CN106192365A - 一种在碳纤维表面快速自组装接枝碳纳米管的方法 - Google Patents

一种在碳纤维表面快速自组装接枝碳纳米管的方法 Download PDF

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CN106192365A
CN106192365A CN201610711327.9A CN201610711327A CN106192365A CN 106192365 A CN106192365 A CN 106192365A CN 201610711327 A CN201610711327 A CN 201610711327A CN 106192365 A CN106192365 A CN 106192365A
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cnts
carbon fiber
fiber surface
self assembly
diazo resin
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袁华
彭乔虹
于冰
丛海林
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Qingdao University
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    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
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    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract

本发明公开了一种在碳纤维表面快速自组装接枝碳纳米管的方法，它涉及碳纳米管技术领域；它的方法如下：步骤一：采用二苯胺重氮盐与甲醛缩合生成感光速度快的二苯胺重氮树脂，其比浓黏度0.10‑0.15dL/g，Mn＝1000‑2000；步骤二：将功能化的CNTs均匀分散在去离子水中；将活化的CF放入重氮树脂中反应1‑10分钟，使碳纤维表面活性官能团与重氮树脂充分自组装连接；将表面含有重氮树脂的CF放入CNTs溶液中，通过静电自组装，使其充分与CNTs发生反应；紫外交联30s，随着重氮基的分解，CF‑CNTs间的弱键变为共价键，得到共价结合的稳定的CNTs/CF多尺度增强体；本发明能实现碳纤维表面接枝结构和接枝密度可控及接枝有序性，工艺简单可控。

Description

一种在碳纤维表面快速自组装接枝碳纳米管的方法
技术领域
本发明涉及碳纳米管技术领域，具体涉及一种在碳纤维表面快速自组装接枝碳纳米管的方法。
背景技术
作为准一维的量子线，碳纳米管(CNTs)具有高强度和高韧性等优点，碳纳米管与聚合物之间的应力传递能力至少是传统纤维增强复合材料的10倍以上，近年来作为增强相在复合材料中有重要的应用。具有多尺度分级结构的CNTs和碳纤维共增强复合材料因可以在界面上形成梯度分级有序结构，使复合材料具有高强高韧的优异力学性而能得到了研究者广泛的关注。碳纤维表面化学接枝技术以及碳纳米管的化学修饰，使得制备碳纳米管/碳纤维多尺度增强体成为可能。
在碳纤维表面接枝CNTs的方法主要有以下四种：化学气相沉积法(CVD)；电泳沉积法(EPD)；化学接枝法和含CNTs上浆剂涂敷法。1991年，Downs等人通过CVD法在碳纤维表面生长了纳米碳纤维。随后，科研人员进行了大量的关于沉积条件(CNTs生长温度、催化剂的选择及碳源气体的选择)对CNTs生长形态影响的研究。研究者也研究了使用含有CNTs的上浆剂处理碳纤维表面，不仅达到保护纤维的目的，而且改善了复合材料界面的应力传递。但是，采用CVD、EPD或者涂覆法生长的CNTs在界面中尺寸分布、空间排列缺乏有力的控制无法定向排布且工艺复杂，使得对界面增强效果有限，难以充分发挥CNTs的强化效应。
发明内容
本发明的目的在于针对现有技术的缺陷和不足，提供一种在碳纤维表面快速自组装接枝碳纳米管的方法。
为了解决背景技术所存在的问题，本发明的一种在碳纤维表面快速自组装接枝碳纳米管的方法，它的方法如下：
步骤一：采用二苯胺重氮盐与甲醛缩合生成感光速度快的二苯胺重氮树脂，其比浓黏度0.10-0.15dL/g，Mn＝1000-2000；
步骤二：将功能化的CNTs均匀分散在去离子水中；将活化的CF放入重氮树脂中反应1-10分钟，使碳纤维表面活性官能团与重氮树脂充分自组装连接；将表面含有重氮树脂的CF放入CNTs溶液中，通过静电自组装，使其充分与CNTs发生反应；紫外交联30s，随着重氮基的分解，CF-CNTs间的弱键变为共价键，得到共价结合的稳定的CNTs/CF多尺度增强体。
作为优选，所述的二苯胺重氮盐为多聚甲醛与二苯胺重氮盐，其摩尔比为1：2。
本发明有益效果为：能实现碳纤维表面接枝结构和接枝密度可控及接枝有序性，工艺简单可控，有利于保持碳纤维的原有力学性能；同时重氮基上一个氮原子的一对电子能与酚羟基(强氢给体)形成氢键，进而转化为共价键连接，有利于提高复合材料的界面性能。
具体实施方式
本具体实施方式采用如下技术方案：它的方法如下：
步骤一：采用二苯胺重氮盐与甲醛缩合生成感光速度快的二苯胺重氮树脂，其比浓黏度0.10-0.15dL/g，Mn＝1000-2000；
步骤二：将功能化的CNTs均匀分散在去离子水中；将活化的CF放入重氮树脂中反应1-10分钟，使碳纤维表面活性官能团与重氮树脂充分自组装连接；将表面含有重氮树脂的CF放入CNTs溶液中，通过静电自组装，使其充分与CNTs发生反应；紫外交联30s(UV＝365nm,power＝100w)，随着重氮基的分解，CF-CNTs间的弱键变为共价键，得到共价结合的稳定的CNTs/CF多尺度增强体。
进一步的，所述的二苯胺重氮盐为多聚甲醛与二苯胺重氮盐，其摩尔比为1：2。
本具体实施方式取适量长度的氧化CF置于0.1M的NaOH溶液中30min，DI(重氮树脂)水洗后，先后放入0.2g/ml的DR溶液和氧化CNTs溶液中浸泡15min，DI水洗并干燥后，将纤维放于紫外灯下曝光15min。能实现碳纤维表面接枝结构和接枝密度可控及接枝有序性，工艺简单可控，有利于保持碳纤维的原有力学性能；同时重氮基上一个氮原子的一对电子能与酚羟基(强氢给体)形成氢键，进而转化为共价键连接，有利于提高复合材料的界面性能。结果表明，CF-CNTs增强复合材料的层间剪切强度可以提高到145％，复合材料的断裂韧性和弯曲性能的提高幅度达15％-45％。
以上所述，仅用以说明本发明的技术方案而非限制，本领域普通技术人员对本发明的技术方案所做的其它修改或者等同替换，只要不脱离本发明技术方案的精神和范围，均应涵盖在本发明的权利要求范围当中。

Claims (2)

1.一种在碳纤维表面快速自组装接枝碳纳米管的方法，其特征在于：它的方法如下：
步骤一：采用二苯胺重氮盐与甲醛缩合生成感光速度快的二苯胺重氮树脂，其比浓黏度0.10-0.15dL/g，Mn＝1000-2000；
步骤二：将功能化的CNTs均匀分散在去离子水中；将活化的CF放入重氮树脂中反应1-10分钟，使碳纤维表面活性官能团与重氮树脂充分自组装连接；将表面含有重氮树脂的CF放入CNTs溶液中，通过静电自组装，使其充分与CNTs发生反应；紫外交联30s，随着重氮基的分解，CF-CNTs间的弱键变为共价键，得到共价结合的稳定的CNTs/CF多尺度增强体。
2.根据权利要求1所述的一种在碳纤维表面快速自组装接枝碳纳米管的方法，其特征在于：所述的二苯胺重氮盐为多聚甲醛与二苯胺重氮盐，其摩尔比为1：2。
CN201610711327.9A 2016-08-24 2016-08-24 一种在碳纤维表面快速自组装接枝碳纳米管的方法 Pending CN106192365A (zh)

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Cited By (4)

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CN109518306A (zh) * 2018-12-12 2019-03-26 深圳烯湾科技有限公司 改性碳纳米纤维及其制备方法和应用
CN111423700A (zh) * 2020-05-27 2020-07-17 北京化工大学 一种具有多尺度快速自组装界面的碳纤维树脂基复合材料及其制备方法
CN116216698A (zh) * 2023-03-31 2023-06-06 清华大学 一种基于大分子重氮盐的碳纳米管接枝改性方法
CN116365171A (zh) * 2023-06-01 2023-06-30 合肥长阳新能源科技有限公司 一种高离子电导率复合锂电池隔膜及其制备方法

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109518306A (zh) * 2018-12-12 2019-03-26 深圳烯湾科技有限公司 改性碳纳米纤维及其制备方法和应用
CN111423700A (zh) * 2020-05-27 2020-07-17 北京化工大学 一种具有多尺度快速自组装界面的碳纤维树脂基复合材料及其制备方法
CN111423700B (zh) * 2020-05-27 2021-08-10 北京化工大学 一种具有多尺度快速自组装界面的碳纤维树脂基复合材料及其制备方法
CN116216698A (zh) * 2023-03-31 2023-06-06 清华大学 一种基于大分子重氮盐的碳纳米管接枝改性方法
CN116365171A (zh) * 2023-06-01 2023-06-30 合肥长阳新能源科技有限公司 一种高离子电导率复合锂电池隔膜及其制备方法
CN116365171B (zh) * 2023-06-01 2023-08-29 合肥长阳新能源科技有限公司 一种高离子电导率复合锂电池隔膜及其制备方法

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