WO2020244609A1 - 可与碳基材料超组装的3,4-乙烯二氧噻吩聚合物及其制备方法 - Google Patents

可与碳基材料超组装的3,4-乙烯二氧噻吩聚合物及其制备方法 Download PDF

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WO2020244609A1
WO2020244609A1 PCT/CN2020/094512 CN2020094512W WO2020244609A1 WO 2020244609 A1 WO2020244609 A1 WO 2020244609A1 CN 2020094512 W CN2020094512 W CN 2020094512W WO 2020244609 A1 WO2020244609 A1 WO 2020244609A1
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ethylenedioxythiophene
preparation
polymer
dibromo
carbon
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孔彪
谢磊
李继超
曾洁
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Fudan University
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  • the invention belongs to the technical field of organic supramolecules, and specifically relates to a 3,4-ethylenedioxythiophene polymer that can be super-assembled with carbon-based materials and a preparation method.
  • Self-assembly refers to a technology in which basic structural units (molecules, nanomaterials, micron or larger-scale substances) spontaneously form an ordered structure.
  • basic structural units molecules, nanomaterials, micron or larger-scale substances
  • the basic structural units spontaneously organize or aggregate into a stable structure with a certain regular geometric appearance under the interaction based on non-covalent bonds.
  • Carbon nanotube is a kind of nanomaterial with hexagonal structure as the main connecting group, and it has excellent mechanical, electrical and chemical properties. Carbon nanotubes are single-walled and multi-walled. The size range of carbon nanotubes is relatively large, with a common diameter of 2-100nm and a length of 10-200 ⁇ m. Due to the strong van der Waals force between the tube walls, carbon nanotubes are often agglomerated, entangled or knotted, which limits the performance of their mechanical properties and also restricts the industrial use of carbon nanotubes.
  • the present invention provides a 3,4-ethylenedioxythiophene polymer that can be super-assembled with carbon-based materials and a preparation method thereof.
  • the 3,4-ethylenedioxythiophene polymer that can be super-assembled with carbon-based materials provided by the present invention is based on 3,4-ethylenedioxythiophene-2-acetylene as the main chain and alkoxy as the side chain
  • a high molecular polymer which can form a supramolecular self-assembly system with carbon nanotubes of different sizes through the main chain ⁇ - ⁇ adsorption and side chain entanglement.
  • the super-assembled system forms a 3,4-ethylene two
  • the oxythiophene-based polymer/carbon nanotube composite has good stability and has a good application prospect in composite materials.
  • the 3,4-ethylenedioxythiophene-based polymer that can be super-assembled with carbon-based materials provided by the present invention has the general structural formula as follows:
  • n is a natural number greater than zero.
  • the present invention also provides a method for preparing the above 3,4-ethylenedioxythiophene polymer, the specific steps are:
  • the specific steps of the Sonogashira reaction are: under the protection of nitrogen, 2,5-dibromo-3,4-ethylenedioxythiophene 2, double-end acetylenic thiophene intermediate 4, CuI, four three Phenylphosphine palladium and triphenylphosphine are added to the reaction flask, and then toluene and triethylamine are added. After nitrogen replacement, react at high temperature (65-75°C (preferably 70°C)) for a certain period of time, then extract, dry, and concentrate to obtain a yellow viscous liquid, and then use methanol/tetrahydrofuran repeated precipitation method to obtain yellow solid powder.
  • high temperature 65-75°C (preferably 70°C)
  • the molar ratio of the 3,4-ethylenedioxythiophene 1 to bromine water is 1: (2.1-2.5).
  • the present invention also provides 3,4-ethylenedioxythiophene-based high molecular polymers synthesized by any of the above methods.
  • the invention also provides a carbon nanotube supramolecular self-assembly system.
  • the functional substance in the self-assembly system is 3,4-ethylenedioxythiophene-based high molecular polymer.
  • the invention also provides the application of the 3,4-ethylenedioxythiophene-based high molecular polymer in the preparation of carbon nanotube composite materials.
  • the present invention provides a polymer based on 3,4-ethylenedioxythiophene Polymers, which can effectively disperse carbon nanotubes under the action of conventional organic solvents, which can promote the application of carbon nanotubes in composite materials, and have great application potential in the fields of equipment and medical devices;
  • the synthesis method of the present invention is simple, easy to operate, easy to control process parameters, and low in cost of raw materials and equipment.
  • Figure 1 is the NMR spectrum of 2,5-dibromo-3,4-ethylenedioxythiophene 2;
  • Figure 2 is the NMR spectrum of bistrimethylsilyl-3,4-ethylenedioxythiophene intermediate 3;
  • Figure 3 is the NMR spectrum of the double-terminal alkyne-3,4-ethylenedioxythiophene intermediate 4;
  • Fig. 4 is a NMR spectrum of 3,4-ethylenedioxythiophene polymer 5.
  • Polymer 5 Under the protection of nitrogen, add 2,5-dibromo-3,4-ethylenedioxythiophene 2 (3.0g, 10mmol), double-end alkyne-3,4-ethylenedioxythiophene into a dry 250mL three-necked flask Oxythiophene intermediate 4 (1.9g, 10mmol), add CuI (0.19g, 1mmol), tetrakistriphenylphosphine palladium (0.24g, 0.2mmol), triphenylphosphine (0.13g, 0.5mmol), and then add dry 100mL of toluene, 20mL of triethylamine, replaced with nitrogen three times, and reacted at 70°C for 24 hours.

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Abstract

本发明属于有机超分子技术领域，具体为可与碳基材料超组装的3,4-乙烯二氧噻吩聚合物及制备方法。本发明聚合物是以3,4-乙烯二氧噻吩-2-乙炔为主链的、以烷氧基为侧链的高分子聚合物；其制备方法为：以3,4-乙烯二氧噻吩为起始原料，先经溴化反应得到2,5-二溴-3,4-乙烯基二氧噻吩，再与三甲基硅基乙炔反应得到双三甲基硅基-3,4-乙烯基二氧噻吩中间体，脱除TMS保护基后再与2,5-二溴-3,4-乙烯基二氧噻吩发生Sonogashira反应，得到3,4-乙烯二氧噻吩基高分子聚合物。本发明聚合物与碳纳米管之间可形成主链π-π吸附、侧链缠绕的超组装体系，该超组装体系形成的3,4-乙烯基二氧噻吩聚合物/碳纳米管复合物具有良好的稳定性，在复合材料中具有广阔应用前景。

Description

可与碳基材料超组装的3,4-乙烯二氧噻吩聚合物及其制备方法
本申请要求于2019年6月5日提交中国专利局、申请号为201910487971.6、发明名称为“可与碳基材料超组装的3,4-乙烯二氧噻吩聚合物及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于有机超分子技术领域，具体涉及一种可与碳基材料超组装的3,4-乙烯二氧噻吩聚合物及制备方法。
背景技术
自组装(self-assembly)，是指基本结构单元(分子，纳米材料，微米或更大尺度的物质)自发形成有序结构的一种技术。在自组装的过程中，基本结构单元在基于非共价键的相互作用下自发的组织或聚集为一个稳定、具有一定规则几何外观的结构。
碳纳米管是一种以六边形结构为主要连接基团的纳米材料，具有优异的力学、电学和化学性能。碳纳米管有单壁的和多壁的，碳纳米管尺寸范围分布比较大，常见的直径在2～100nm，长度在10～200μm。由于管壁之间存在较强的范德华力，碳纳米管常呈团聚、缠绕或打结状态，限制了其力学等性能的发挥，也制约了碳纳米管的工业使用。
发明内容
为了克服现有碳纳米管易团聚、难分散的缺陷，本发明提供一种可与碳基材料超组装的3,4-乙烯二氧噻吩聚合物及制备方法。
本发明提供的可与碳基材料超组装的3,4-乙烯二氧噻吩聚合物，是以3,4-乙烯二氧噻吩-2-乙炔为主链的、以烷氧基为侧链的高分子聚合物，该高分子聚合物可与不同尺寸的碳纳米管之间通过主链π-π吸附、侧链缠绕形成超分子自组装体系，该超组装体系形成的3,4-乙烯二氧噻吩基聚合物/碳纳米管复合物具有良好的稳定性，在复合材料中具有良好的应用前景。
本发明提供的可与碳基材料超组装的3,4-乙烯二氧噻吩基聚合物，其结构通式如下所示：
Figure PCTCN2020094512-appb-000001
其中，n为大于零的自然数。
本发明还提供上述3,4-乙烯二氧噻吩聚合物的制备方法，具体步骤为：
(1)以3,4-乙烯二氧噻吩1为原料，经溴代反应，制得2,5-二溴-3,4-乙烯二氧噻吩2；
(2)将上述的2,5-二溴-3,4-乙烯二氧噻吩2与三甲基硅基乙炔反应，得到双三甲基硅基-3,4-乙烯二氧噻吩中间体3，双三甲基硅基-3,4-乙烯二氧噻吩中间体3脱除TMS后得到双端炔-3,4-乙烯二氧噻吩中间体4；
(3)将双端炔-3,4-乙烯二氧噻吩中间体4与2,5-二溴-3,4-乙烯二氧噻吩2发生Sonogashira偶联反应，生成的产物即为噻吩乙炔基高分子聚合物5。
在一些实施例中，所述Sonogashira反应的具体步骤为：在氮气保护下，将2,5-二溴-3,4-乙烯二氧噻吩2、双端炔噻吩中间体4、CuI、四三苯基膦钯、三苯基膦加入反应瓶中，再加入甲苯、三乙胺。氮气置换后，于高温下(65～75℃(优选70℃))下反应一定时间、再经萃取、干燥、浓缩处理得到黄色粘液，再经甲醇/四氢呋喃反复沉淀法得到黄色固体粉末。
在一些实施例中，所述3,4-乙烯二氧噻吩1与溴水的摩尔比为1：(2.1～2.5)。
本发明还提供任一上述方法合成的3,4-乙烯二氧噻吩基高分子聚合物。
本发明还提供一种碳纳米管超分子自组装体系，所述自组装体系中的功能物质为3,4-乙烯二氧噻吩基高分子聚合物。
本发明还提供了3,4-乙烯二氧噻吩基高分子聚合物在制备碳纳米管复合材料中的应用。
本发明的有益之处主要体现在：
(1)本发明所提供的3,4-乙烯二氧噻吩基高分子聚合物与碳纳米管 之间发生主链吸附，侧链缠绕作用，通过π-π作用，在不破坏碳纳米管的前提下，实现对碳纳米管的超分子自组装，从而实现了对碳纳米管的分散；
(2)为了保证碳纳米管的本征特性，在不破坏碳纳米管表面结构的前提下增进碳纳米管的分散性，本发明提供了一种基于3,4-乙烯二氧噻吩的高分子聚合物，该聚合物在常规有机溶剂的作用下，能有效的分散碳纳米管，从而可推动碳纳米管在复合材料中的应用，在仪器设备、医疗器械领域具有较大应用潜力；
(3)本发明的合成方法简单，易操作，工艺参数便于控制，原料及仪器设备成本低廉。
说明书附图
图1是2,5-二溴-3,4-乙烯二氧噻吩2的核磁共振谱图；
图2是双三甲基硅基-3,4-乙烯二氧噻吩中间体3的核磁共振谱图；
图3是双端炔-3,4-乙烯二氧噻吩中间体4的核磁共振谱图；
图4是3,4-乙烯二氧噻吩基聚合物5的核磁共振谱图。
具体实施方式
为了进一步说明本发明，下面结合实例和附图对本发明进行详细描述。附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。除非另有指明，本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
实施例1.
3,4-乙烯二氧噻吩基高分子聚合物5的制备流程：
Figure PCTCN2020094512-appb-000002
中间体2～4的合成参照Chem.Eur.J.2011,17,1473-1484报道的步骤进行。制得的2,5-二溴-3,4-乙烯二氧噻吩2为白色固体。 1H NMR(500MHz,Chloroform-d)δ4.26–4.24(m,4H)；双三甲基硅基-3,4-乙烯二氧噻吩中间体3，白色固体。 1H NMR(500MHz,Chloroform-d)δ4.24(m,4H),0.25(s,18H)。双端炔-3,4-乙烯二氧噻吩中间体4，白色固体。 1H NMR(500MHz,Chloroform-d)δ4.24(s,4H),3.29(s,2H)。
聚合物5：在氮气保护下，向干燥的250mL三口烧瓶中加入2,5-二溴-3,4-乙烯二氧噻吩2(3.0g,10mmol)，双端炔-3,4-乙烯二氧噻吩中间体4(1.9g,10mmol)，加入CuI(0.19g，1mmol)，四三苯基膦钯(0.24g，0.2mmol)，三苯基膦(0.13g，0.5mmol)，再加入干燥甲苯100mL，三乙胺20mL，氮气置换三次后于70℃下反应24小时，待反应体系降至室温后，再经萃取、干燥、旋蒸浓缩，得到黄色粘液，再经甲醇/四氢呋喃沉淀法得到黄绿色固体粉末2.6g。 1H NMR(500MHz,Chloroform-d)δ4.26(m,19H),2.23(s,2H),1.99(s,2H)。
以上所述仅为本发明的较佳实施例。凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (10)

  1. 一种可与碳基材料超组装的3,4-乙烯二氧噻吩聚合物，其结构通式如下式所示：
    Figure PCTCN2020094512-appb-100001
    其中，n为大于零的自然数。
  2. 一种如权利要求1所述的可与碳基材料超组装的3,4-乙烯二氧噻吩高分子聚合物制备方法，其特征在于，具体步骤为：
    (1)3,4-乙烯二氧噻吩1为原料，经溴代反应，制得2,5-二溴-3,4-乙烯二氧噻吩2；
    (2)将上述的2,5-二溴-3,4-乙烯二氧噻吩2与三甲基硅基乙炔反应，得到双三甲基硅基-3,4-乙烯二氧噻吩中间体3，双三甲基硅基-3,4-乙烯二氧噻吩中间体3脱除TMS后得到双端炔-3,4-乙烯二氧噻吩中间体4；
    (3)将双端炔-3,4-乙烯二氧噻吩中间体4与2,5-二溴-3,4-乙烯二氧噻吩2发生Sonogashira偶联反应，生成的产物即为3,4-乙烯二氧噻吩聚合物5。
  3. 如权利要求2的制备方法，其特征在于，所述Sonogashira偶联反应的具体步骤为：在氮气保护下，将2,5-二溴-3,4-乙烯二氧噻吩2、双端炔-3,4-乙烯二氧噻吩中间体4、CuI、四三苯基膦钯、三苯基膦加入反应瓶中，再加入甲苯、三乙胺；氮气置换后，于高温下反应、冷却、萃取、干燥、浓缩，得到黄色粘液，再经甲醇/四氢呋喃沉淀法得到黄色固体粉末。
  4. 根据权利要求3所述的制备方法，其特征在于，所述高温下反应的温度为65～75℃。
  5. 根据权利要求4所述的制备方法，其特征在于，所述高温下反应的温度为70℃。
  6. 根据权利要求5所述的制备方法，其特征在于，所述高温下反应的 时间为24小时。
  7. 如权利要求2或3的制备方法，其特征在于，所述溴代反应用溴化剂为溴水，所述3,4-乙烯二氧噻吩1与溴水的摩尔比为1：(2.0～2.5)。
  8. 根据权利要求7所述的制备方法，其特征在于，所述3,4-乙烯二氧噻吩1与溴水的摩尔比为1：(2.1～2.5)。
  9. 一种碳纳米管超分子自组装体系，其功能物质为权利要求1所述的3,4-乙烯二氧噻吩聚合物中的任意一种。
  10. 如权利要求1所述的3,4-乙烯二氧噻吩聚合物、如权利要求9所述的碳纳米管超分子自组装体系在复合材料中的应用。
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