再将其浸入聚苯胺反应液并加入质子酸溶液,苯胺单体在模板纤维外层的棉纱线表面形成均匀的酸掺杂聚苯胺导电层,使得该纤维在具有氨纶包芯棉纱优良的拉伸弯曲性能的同时具有聚苯胺的导电性和湿度敏感性能,制得的纤维在拉伸弯曲形变时,包裹有聚苯胺导电层的棉纱线仅被拉直, 其总长度不发生变化,可以保证聚苯胺导电层的完整性,即在纤维拉伸弯曲的过程中聚苯胺导电层不发生破损和断裂,因此纤维的导电性基本不随其拉伸弯曲形变而变化,仅由于聚苯胺本身的湿度敏感特性,使纤维的导电率 [0011] As a template spandex core yarn fibers, inside the spandex and cotton yarn wound on the bending line spandex composition, when stretched spandex core yarn, which is inside the drawing, the line including cotton yarn wrapped only by curved shape is straightened, the total length of the cotton yarn does not change, the stretched form of the template fibers wound on the hollow holder, and then immersed in the reaction solution and polyaniline solution, adding a protic acid, aniline monomer in the outer layer of the fiber template cotton yarn to form a uniform surface of the conductive acid-doped polyaniline layer, such that the fiber has a conductive polyaniline and humidity while having excellent tensile flexural properties of sensitive spandex core yarn can be prepared in a tensile fibers when the bending deformation, wrapped with cotton yarn polyaniline layer is only straightened, the total length does not change, can guarantee the integrity of the conductive polyaniline layers, i.e. polyaniline conductive layer does not occur the bending in the fiber drawing process damaged and broken, thus the conductive fiber does not vary substantially its tensile bending deformation varies, since only the characteristics of the polyaniline itself moisture-sensitive, so that the electrical conductivity of the fibers 环境湿度变化而变化。 Ambient humidity changes. 同时,模板纤维在拉伸状态下其外部比表面积增大,相较于松弛状态的模板纤维,拉伸状态的模板纤维外层的棉纱线与聚苯胺反应液接触更充分,聚苯胺导电层在棉纱线表面能够形成更加均匀致密的包裹层,在一定程度上提高纤维的导电性能。 Meanwhile, external template fiber surface area increases in tension, a relaxed state as compared to the fibers of the template, contacting the reaction liquid cotton yarn with polyaniline fibers stretched state template layer more fully, polyaniline conductive layer cotton yarn surface capable of forming a uniform and dense layer of wrapping, to improve the conductivity properties of the fibers to a certain extent.

[0012] 优选的,所述步骤⑴所述的质子酸为磺基水杨酸、盐酸、高氯酸、硫酸、磷酸、对甲基苯磺酸、十二烷基苯磺酸中的一种;所述氧化剂为过硫酸铵、双氧水、过氧乙酸、重铬酸钠、铬酸、硝酸、高锰酸钾中的一种。 [0012] Preferably, said step ⑴ said protic acid is sulfosalicylic acid, hydrochloric acid, perchloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, of one ; the oxidizing agent is ammonium persulfate, hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid, a potassium permanganate.

[0013] 优选的,所述步骤⑴配制反应液:称取5.0844克磺基水杨酸溶于100毫升去离子水,用磁力搅拌器进行搅拌5至10分钟使溶剂溶化均匀制得溶液1;称取9.128克过硫酸铵加入100毫升去离子水中,再滴加3.725克苯胺,用磁力搅拌器进行搅拌至溶液变成乳浊液即制得溶液2。 [0013] Preferably, said step ⑴ reaction mixture was prepared: Weigh 5.0844 g sulfosalicylic acid dissolved in 100 ml of deionized water and stirred with a magnetic stirrer for 5 to 10 minutes so uniformly dissolved in a solvent to prepare a solution; Weigh 9.128 g of ammonium persulfate was added to 100 ml of deionized water, 3.725 g of aniline was added dropwise, with stirring until the solution became emulsion was prepared 2 i.e. with a magnetic stirrer.

[0014] 优选的,所述步骤(2)模板纤维表面原位聚合导电层:将氨纶包芯棉纱作为模板纤维拉伸缠绕在镂空支架上,将缠绕有模板纤维的镂空支架浸入装有溶液2的烧杯中,再用胶头滴管向溶液2中逐滴加入溶液1,待步骤(1)配制的溶液1完全加入溶液2后将烧杯密封放置于-2°C冷藏箱中,静置8小时形成导电纤维。 [0014] Preferably, the step (2) in-situ polymerization of the conductive fiber surface template layer: the spandex core yarn is wound as a template in the hollow fiber drawing frame, template wound hollow fiber by immersing the stent a solution of 2 beaker, then the first plastic dropper wise to the solution was added dropwise a solution 1 2, until step (1) was prepared 1 2 after complete addition the beaker was placed in a sealed -2 ​​° C freezer and allowed to stand 8 hour to form the conductive fiber.

[0015] 优选的,所述步骤(3)清洗纤维:将步骤(2)所得的缠有导电纤维从镂空支架从步骤(2)的混合液体中取出,把导电纤维从镂空支架上取下,用去离子水冲洗所得纤维15分钟。 [0015] Preferably, the step (3) washing the fibers: the step (2) is wrapped around the resulting conductive fibers, the conductive fibers removed from the hollow holder (2) is removed from the mixed liquid from the hollow holder step, The resulting fiber rinsed with deionized water for 15 minutes.

[0016] 优选的,所述步骤⑷干燥纤维:将步骤(3)清洗干净的导电纤维置于真空干燥箱中常温干燥即得湿度敏感可伸缩聚苯胺导电纤维。 [0016] Preferably, the step of drying the fiber ⑷: The cleaning step (3) Clean conductive fibers dried in a vacuum oven at room temperature to give the moisture sensitive telescopically polyaniline fibers.

[0017] 本发明还公开了所述的制备方法制得的湿度敏感可伸缩聚苯胺导电纤维,所述导电纤维包括模板纤维和包覆于模板纤维上的酸掺杂聚苯胺导电层,所述模板纤维为氨纶包芯棉纱,所述氨纶包芯棉纱以氨纶为内线,弯曲缠绕在氨纶内线上的棉纱线包裹内线,酸掺杂聚苯胺形成的导电层均匀包覆在棉纱线上。 [0017] The present invention also discloses a preparation method was the moisture sensitive telescopic polyaniline fibers, the conductive fibers comprise fibers and a template to the template fibers coated acid-doped polyaniline conductive layer, the template fiber spandex core yarn, the spandex core yarn is a spandex inside curved cotton yarn wound spandex package inside the line, the conductive acid-doped polyaniline layer is formed uniformly coated cotton line.

[0018] 进一步的,所述导电纤维拉伸弯曲形变时其导电率的变化率小于5%,所述导电纤维的导电率随环境湿度的变化而变化。 [0018] Further, the conductive fibers of the rate of change of conductivity upon stretching bending strain of less than 5%, the electrical conductivity of the conductive fibers varies with the ambient humidity.

[0019] 进一步的,所述导电纤维的最大拉伸率大于200%,纤维拉伸至最大拉伸率时,纤维的导电率的变化率仍小于5%。 When [0019] Further, the maximum draw ratio of the conductive fibers is greater than 200%, the fiber stretched to the maximum stretching ratio, the conductivity change rate is still less than 5% fiber.

[0020] 本发明的有益效果为:本发明克服了现有技术的不足,提供了一种湿度敏感可伸缩聚苯胺导电纤维及其制备方法,该导电纤维具有优越的拉伸弯曲性能,其导电率在拉伸弯曲形变时可保持稳定,该导电纤维对湿度感应灵敏,其导电率随湿度明显变化,且制备方法简单,成本较低,适宜大批量生产,可用于制备柔性湿敏传感器。 [0020] Advantageous effects of the present invention are: The present invention overcomes the disadvantages of the prior art, there is provided a moisture-sensitive and scalable method for preparing polyaniline fibers, the conductive fibers have excellent tensile flexural properties, electrical conductivity bending strain rate during stretching is stable, the conductive fibers sensitive to humidity sensor, significant changes in its conductivity with humidity, and the preparation method is simple, low cost, suitable for mass production, can be used to prepare a flexible moisture sensor. 本发明的导电以氨纶包芯棉纱作为模板纤维,氨纶包芯棉纱由氨纶内线和弯曲缠绕在氨纶内线上的棉纱线组成, 氨纶包芯棉纱拉伸时,其内线拉伸,而包裹在内线上的棉纱线仅由弯曲状被拉直,棉纱线的总长不发生变化,将模板纤维以拉伸的形式缠绕在镂空支架上,再将其浸入聚苯胺反应液并加入质子酸溶液,苯胺单体在模板纤维外层的棉纱线表面形成均匀的酸掺杂聚苯胺导电层,使得该纤维在具有氨纶包芯棉纱优良的拉伸弯曲性能的同时具有聚苯胺的导电性和湿度敏感性能,该纤维的最大拉伸率大于200%,制得的纤维在拉伸弯曲形变时,包裹有聚苯胺导电层的棉纱线仅被拉直,其总长度不发生变化,可以保证聚苯胺导电层的完整性,即在纤维拉伸弯曲的过程中聚苯胺导电层不发生破损和断裂,因此纤维的导电性能基本不随其拉伸弯曲形变而形变( In the present invention the conductive spandex core yarn fibers as a template, a spandex core yarn and spandex inside curved line wound around the spandex composition cotton yarn when stretched spandex core yarn, which is inside the drawing, while the inner line parcel cotton yarn only be straightened by the curved shape, the total length of the cotton yarn does not change, the stretched form of the template fibers wound on the hollow holder, and then immersed in the reaction solution and polyaniline solution, adding a protic acid, aniline monomer acid-doped polyaniline to form a uniform conductive layer of cotton yarn fiber outer surface of the template, such that the fiber has a conductive polyaniline and humidity while having excellent flexural spandex core yarn tensile properties can sensitivity, the fibers the maximum elongation greater than 200%, the resulting fiber bending strain during stretching, wrapped with cotton yarn polyaniline layer is only straightened, the total length does not change, we can guarantee the integrity of the conductive polyaniline layer , i.e. polyaniline conductive layer damage and breakage does not occur in bending the fiber drawing process, so the conductive property of the fiber with substantially no bending deformation and tensile deformation ( 电率变化率小于5%),仅由于聚苯胺本身的湿度敏感特性,使纤维的导电率随环境湿度变化而变化。 Dependent variation rate of less than 5%), only due to the moisture-sensitive characteristics of polyaniline itself, the electrical conductivity of the fibers with the ambient humidity changes. 同时,模板纤维在拉伸状态下其外层棉纱线与聚苯胺反应液的接触面积增大,有利于在模板纤维外部包裹更致密的聚苯胺导电层,提高纤维的导电性能。 Meanwhile, the contact area outer template fiber cotton yarn with polyaniline reaction liquid increases in tension, conducive fibers outside the package template denser polyaniline conductive layer, to improve the conductivity properties of the fibers.

附图说明 BRIEF DESCRIPTION

[0021] 图1为本发明的湿度敏感可伸缩聚苯胺导电纤维的制备方法的流程图; A flowchart of a method of conductive polyaniline fibers sensitive to humidity [0021] FIG. 1 of the present invention is scalable;

[0022] 图2为实施例1的纤维的电阻随拉伸次数变化曲线; [0022] FIG. 2 is a resistance of the fiber of Example 1 with tensile frequency curve;

[0023] 图3为实施例1的纤维的电阻随拉伸率变化曲线; [0023] FIG. 3 is a resistance of the fiber of Example 1 with the elongation curve;

[0024] 图4为实施例1的纤维在RH 20%和RH 90%情况下交替变化的频率响应曲线。 [0024] FIG. 4 is a frequency response curve of the fiber in Example 1 where 90% RH 20% RH and the alternate embodiment.

具体实施方式 Detailed ways

[0025] 根据下述实施例,可以更好地理解本发明。 [0025] The following examples, the present invention may be better understood. 然而,本领域的技术人员容易理解,实施例所描述的具体的物料配比、工艺条件及其结果仅用于说明本发明而不应当也不会限制权利要求书中所详细描述的本发明。 However, those skilled in the art will readily appreciate the specific materials described embodiments ratio, the process conditions and the results of the present invention are for illustration only and should not be described in detail without restricting the claims of the present invention.

[0026] 实施例1 [0026] Example 1

[0027] —种湿度敏感可伸缩聚苯胺导电纤维的制备方法,包括以下步骤: [0027] - humidity sensitive species scalable method for preparing polyaniline fibers, comprising the steps of:

[0028] (1)配制反应液:称取5.0844克磺基水杨酸溶于100毫升去离子水,用磁力搅拌器进行搅拌5至10分钟使溶剂溶化均匀制得溶液1;称取9.128克过硫酸铵加入100毫升去离子水中,再滴加3.725克苯胺,用磁力搅拌器进行搅拌至溶液变成乳浊液即制得溶液2; [0028] (1) Preparation of the reaction solution: Weigh 5.0844 g sulfosalicylic acid dissolved in 100 ml of deionized water and stirred with a magnetic stirrer for 5 to 10 minutes so uniformly dissolved in a solvent to prepare a solution; Weigh 9.128 g ammonium persulfate was added 100 ml of deionized water, 3.725 g of aniline was added dropwise, with stirring until the solution became i.e. prepared emulsion solution with a magnetic stirrer 2;

[0029] (2)模板纤维表面原位聚合导电层:将氨纶包芯棉纱作为模板纤维拉伸缠绕在镂空支架上,将缠绕有模板纤维的镂空支架浸入装有溶液2的烧杯中,再用胶头滴管向溶液2 中逐滴加入溶液1,待步骤(1)配制的溶液1完全加入溶液2后将烧杯密封放置于-2°C冷藏箱中,静置8小时形成导电纤维; [0029] (2) in-situ polymerization of the conductive fiber surface template layer: the spandex core yarn is wound as a template in the hollow fiber drawing frame, template wound hollow fiber scaffold was immersed in a beaker containing solution 2, and then plastic head dropper wise to the solution was added dropwise a solution of 2 1, until in step (1) was prepared 1 2 after complete addition the beaker was placed in a sealed -2 ​​° C freezer, allowed to stand for 8 hours to form the conductive fiber;

[0030] (3)清洗纤维:将步骤(2)所得的缠有导电纤维从镂空支架从步骤(2)的混合液体中取出,把导电纤维从镂空支架上取下,用去离子水冲洗所得纤维15分钟; [0030] (3) washing the fibers: the step (2) is wound with electrically conductive fibers obtained from the mixed liquid withdrawn from the hollow holder step (2), the conductive fibers removed from the hollow holder, rinsed with deionized water The resulting fibers 15 min;

[0031] (4)干燥纤维:将步骤(3)清洗干净的导电纤维置于真空干燥箱中常温干燥即得湿度敏感可伸缩聚苯胺导电纤维。 [0031] (4) drying the fiber: the step (3) clean conductive fibers dried in a vacuum oven at room temperature to give the moisture sensitive telescopically polyaniline fibers.

[0032] 性能测试: [0032] Performance Testing:

[0033] (1)拉伸性能测试:取一小段实施例1制得的湿度敏感可伸缩聚苯胺导电纤维进行拉伸测试其最大拉伸率,最大拉伸率的计算公式如下: [0033] (1) Tensile test: Take a short stretch obtained in Example moisture sensitive conductive polyaniline fibers retractable embodiment tested produced a maximum stretching ratio, the maximum stretching ratio is calculated as follows:

[0034] [0034]

Figure CN105603761BD00061

[0035] 由此公式计算得到本发明实施例1的纤维的最大拉伸率大于200%。 [0035] The thus obtained formula embodiment of the present invention the maximum draw ratio of the fiber of Example 1 is greater than 200%.

[0036] (2)纤维电学性能与拉伸形变的关系:取实施例1制得的自然长度为3厘米的一段纤维,将纤维两端接上铜线制作电极,并在铜线与纤维连接端涂上银胶确保连接处导通,待银胶溶剂挥发凝固后,将该纤维联入电路,反复拉伸纤维,测试其在自然长度的电阻随拉伸次数的变化,测试结果如图2所示,由图2可以看出该纤维可重复拉伸数千次,其导电性能仍然得以保持;然后测试该纤维在不同拉伸程度下的电阻变化,测试结果如图3所示,由图3可以看出该纤维的电阻随纤维拉伸形变的变化很小,其变化率在5%以内,当纤维拉伸率至200%时,其电阻变化率仍在5%以内,纤维的电阻变化情况也反应了其导电率的变化情况。 [0036] (2) the relationship between electrical properties and fiber tensile deformation: Example 1 was taken natural length of 3 cm length of the fiber, the ends of the fiber connected to an electrode made of copper wire, copper wire and fiber connected coated with silver paste to ensure that the end connection turned after evaporation of the solvent solidified silver paste, linked into the fiber circuit, is repeatedly drawn fiber, which changes with tensile testing times, the test results shown in Figure 2 the length of the resistor NATURAL shown, it can be seen from Figure 2 that the tensile fiber may be repeated thousands of times, its conductivity is still maintained; then tested for resistance variation of the fiber at different degree of stretching, the test results shown in Figure 3, FIG. 3 shows that the resistance of the fibers with the fiber drawing deformation little change in the rate of change within 5%, when the fiber drawing rate of 200%, the resistance change rate is still less than 5%, the resistance change of the fiber also it reflects the situation changes its electrical conductivity.

[0037] (3)纤维电学性与外界环境湿度的变化关系:测试该纤维在RH20%和RH 90%情况下交替变化的频率响应曲线如图4所示,由图4看出该纤维具有良好的湿敏性能,对湿度变化响应快且灵敏度高较高,并且具备极佳的恢复性。 [0037] (3) the relationship between changes in electrical properties with the environment fibrous humidity: The test frequency of 90% in the case of fibers RH20% RH and alternating response curve is shown, see FIG. 4 of the fiber has good 4 the humidity performance, high speed and high sensitivity in response to changes in humidity, and have excellent recovery.

[0038] 以上所述,仅为本发明的说明实施例,并非对本发明任何形式上和实质上的限制, 如步骤⑴中所述的质子酸可以为磺基水杨酸、盐酸、高氯酸、硫酸、磷酸、对甲基苯磺酸、十二烷基苯磺酸中的一种;氧化剂可以为过硫酸铵、双氧水、过氧乙酸、重铬酸钠、铬酸、硝酸、 高锰酸钾中的一种;步骤(4)还可以采用真空冷冻干燥等干燥方法。 [0038] The above are only embodiments of the present invention described, in any form and not limit the present invention substantially as described in step ⑴ protic acid may be sulfosalicylic acid, hydrochloric acid, perchloric , sulfuric acid, phosphoric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid of one; oxidizing agent may be ammonium persulfate, hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid, permanganic acid one kind of potassium; step (4) was dried in vacuo and freeze drying method may also be employed. 应当指出,对于本技术领域的普通技术人员,在不脱离本发明方法的前提下,做出的若干改进和补充也应视为本发明的保护范围,本发明未详尽说明处均为本领域技术人员所公知的现有技术,凡熟悉本专业的技术人员,在不脱离本发明的精神和范围的情况下,利用以上所揭示的技术内容做出的些许更动、修饰与演变的等同变化,均为本发明的等效实施例;同时,凡依据本发明的实质技术对上述实施例所做的任何等同变化的更动、修饰与演变,均仍属于本发明的技术方案的范围。 It should be noted that one of ordinary skill in the art, without departing from the method of the invention premise, made a number of improvements and additions shall also be deemed scope of the present invention, a detailed description of the present invention are not skilled in the art well known to those of prior art, where Those skilled in the art, without departing from the spirit and scope of the present invention, with the above disclosed technical contents make minor modifications, equivalents, changes and modifications evolution, It is equivalent to the present embodiment of the invention; and, where the modifier according to any equivalent change in the essence of the technical disclosure of the above-described embodiment of the present embodiment did, modifications and evolution are still within the scope of the technical solutions of the present invention.

Claims (7)

  1. 1. 一种湿度敏感可伸缩聚苯胺导电纤维,其特征在于,所述导电纤维包括模板纤维和包覆于模板纤维上的酸掺杂聚苯胺导电层,所述模板纤维为氨纶包芯棉纱,所述氨纶包芯棉纱以氨纶为内线,弯曲缠绕在氨纶内线上的棉纱线包裹内线,酸掺杂聚苯胺形成的导电层均匀包覆在棉纱线上,所述导电纤维拉伸弯曲形变时其导电率的变化率小于5%,所述导电纤维的导电率随环境湿度的变化而变化,所述的湿度敏感可伸缩聚苯胺导电纤维的制备方法包括以下步骤: (1) 配制反应液:质子酸溶于去离子水配制成质子酸溶液记为溶液1,氧化剂和苯胺加入去离子水中搅拌得乳浊液状的聚苯胺反应液记为溶液2; (2) 模板纤维表面原位聚合导电层:将氨纶包芯棉纱作为模板纤维拉伸缠绕在镂空支架上,将缠绕有模板纤维的镂空支架浸入装有溶液2的容器中,再向溶液2中逐 A moisture-sensitive telescopic polyaniline fibers, wherein said fibers comprise conductive fibers and coated on the template acid-doped polyaniline fiber layer on the template, the template is a spandex core yarn fibers, when the spandex core yarn is a spandex inside curved cotton yarn wound spandex package inside the line, the conductive acid-doped polyaniline layer formed uniformly coated cotton line, the conductive fibers which stretch bending strain rate of change of conductivity of less than 5%, the electrical conductivity of the conductive fibers varies with the ambient humidity, said humidity sensitive method for preparing polyaniline fibers may be telescopically comprising the steps of: (1) preparation of the reaction solution: proton acid was dissolved in deionized water to a formulation protic acid solution referred to deionized water with stirring to obtain an emulsion of a liquid solution of 1, aniline and an oxidizing agent the reaction solution referred to as polyaniline solution 2; (2) the template-situ polymerization fiber surface conductive layer: the spandex core yarn wound fiber drawing as a template in the hollow holder, the hollow fiber is wound template holder is immersed in a vessel containing a solution of 2, again by a solution of 2 加入溶液1,待步骤(1)配制的溶液1完全加入溶液2后将容器密封放置于冷藏箱中,静置待聚苯胺导电层完全包覆模板纤维表面,形成导电纤维; (3) 清洗纤维:将步骤(2)所得的缠有导电纤维的镂空支架从步骤(2)的混合液体中取出,把导电纤维从镂空支架上取下,用去离子水反复冲洗所得纤维; (4) 干燥纤维:干燥步骤(3)清洗干净的导电纤维即得湿度敏感可伸缩聚苯胺导电纤维。 1, until in step (1) was added a solution prepared by adding 2 completely sealed after the container was placed in a refrigerator and allowed to stand until completely cover the surface of the fiber template layer conductive polyaniline, electrically conductive fibers is formed; (3) washing the fibers : the step (2) is wound with electrically conductive fibers obtained hollow holder (2) in the mixed liquid was removed from the step, the conductive fiber is removed from the hollow holder, repeatedly washed with deionized water, the resulting fiber; (4) drying the fiber : drying step (3) clean conductive fibers to obtain moisture-sensitive fibers may be telescopically polyaniline.
  2. 2. 如权利要求1所述的一种湿度敏感可伸缩聚苯胺导电纤维,其特征在于,所述步骤(1)所述的质子酸为磺基水杨酸、盐酸、高氯酸、硫酸、磷酸、对甲基苯磺酸、十二烷基苯磺酸中的一种;所述氧化剂为过硫酸铵、双氧水、过氧乙酸、重铬酸钠、铬酸、硝酸、高锰酸钾中的一种。 2. A moisture sensitive claimed in claim 1, said retractable polyaniline fibers, wherein said protic acid in step (1) is a sulfosalicylic acid, hydrochloric acid, perchloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid of one; the oxidizing agent is ammonium persulfate, hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid, potassium permanganate a.
  3. 3. 如权利要求2所述的一种湿度敏感可伸缩聚苯胺导电纤维,其特征在于,所述步骤(1) 配制反应液:称取5.0844克磺基水杨酸溶于100毫升去离子水,用磁力搅拌器进行搅拌5 至10分钟使溶质溶化均匀制得溶液1;称取9.128克过硫酸铵加入100毫升去离子水中,再滴加3.725克苯胺,用磁力搅拌器进行搅拌至溶液变成乳浊液即制得溶液2。 A moisture sensitive telescopic polyaniline fibers as claimed in claim 2, wherein said step (1) Preparation of the reaction solution: Weigh 5.0844 g sulfosalicylic acid dissolved in 100 ml of deionized water and stirred with a magnetic stirrer for 5 to 10 minutes to prepare a uniform melt solute solution 1; Weigh 9.128 g of ammonium persulfate was added to 100 ml of deionized water, 3.725 g of aniline was added dropwise, and stirred with a magnetic stirrer until the solution became i.e. into the emulsion solution 2 was prepared.
  4. 4. 如权利要求1所述的一种湿度敏感可伸缩聚苯胺导电纤维,其特征在于,所述步骤(2) 模板纤维表面原位聚合导电层:将氨纶包芯棉纱作为模板纤维拉伸缠绕在镂空支架上, 将缠绕有模板纤维的镂空支架浸入装有溶液2的烧杯中,再用胶头滴管向溶液2中逐滴加入溶液1,待步骤⑴配制的溶液1完全加入溶液2后将烧杯密封放置于_2°C冷藏箱中,静置8小时形成导电纤维。 4. A moisture-sensitive claimed in claim 1, said retractable polyaniline fibers, wherein said step (2) in-situ polymerization of the conductive fiber surface template layer: the spandex core yarn wound fiber drawing as a template after the hollow holder, the hollow fiber is wound template holder immersed in a beaker containing a solution of 2, then the first plastic dropper wise to the solution was added dropwise a solution 2 1, step ⑴ be fully formulated solution was added 2 1 the beaker was placed in a sealed _2 ° C freezer, allowed to stand for 8 hours to form the conductive fiber.
  5. 5. 如权利要求1所述的一种湿度敏感可伸缩聚苯胺导电纤维,其特征在于,所述步骤(3) 清洗纤维:将步骤(2)所得的缠有导电纤维的镂空支架从步骤(2)的混合液体中取出,把导电纤维从镂空支架上取下,用去离子水冲洗所得纤维15分钟。 A moisture sensitive telescopic polyaniline fibers as claimed in claim 1, wherein said step (3) washing the fibers: the step (2) is wound with the resulting hollow holder conductive fibers from step ( 2) mixing the liquid removed, a conductive hollow fibers is removed from the holder, rinsed with deionized water the resulting fibers 15 minutes.
  6. 6. 如权利要求1所述的一种湿度敏感可伸缩聚苯胺导电纤维,其特征在于,所述步骤⑷干燥纤维:将步骤⑶清洗干净的导电纤维置于真空干燥箱中常温干燥即得湿度敏感可伸缩聚苯胺导电纤维。 6. A moisture sensitive telescopic polyaniline fibers according to claim 1, wherein said step of drying the fiber ⑷: Step ⑶ clean conductive fibers dried in a vacuum oven at room temperature to yield the humidity scalable sensitive conductive polyaniline fibers.
  7. 7. 如权利要求1所述的湿度敏感可伸缩聚苯胺导电纤维,其特征在于,所述导电纤维的最大拉伸率大于200 %。 7. The humidity sensitive according to claim 1 retractable polyaniline fibers, wherein the maximum elongation of the conductive fibers is greater than 200%.
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