CN105820317B - 一种序列可控的三嵌段共聚物的制备方法 - Google Patents

一种序列可控的三嵌段共聚物的制备方法 Download PDF

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CN105820317B
CN105820317B CN201610305108.0A CN201610305108A CN105820317B CN 105820317 B CN105820317 B CN 105820317B CN 201610305108 A CN201610305108 A CN 201610305108A CN 105820317 B CN105820317 B CN 105820317B
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吴宗铨
余志鹏
刘娜
周丽
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Hefei University of Technology
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Abstract

本发明提供了一种序列可控的三嵌段共聚物的一锅法制备方法，利用二价镍盐为单一催化剂，顺序加入共轭结构单体a，联烯单体b，异腈单体c，机理不同的得到一系列abc型共聚物，其聚合过程活性可控，产物结构明确且易分离。并且，通过改变单体的投料顺序，本发明还制备了bac、acb型共聚物，实现了序列可控聚合。

Description

一种序列可控的三嵌段共聚物的制备方法
技术领域
本发明属于高分子材料技术领域，具体涉及一种序列可控的三嵌段共聚物的制备方法及其及其在发光材料上的应用。
背景技术
碱基对有序排列的DNA在生物信息的遗传、繁衍等方面起到决定性的用。基于此，序列可控的聚合物(Sequence-Controlled Polymers)的合成备受关注。通过控制高分子的精密结构，建立精确控制聚合物单体序列的新方法，深入揭示聚合物结构与性能的关系。从本质上理解单个高分子链内及高分子链间的相互作用，实现单个或几个高分子链的可控链折叠和精密自组装，发展新型功能材料。目前报道的序列可控的聚合物的合成方法，主要分为生物合成与化学合成。其中，化学合成法底物多样性高，日益受到科学家的广泛关注。
目前化学合成序列可控的聚合物的方法大概可分为固相法、模板法、逐步反应法和链式反应法。其中，模板聚合与固相合成需要特殊的反应体系，合成相对复杂并且聚合效率不高。而利用click反应等实现的逐步聚合法只适用于制备周期序列高分子，合成、纯化难度较大，并且难以控制链段长度。链式聚合的活性中心包括自由基、正/负离子、配位点等高反应性物种，单体聚合通常较快。在序列可控聚合上，展现了其独特的优势。
因此，建立一种新型序列可控的方法是当前科研领域的一个难点。
发明内容
针对现有技术的不足，本发明提供了一种序列可控的三嵌段共聚物的制备方法。
为了实现上述目的，本发明提供如下技术方案：
一种序列可控的三嵌段共聚物的制备方法，包括以下步骤：
A、在单体a的THF溶液中加入Ni(II)催化剂，搅拌反应，凝胶渗透色谱跟踪反应至分子链不再增长；
B、单体b溶于THF中，加入步骤A所得溶液，20～30℃反应，凝胶渗透色谱跟踪至分子链不再增长；
C、单体c溶于THF中，加入步骤B所得溶液，20～30℃反应，凝胶渗透色谱跟踪至分子链不再增长；淬灭反应体系，浓缩后加入溶剂析出产物，离心后得到abc序列的三嵌段共聚物；
以上各步反应均在氮气保护下进行，其中单体a为共轭结构单体，单体b为联烯单体，单体c为异腈单体。
一种序列可控的三嵌段共聚物的制备方法，包括以下步骤：
A、单体b溶于THF中，搅拌半小时后，加入Ni(II)催化剂，20～30℃反应，凝胶渗透色谱跟踪反应，至分子链不再增长；
B、单体a的THF溶液加入步骤A所得溶液，20～30℃反应，凝胶渗透色谱跟踪反应，至分子链不再增长；
C、单体c溶于THF中，加入步骤B所得溶液，20～30℃反应，凝胶渗透色谱跟踪至分子链不再增长；淬灭反应体系，浓缩后加入溶剂析出产物，离心后得到bac序列的三嵌段共聚物；
以上各步反应均在氮气保护下进行，其中单体a为共轭结构单体，单体b为联烯单体，单体c为异腈单体。
一种序列可控的三嵌段共聚物的制备方法，包括以下步骤：
A、在单体a的THF溶液中加入Ni(II)催化剂，搅拌反应，凝胶渗透色谱跟踪反应至分子链不再增长；
B、单体c溶于THF中，加入步骤A所得溶液，20～30℃反应，凝胶渗透色谱跟踪至分子链不再增长；
C、单体b溶于THF中，加入步骤B所得溶液，20～30℃反应，凝胶渗透色谱跟踪至分子链不再增长；淬灭反应体系，浓缩后加入溶剂析出产物，离心后得到acb序列的三嵌段共聚物；
以上各步反应均在氮气保护下进行，其中单体a为共轭结构单体，单体b为联烯单体，单体c为异腈单体。
进一步地，所述单体a的结构式为：
进一步地，所述单体b的结构式为：
其中R2为
进一步地，所述单体c的结构式为：
其中R3为
进一步地，上述第1和3种序列可控的三嵌段共聚物的制备方法中所述Ni(II)催化剂的结构式为：
所述的溶剂为四氢呋喃，所述淬灭反应体系所用溶剂为醇类溶剂。
进一步地，上述第2种序列可控的三嵌段共聚物的制备方法中，所述Ni(II)催化剂的结构式为：
所述的溶剂为四氢呋喃，所述淬灭反应体系所用溶剂为醇类溶剂。
进一步地，所述单体a、单体b、单体c之间的物质的量之比为1：(0.1-10)：(0.1-10)。
进一步地，所述单体a与Ni(II)催化剂的物质的量之比为1：(0.01-0.5)。
本发明的有益效果在于，本发明利用一锅法、通过控制加料顺序，活性可控的聚合，得到序列可控的三嵌段共聚物。而且产物结构明确，易分离。
附图说明
图1、2、3分别为abc序列多嵌段共聚物、bac序列多嵌段共聚物、acb序列多嵌段共聚物的反应历程图；
其中：
图4为实施例1制备的abc型聚合物与其前驱体的的SEC图；
图5为实施例1制备的abc型聚合物与其前驱体的1H NMR图；
图6为实施例2制备的bca型聚合物与其前驱体的的SEC图；
图7为实施例3制备的acb型聚合物与其前驱体的的SEC图。
具体实施方式
实施例1
一种abc序列的三嵌段共聚物的制备方法，步骤包括：
A、氮气氛围下，2，5-二溴-3-己基噻吩溶于THF(96mg,0.2M)中，加入异丙基氯化镁(2.0mol/L，0.16mL，0.33mM)，20-30℃搅拌2h。得到单体a的THF溶液。然后加入Ni(dppp)Cl2(5.4mg，0.01mmol)，20-30℃下搅拌。凝胶渗透色谱(SEC)跟踪反应，至分子链不再增长。
B、十六烷基氧联烯(0.2M,十六烷基氧联烯与Ni(dppp)Cl2的摩尔比为40)溶于THF中，加入步骤A所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。
C、叔丁基异腈(0.2M,叔丁基异腈与Ni(dppp)Cl2的摩尔比为30)溶于THF中，加入步骤B所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。加入MeOH淬灭反应，浓缩后加入不良溶剂析出产物。离心后可得目标聚合物。
实施例2
一种abc序列的三嵌段共聚物的制备方法，步骤包括：
A、氮气氛围下，2，5-二溴-3-己基噻吩溶于THF(320mg,0.2M)中，加入异丙基氯化镁(2.0mol/L，0.56mL，1.1mM)，20-30℃搅拌2h。得到单体a的THF溶液。然后加入Ni(dppp)Cl2(5.4mg，0.01mmol)，20-30℃搅拌。凝胶渗透色谱(SEC)跟踪反应，至分子链不再增长。
B、十六烷基氧联烯(0.2M,十六烷基氧联烯与Ni(dppp)Cl2的摩尔比为10)溶于THF中，加入步骤A所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。
C、叔丁基异腈(0.2M,叔丁基异腈与Ni(dppp)Cl2的摩尔比为10)溶于THF中，加入步骤B所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。加入MeOH淬灭反应，浓缩后加入不良溶剂析出产物。离心后可得目标聚合物。
实施例3
一种abc序列的三嵌段共聚物的制备方法，步骤包括：
A、氮气氛围下，2，5-二溴-3-己基噻吩溶于THF(32mg,0.2M)中，加入异丙基氯化镁(2.0mol/L，0.06mL，0.11mM)，20-30℃搅拌2h。得到单体a的THF溶液。然后加入Ni(dppp)Cl2(5.4mg，0.01mmol)，20-30℃搅拌。凝胶渗透色谱(SEC)跟踪反应，至分子链不再增长。
B、十六烷基氧联烯(0.2M，十六烷基氧联烯与Ni(dppp)Cl2的摩尔比为100)溶于THF中，加入步骤A所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。
C、叔丁基异腈(0.2M，叔丁基异腈与Ni(dppp)Cl2的摩尔比为100)溶于THF中，加入步骤B所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。加入MeOH淬灭反应，浓缩后加入不良溶剂析出产物。离心后可得目标聚合物。
实施例4
一种bac序列的三嵌段共聚物的制备方法，步骤包括：
A、Ni(COD)250mg溶于7mL THF，加入50mL EtOCOCF3，搅拌20min后，加入48mg PPh3，搅拌过夜，制得π-烯丙基镍催化剂，备用。
B、十六烷基氧联烯(56mg，0.20M)溶于THF中，然后加入π-烯丙基镍催化剂(5.4mg，0.01mM)，20-30℃搅拌。凝胶渗透色谱(SEC)跟踪反应，至分子链不再增长。
C、2，5-二溴-3-己基噻吩(65mg，0.20M)溶于THF中，加入异丙基氯化镁(2.0mol/L，0.11mL，0.22mM)，20-30℃搅拌2h。得到单体a的THF溶液。然后加入步骤A所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。
D、叔丁基异腈(40mg，0.20M)溶于THF中，加入步骤B所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。加入MeOH淬灭反应，浓缩后加入不良溶剂析出产物。离心后可得目标聚合物。
实施例5
一种bac序列的三嵌段共聚物的制备方法，步骤包括：
A、Ni(COD)250mg溶于7mL THF，加入50mL EtOCOCF3，搅拌20min后，加入48mg PPh3，搅拌过夜，制得π-烯丙基镍催化剂，备用。
B、十六烷基氧联烯(28mg，0.10mM)溶于THF中，然后加入π-烯丙基镍催化剂(5.4mg，0.01mM)，20-30℃搅拌。凝胶渗透色谱(SEC)跟踪反应，至分子链不再增长。
C、2，5-二溴-3-己基噻吩(326mg，0.20M)溶于THF(1mL)中，加入异丙基氯化镁(2.0mol/L，0.56mL，1.1mmol)，20-30℃搅拌2h。得到单体a的THF溶液。然后加入步骤A所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。
D、叔丁基异腈(20mg，0.1mM)溶于THF中，加入步骤B所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。加入MeOH淬灭反应，浓缩后加入不良溶剂析出产物。离心后可得目标聚合物。
实施例6
一种bac序列的三嵌段共聚物的制备方法，步骤包括：
A、Ni(COD)250mg溶于7mL THF，加入50mL EtOCOCF3，搅拌20min后，加入48mg PPh3，搅拌过夜，制得π-烯丙基镍催化剂，备用。
B、十六烷基氧联烯(28mg，0.10mM)溶于THF中，然后加入π-烯丙基镍催化剂(5.4mg，0.01mM)，20-30℃搅拌。凝胶渗透色谱(SEC)跟踪反应，至分子链不再增长。
C、2，5-二溴-3-己基噻吩溶于THF中(32.6mg，0.20M)，加入异丙基氯化镁(2.0mol/L，0.06mL，0.11mmol)，20-30℃搅拌2h。得到单体a的THF溶液。然后加入步骤A所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。
D、叔丁基异腈(200mg，0.2M)溶于THF中，加入步骤B所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。加入MeOH淬灭反应，浓缩后加入不良溶剂析出产物。离心后可得目标聚合物。
实施例7
一种acb序列的三嵌段共聚物的制备方法，步骤包括：
A、氮气氛围下，2，5-二溴-3-己基噻吩(65mg，0.20mM)溶于THF(1mL)中，加入异丙基氯化镁(2.0mol/L，0.11mL，0.22mM)，20-30℃搅拌2h。得到单体a的THF溶液。加入Ni(dppp)Cl2(5.4mg，0.01mM)，20-30℃反应，SEC跟踪至分子链不再增长。
B、叔丁基异腈(40mg，0.2mM)溶于THF中，然后加入步骤A所得溶液，20-30℃搅拌。凝胶渗透色谱(SEC)跟踪反应，至分子链不再增长。
C、十六烷基氧联烯(56mg，0.20mM)溶于THF中，加入步骤B所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。加入MeOH淬灭反应，浓缩后加入不良溶剂析出产物。离心后可得目标聚合物。
实施例8
一种acb序列的三嵌段共聚物的制备方法，步骤包括：
A、氮气氛围下，2，5-二溴-3-己基噻吩(326mg，0.20M)溶于THF中，加入异丙基氯化镁(2.0mol/L，0.56mL，0.22mmol)，20-30℃搅拌2h。得到单体a的THF溶液。加入Ni(dppp)Cl2(5.4mg，0.01mM)，20-30℃反应，SEC跟踪至分子链不再增长。
B、叔丁基异腈(20mg，0.2M)溶于THF中，然后加入步骤A所得溶液，20-30℃搅拌。凝胶渗透色谱(SEC)跟踪反应，至分子链不再增长。
C、十六烷基氧联烯(28mg，0.20M)溶于THF中，加入步骤B所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。加入MeOH淬灭反应，浓缩后加入不良溶剂析出产物。离心后可得目标聚合物。
实施例9
一种acb序列的三嵌段共聚物的制备方法，步骤包括：
A、氮气氛围下，2，5-二溴-3-己基噻吩(32mg，0.20M)溶于THF中，加入异丙基氯化镁(2.0mol/L，0.05mL，0.11mM)，20-30℃搅拌2h。得到单体a的THF溶液。加入Ni(dppp)Cl2(5.4mg，0.01mM)，20-30℃反应，SEC跟踪至分子链不再增长。
B、叔丁基异腈(200mg，0.2M)溶于THF中，然后加入步骤A所得溶液，20-30℃搅拌。凝胶渗透色谱(SEC)跟踪反应，至分子链不再增长。
C、十六烷基氧联烯(28mg，0.20M)溶于THF中，加入步骤B所得溶液，20-30℃反应，SEC跟踪至分子链不再增长。加入MeOH淬灭反应，浓缩后加入不良溶剂析出产物。离心后可得目标聚合物。
上述参照实施例对序列可控的三嵌段共聚物的制备方法进行的详细描述，是说明性的而不是限定性的，可按照所限定范围列举出若干个实施例，因此在不脱离本发明总体构思下的变化和修改，应属本发明的保护范围之内。

Claims (10)

1.一种序列可控的三嵌段共聚物的制备方法，其特征在于，包括以下步骤：
A、在单体a的THF溶液中加入Ni(II)催化剂，搅拌反应，凝胶渗透色谱跟踪反应至分子链不再增长；
B、单体b溶于THF中，加入步骤A所得溶液，20～30℃反应，凝胶渗透色谱跟踪至分子链不再增长；
C、单体c溶于THF中，加入步骤B所得溶液，20～30℃反应，凝胶渗透色谱跟踪至分子链不再增长；淬灭反应体系，浓缩后加入溶剂析出产物，离心后得到abc序列的三嵌段共聚物；
以上各步反应均在氮气保护下进行，其中单体a为共轭结构单体，单体b为联烯单体，单体c为异腈单体。
2.一种序列可控的三嵌段共聚物的制备方法，其特征在于，包括以下步骤：
A、单体b溶于THF中，搅拌半小时后，加入Ni(II)催化剂，20～30℃反应，凝胶渗透色谱跟踪反应，至分子链不再增长；
B、单体a的THF溶液加入步骤A所得溶液，20～30℃反应，凝胶渗透色谱跟踪反应，至分子链不再增长；
C、单体c溶于THF中，加入步骤B所得溶液，20～30℃反应，凝胶渗透色谱跟踪至分子链不再增长；淬灭反应体系，浓缩后加入溶剂析出产物，离心后得到bac序列的三嵌段共聚物；
以上各步反应均在氮气保护下进行，其中单体a为共轭结构单体，单体b为联烯单体，单体c为异腈单体。
3.一种序列可控的三嵌段共聚物的制备方法，其特征在于，包括以下步骤：
A、在单体a的THF溶液中加入Ni(II)催化剂，搅拌反应，凝胶渗透色谱跟踪反应至分子链不再增长；
B、单体c溶于THF中，加入步骤A所得溶液，20～30℃反应，凝胶渗透色谱跟踪至分子链不再增长；
C、单体b溶于THF中，加入步骤B所得溶液，20～30℃反应，凝胶渗透色谱跟踪至分子链不再增长；淬灭反应体系，浓缩后加入溶剂析出产物，离心后得到acb序列的三嵌段共聚物；
以上各步反应均在氮气保护下进行，其中单体a为共轭结构单体，单体b为联烯单体，单体c为异腈单体。
4.根据权利要求1或2或3所述的序列可控的三嵌段共聚物的制备方法，其特征在于，所述单体a的结构式为：
5.根据权利要求1或2或3所述的序列可控的三嵌段共聚物的制备方法，其特征在于，所述单体b的结构式为：
其中R2为
6.根据权利要求1或2或3所述的序列可控的三嵌段共聚物的制备方法，其特征在于，所述单体c的结构式为：
其中R3为
7.根据权利要求1或3所述的序列可控的三嵌段共聚物的制备方法，其特征在于，所述Ni(II)催化剂的结构式为：
所述的溶剂为四氢呋喃，所述淬灭反应体系所用溶剂为醇类溶剂。
8.根据权利要求2所述的序列可控的三嵌段共聚物的制备方法，其特征在于，所述Ni(II)催化剂的结构式为：
所述的溶剂为四氢呋喃，所述淬灭反应体系所用溶剂为醇类溶剂。
9.根据权利要求1或2或3所述的序列可控的三嵌段共聚物的制备方法，其特征在于，所述单体a、单体b、单体c之间的物质的量之比为1：(0.1-10)：(0.1-10)。
10.根据权利要求1或2或3所述的序列可控的三嵌段共聚物的制备方法，其特征在于，所述单体a与Ni(II)催化剂的物质的量之比为1：(0.01-0.5)。
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