WO2020244608A1 - 可与碳纳米管有序超组装的噻吩乙炔基聚合物及制备方法 - Google Patents

可与碳纳米管有序超组装的噻吩乙炔基聚合物及制备方法 Download PDF

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WO2020244608A1
WO2020244608A1 PCT/CN2020/094511 CN2020094511W WO2020244608A1 WO 2020244608 A1 WO2020244608 A1 WO 2020244608A1 CN 2020094511 W CN2020094511 W CN 2020094511W WO 2020244608 A1 WO2020244608 A1 WO 2020244608A1
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thiophene
dialkoxythiophene
preparation
ethynyl
dibromo
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孔彪
谢磊
李继超
曾洁
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Fudan University
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    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/415—Sonogashira / Hagihara reactions

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  • the invention belongs to the technical field of organic supramolecular materials, and specifically relates to a thiophene ethynyl polymer capable of orderly super-assembly with carbon nanotubes 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 one-dimensional nanomaterial with a hexagonal structure as the main connecting group.
  • the surface is rich in ⁇ electrons and has excellent mechanical, electrical and chemical properties. It is widely used in the preparation of military and civilian applications.
  • Carbon nanotubes have single-wall and multi-wall. 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.
  • the chemical structure of carbon nanotubes is very stable, which also makes the interface bond not strong when combined with the composite body, which limits the excellent performance of composite materials and restricts the industrial use of carbon nanotubes.
  • the present invention provides a thiopheneethynyl polymer with good stability and orderly super-assembly with carbon nanotubes and a preparation method thereof.
  • the thiophene ethynyl polymer that can be super-assembled with carbon nanotubes in the present invention is a high molecular polymer with thiophene-2-acetylene as the main chain and alkoxy as the side chain.
  • the polymer can be combined with Carbon nanotubes of different sizes can form a supramolecular self-assembly system through main chain ⁇ - ⁇ adsorption and side chain entanglement.
  • the thiophene acetylene-based polymer/carbon nanotube composite formed by the super-assembled system has good stability. It has good application prospects in composite materials.
  • the thiophene ethynyl polymer that can be super-assembled with carbon nanotubes in the present invention has a general structural formula shown in formula 1:
  • n is a natural number greater than zero, and the R group is C 4 H 9 or C 6 H 13 .
  • the present invention also provides a method for preparing the above-mentioned thiopheneethynyl polymer that can be super-assembled with carbon nanotubes in an orderly manner, and the specific steps are:
  • 3,4-dialkoxythiophene is prepared under alkaline conditions, and then brominated reaction to prepare 2,5-dibromo-3,4- Dialkoxythiophene;
  • the specific steps of the Sonogashira cross-coupling reaction are: under the protection of nitrogen, 2,5-dibromo-3,4-dialkoxythiophene, double-terminal acetylenic thiophene intermediate, CuI, Tetratriphenylphosphine palladium and triphenylphosphine are added to the reaction flask, and then toluene and triethylamine are added. After nitrogen replacement, react at a high temperature (65-75°C (preferably 70°C)), and then undergo extraction, drying, and concentration treatments to obtain a yellow viscous liquid, and then undergo repeated methanol/tetrahydrofuran precipitation to obtain a yellow solid powder.
  • a high temperature 65-75°C (preferably 70°C)
  • the 3,4-dialkoxythiophene is 3,4-dibutoxythiophene or 3,4-dihexoxythiophene.
  • the molar ratio of the 3,4-dialkoxythiophene to bromine is 1: (2.1-2.5).
  • the present invention also provides a thiophene ethynyl polymer synthesized by any of the above methods and capable of orderly super-assembly with carbon nanotubes.
  • the present invention also provides a carbon nanotube supramolecular self-assembly system, and the functional substance in the self-assembly system is any of the above-mentioned thiophene ethynyl polymers.
  • the present invention also provides the application of any of the above-mentioned thiophene ethynyl polymers or carbon nanotube supramolecular self-assembly systems in the preparation of carbon nanotube composite materials.
  • the present invention provides a high molecular weight polymer based on thiophene acetylene. Under the action of conventional organic solvents, carbon nanotubes can be effectively dispersed, which can promote the application of carbon nanotubes in composite materials, and has 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 3,4-dialkoxythiophene 2a
  • Figure 2 is the NMR spectrum of 2,5-dibromo-3,4-dialkoxythiophene 3a;
  • Figure 3 is a nuclear magnetic resonance spectrum of bistrimethylsilylthiophene intermediate 4a
  • Figure 4 is the NMR spectrum of the double-end acetylenic thiophene intermediate 5a;
  • Figure 5 is a NMR spectrum of the thiophene ethynyl polymer 6a.
  • the intermediate 2a is a colorless liquid.

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Abstract

本发明属于有机超分子材料技术领域，具体为一种可与碳纳米管有序超组装的噻吩乙炔基聚合物及其制备方法。本发明聚合物的主链为噻吩-2-乙炔、侧链为含有不同长度碳链的烷氧基。其制备方法为：以3,4-二羟基噻吩为起始原料，经醚化反应，再经溴化反应得到2,5-二溴-3,4-二烷氧基噻吩；再与三甲基硅基乙炔反应得到双三甲基硅基噻吩中间体；再脱除TMS保护基后得到双端炔噻吩中间体，再与2,5-二溴-3,4-二烷氧基噻吩发生Sonogashira交叉偶联反应得到噻吩乙炔基聚合物。本发明的噻吩乙炔基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，形成的复合物具有良好的稳定性，具有良好的应用前景。

Description

可与碳纳米管有序超组装的噻吩乙炔基聚合物及制备方法
本申请要求于2019年6月5日提交中国专利局、申请号为201910488504.5、发明名称为“可与碳纳米管有序超组装的噻吩乙炔基聚合物及制备方法”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材料技术领域，具体涉及一种可与碳纳米管有序超组装的噻吩乙炔基聚合物及制备方法。
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一维纳米材料，表面具有丰富的π电子，具有优异的力学、电学和化学性能，是广泛应用于制备军事、民用方面质轻高强的复合材料。碳纳米管有单壁和多壁，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。同时，碳纳米管的化学结构十分稳定，这也使其在与复合物本体复合时界面结合并不牢固，从而限制了复合材料的优异性能的发挥，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，本发明提供一种稳定性好、可与碳纳米管有序超组装的噻吩乙炔基聚合物及其制备方法。
本发明提供的可与碳纳米管有序超组装的噻吩乙炔基聚合物，是以噻吩-2-乙炔为主链的、以烷氧基为侧链的高分子聚合物，该聚合物可与不同尺寸的碳纳米管之间可通过主链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噻吩乙炔基聚合物/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纳米管有序超组装的噻吩乙炔基聚合物，其结构通式如式1所示：
Figure PCTCN2020094511-appb-000001
其中，n为大于零的自然数，R基团为C 4H 9或C 6H 13。
本发明还提供上述可与碳纳米管有序超组装的噻吩乙炔基聚合物的制备方法，具体步骤为：
(1)以3,4-二羟基噻吩为原料，在碱性条件下制得3,4-二烷氧基噻吩，再经溴代反应，制得2,5-二溴-3,4-二烷氧基噻吩；
(2)将上述的2,5-二溴-3,4-二烷氧基噻吩与三甲基硅基乙炔反应，得到双三甲基硅基噻吩中间体，双三甲基硅基噻吩中间体脱除TMS后得到双端炔噻吩中间体；
(3)将双端炔噻吩中间体与2,5-二溴-3,4-二烷氧基噻吩发生Sonogashira交叉偶联反应，生成的产物即为噻吩乙炔基聚合物。
在一些实施例中，所述Sonogashira交叉偶联反应的具体步骤为：在氮气保护下，将2,5-二溴-3,4-二烷氧基噻吩、双端炔噻吩中间体、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、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3,4-二烷氧基噻吩为3,4-二丁氧基噻吩或3,4-二己氧基噻吩。
在一些实施例中，所述3,4-二烷氧基噻吩与溴的摩尔比为1：(2.1～2.5)。
本发明还提供任一上述方法合成的可与碳纳米管有序超组装的噻吩乙炔基聚合物。
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任一上述的噻吩乙炔基聚合物。
本发明还提供了任一上述噻吩乙炔基聚合物或碳纳米管超分子自组 装体系在制备碳纳米管复合材料中的应用。
本发明的有益效果
(1)本发明所提供的噻吩乙炔基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噻吩乙炔的高分子聚合物，该聚合物在常规有机溶剂的作用下，能有效地分散碳纳米管，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3,4-二烷氧基噻吩2a的核磁共振谱图；
图2是2,5-二溴-3,4-二烷氧基噻吩3a的核磁共振谱图；
图3是双三甲基硅基噻吩中间体4a的核磁共振谱图；
图4是双端炔噻吩中间体5a的核磁共振谱图；
图5是噻吩乙炔基聚合物6a的核磁共振谱图。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本申请提供进一步的说明。说明书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
噻吩乙炔基高分子聚合物6a的制备流程如式A所示：
Figure PCTCN2020094511-appb-000002
中间体2a～5a的合成参照Chem.Eur.J.2011,17,1473-1484.报道的步骤进行。
中间体2a为无色液体。 1H NMR(500MHz,Chloroform-d)δ6.34(s,2H),4.02(t,J＝6.1Hz,4H),1.81–1.69(m,4H),1.58–1.46(m,4H),0.96(t,J＝7.6Hz,6H).
中间体3a为白色固体。 1H NMR(500MHz,Chloroform-d)δ4.08(t,J＝6.1Hz,4H),1.79–1.69(m,4H),1.58–1.49(m,4H),0.97(t,J＝7.6Hz,6H).
中间体4a，白色固体。 1H NMR(500MHz,Chloroform-d)δ4.09(t,J＝6.1Hz,4H),1.77–1.67(m,4H),1.49–1.39(m,4H),0.95(t,J＝7.6Hz,6H),0.25(s,18H).
中间体5a，白色固体。 1H NMR(500MHz,Chloroform-d)δ4.07(t,J＝6.1Hz,4H),3.32(s,2H),1.79–1.72(m,4H),1.57–1.47(m,4H),0.96(t,J＝7.6Hz,6H).
聚合物6a：在氮气保护下，向干燥的250mL三口烧瓶中加入中间体3a(3.84g,10mmol)，中间体5a(2.76g,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/四氢呋喃重结晶得到黄绿色固体粉末4.4g。1H NMR(500MHz,Chloroform-d)δ4.03(ddt,J＝9.1,6.3,3.4Hz,20H),2.20(s, 2H),1.99(s,2H),1.79-1.73(m,20H),1.55-1.49(m,20H),0.99-0.94(m,30H)。

Claims (9)

  1. 一种可与碳纳米管有序超组装体系的噻吩乙炔基聚合物，结构通式如式1所示：
    Figure PCTCN2020094511-appb-100001
    其中，n为大于零的自然数，R基团为-C 4H 9或-C 6H 13。
  2. 一种如权利要求1所述的噻吩乙炔基聚合物制备方法，其特征在于，具体步骤为：
    (1)3,4-二羟基噻吩为原料，在碱性条件下制得3,4-二烷氧基噻吩，再经溴代反应，制得2,5-二溴-3,4-二烷氧基噻吩；所述3,4-二烷氧基噻吩的烷氧基为-OC 4H 9或-OC 6H 13；
    (2)将所述2,5-二溴-3,4-二烷氧基噻吩与三甲基硅基乙炔反应，得到双三甲基硅基噻吩中间体，所述双三甲基硅基噻吩中间体脱除TMS后得到双端炔噻吩中间体；
    (3)将所述双端炔噻吩中间体与2,5-二溴-3,4-二烷氧基噻吩发生Sonogashira交叉偶联反应，生成的产物即为噻吩乙炔基聚合物。
  3. 如权利要求2的制备方法，其特征在于，所述Sonogashira交叉偶联反应的具体步骤为：在氮气保护下，将双端炔噻吩中间体、2,5-二溴-3,4-二烷氧基噻吩、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. 如权利要求3的制备方法，其特征在于，所述双端炔噻吩中间体、2,5-二溴-3,4-二烷氧基噻吩、CuI、四三苯基膦钯和三苯基膦的摩尔比为10:10:1:0.2:0.5。
  5. 如权利要求3的制备方法，其特征在于，所述3,4-二烷氧基噻吩为3,4-二丁氧基噻吩或3,4-二己氧基噻吩。
  6. 如权利要求2的制备方法，其特征在于，所述溴代反应为3,4-二烷氧基噻吩与溴水反应，所述3,4-双烷氧基噻吩与溴水的摩尔比为1： (2.0～2.5)。
  7. 如权利要求3的制备方法，其特征在于，所述高温下反应的温度为60～75℃。
  8. 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所述的噻吩乙炔基聚合物中的任意一种或权利要求2～7任意一项制备方法制备得到的噻吩乙炔基聚合物任意一种。
  9. 如权利要求1所述的噻吩乙炔基聚合物或权利要求2～7任意一项制备方法制备得到的噻吩乙炔基聚合物、如权利要求8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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