CN114369231B - 一种聚异腈苯乙烯主链/hemiphasmid型液晶基元的侧链液晶高分子 - Google Patents
一种聚异腈苯乙烯主链/hemiphasmid型液晶基元的侧链液晶高分子 Download PDFInfo
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Abstract
本发明公开了一种聚异腈苯乙烯主链/hemiphasmid型液晶基元的侧链液晶高分子（VI‑n，n=4―12），其主链与液晶基元之间通过较短的间隔基相连。随烷基尾链长度增加，聚合物（VI‑n）从层状液晶相（n=4）演变为柱状液晶相（n=8,12）。聚合物（VI‑n）的主链为典型的螺旋高分子，液晶基元的接枝密度高，主链与液晶基元间的间隔基短。这三个结构因素提高了聚合物（VI‑n）的液晶相的热稳定性，以致液晶相在样品分解温度（～350°C）以下稳定存在。因而，本发明聚合物（VI‑n）是一种很好的耐高温液晶材料。
Description
技术领域
本发明涉及一种聚异腈苯乙烯主链/hemiphasmid型液晶基元的侧链液晶高分子，属于耐热液晶高分子材料技术领域。
背景技术
小分子液晶基元可粗分为棒状和盘状两大类。其它形状的液晶基元，如香蕉状液晶基元、hemiphasmid型液晶基元可看作棒状和盘状液晶基元的某种组合。例如，hemiphasmid型液晶基元的一端为盘状液晶基元，另一端为棒状液晶基元，因而可看作二者的“杂化”液晶基元。
把小分子液晶基元连接于高分子主链可以得到侧链液晶高分子(SCLCPs)。SCLCPs兼具小分子液晶的功能性、高分子的加工性、以及侧链高分子的化学结构和凝聚态结构可调性的优点，因而其在液晶显示、光电器件、智能材料等领域有重要应用价值。由于升高温度不利于液晶基元的有序排列，所以SCLCPs的液晶相的稳定性随温度升高而降低，在较高温度下失去液晶性。这一缺点大大限制了SCLCPs在高温条件下的应用。
上世纪80年代末，周其凤等提出了SCLCPs设计的新思路，即把棒状液晶基元作为侧基通过足够短的连接基团横挂到高分子主链上。由于侧基离主链很近，棒状侧基排列对空间的要求(“甲壳效应”)迫使主链伸展，以致主链和侧基作为一个整体形成一根柱子，进而形成柱状液晶相。周其凤等把这类SCLCPs称之为甲壳型液晶高分子(MJLCPs)。研究表明，MJLCPs的液晶相通常可以在高温下(比如200℃以上)稳定存在，是一种耐高温液晶材料。然而，MJLCPs通常在低温下(即玻璃化转变温度以下)液晶相难以发育，液晶相有序度低。目前，低温和高温都具有稳定液晶相的SCLCPs依旧缺乏。
发明内容
针对以上问题，本发明的目的是提供一种低温和高温都具有稳定液晶相的聚异腈苯乙烯主链/hemiphasmid型液晶基元的侧链液晶高分子。
为实现上述目的，本发明具有如下技术方案：
一种聚异腈苯乙烯主链/hemiphasmid型液晶基元的SCLCPs，其主链为典型的螺旋高分子；侧链液晶基元接枝密度高；主链与侧链液晶基元之间的间隔基短，具体结构如如式(VI-n)所示：
其中n为介于4和12之间的自然数。
一种聚异腈苯乙烯主链/hemiphasmid型液晶基元的SCLCPs(VI-n)的制备方法，包括如下步骤：
(1)化合物(I-n)、4'-羟基-4-联苯基羧酸甲酯、碳酸钾、四丁基溴化铵(TBAB)的混合物在丙酮中回流24h；旋蒸除去丙酮，剩余物经二氯甲烷(DCM)萃取、饱和NaCl水溶液洗涤、无水NaSO4干燥，旋蒸除去DCM得到粗品，再在乙醇中重结晶两次得到纯品；纯品、KOH在乙醇/H2O(V/V＝3)中回流4h，盐酸酸化，旋蒸除去乙醇，过滤得到化合物(II-n)；
(2)化合物(II-n)、2-溴乙醇、K2CO3、KI在N,N-二甲基甲酰胺(DMF)中于80℃下搅拌24h；旋蒸除去DMF，剩余物再经柱层析分离(洗脱剂：EtOAc/石油醚＝1:3)、真空干燥得到化合物(III-n)；
(3)化合物(III-n)、4-甲酰胺基苯甲酸、DCC、DMAP在DCM中于室温下搅拌24小时；过滤除去反应液中的不溶物，旋蒸除去滤液中的DCM得到剩余物，剩余物再经柱层析分离(洗脱剂：EtOAc/石油醚＝2:3)，真空干燥得到化合物(IV-n)；
(4)Schlenk反应瓶经抽真空-充氮气循环两次，然后在充氮气循环中加入化合物(IV-n)和三光气(BTC)，再通过注射器加入干燥Et3N和DCM，在冰盐浴下反应4h；反应液经DCM萃取、饱和NaHCO3水溶液洗涤、饱和NaCl水溶液洗涤、无水Na2SO4干燥，旋蒸除去有机相得到粗品；粗品再经柱层析分离(洗脱剂：DCM)、真空干燥得到化合物(V-n)；
(5)Schlenk反应瓶经抽真空―充氮气循环两次，然后在充氮气循环中加入单体(V-n)和Ni(ClO4)2·6H2O，再通过注射器加入干燥的、除气的DCM，室温聚合24h；将反应液滴入CH3OH/DCM(V/V＝3)中，过滤得到粗品，再重复溶解―沉淀―过滤两次，真空干燥得到聚合物(VI-n)；
反应方程式：
其中n为介于4和12之间的自然数。
对上述聚合物(VI-n)进行液晶相结构分析。
对上述聚合物(VI-n)的液晶相进行热稳定性分析。
本发明的有益效果：
(1)本发明所述聚异腈苯乙烯主链/hemiphasmid型液晶基元的SCLCPs(VI-n)，可形成层状液晶相(n＝4)和柱状液晶相(n＝8,12)，液晶相结构易于调控。
(2)与传统SCLCPs相比，本发明所述SCLCPs(VI-n)的主链为典型的螺旋高分子，液晶基元的接枝密度高，主链与液晶基元间的间隔基短。这三个结构因素提高了液晶相的热稳定性，以致液晶相在样品分解温度(～350℃)以下稳定存在。因而，本发明所述SCLCPs(VI-n)是一种很好的耐高温液晶材料。
附图说明
图1.单体(V-12)的1H NMR图；
图2.聚合物(VI-12)的1H NMR图；
图3.聚合物(VI-12)的GPC图；
图4.单体(V-4)的1H NMR图；
图5.聚合物(VI-4)的1H NMR图；
图6.单体(V-8)的1H NMR图；
图7.聚合物(VI-8)的1H NMR图；
图8.聚合物(VI-n)的TG图；
图9(a).聚合物(VI-4)在室温(25℃)下的PLM图；
图9(b).聚合物(VI-8)在室温(25℃)下的PLM图；
图9(c).聚合物(VI-12)在室温(25℃)下的PLM图；
图10.聚合物(VI-n)在室温下的1D XRD图；
图11(a).聚合物(VI-4)在300℃的PLM图；
图11(b).聚合物(VI-8)在300℃的PLM图；
图11(c).聚合物(VI-12)在300℃的PLM图；
图12.聚合物(VI-12)在300℃的1D XRD图。
具体实施方式
下面结合试试对本发明作进一步详细的说明。
除特别说明外，本发明所有测试发生在25℃的室温环境。
核磁共振(NMR)：1H NMR测试所用仪器为ARX400(Bruker)，溶剂为氘代氯仿(CDCl3)，内标为四甲基硅烷(TMS)。
凝胶渗透色谱(GPC)：GPC测试采用Waters 515凝胶渗透色谱仪，样品浓度为10mg/mL，淋洗剂为四氢呋喃(THF)，流速为1.0mL/min，柱温为35℃，工作曲线通过聚苯乙烯标定。
一维X-射线衍射(1D-XRD)：1D-XRD测试采用高通量小角X射线散射仪(Anton PaarSAXSess)，同时收集小角和广角散射信息(2θ＝0.1―40.0°)，X-射线波长(λ)为0.154nm，散射矢量q＝4πsinθ/λ，控温范围为室温至350℃。
偏光显微镜(PLM)：样品织构观察采用Leica DML偏光显微镜，通过Mettler热台控温，通过熔融法得到薄膜样品。
热失重(TG)：TG测试采用美国TA Q5000 IR热失重分析仪，温度范围为室温至800℃，升温速率为10℃/min。
实施例1
一种聚异腈苯乙烯主链/hemiphasmid型液晶基元的SCLCP(VI-12)的制备方法，包括如下步骤：
(1)化合物(I-12)的合成
没食子酸甲酯5.00g、1-溴正十二烷22.33g、K2CO3 11.26g、四丁基溴化铵(TBAB)0.50g、丙酮200mL加入500mL反应瓶中，混合液回流直至目食子酸甲酯消耗完毕。反应液经旋蒸得到剩余物，剩余物依次经DCM萃取、饱和NaCl水溶液洗涤、无水Na2SO4干燥、旋蒸、真空干燥得到粗品。上述粗品、LiAlH4 2.06g、THF 200mL加入500mL反应瓶中，混合液在氮气保护下回流2h。反应液在冰浴下经稀盐酸调节PH值至～2，静置2h后倒出上层清液，再经旋蒸、真空干燥得到粗品。上述粗品、DCM 100mL加入250mL反应瓶中，依次滴入SOCl2 6.46g、DMF2滴，混合液在氮气保护下室温搅拌1h。反应液经旋蒸得到白色固体，再通过丙酮重结晶、真空干燥得到化合物(I-12)(13.80g，产率75％)。(2)化合物(II-12)的合成
化合物(I-12)10.00g、4'-羟基-4-联苯基羧酸甲酯3.36g、TBAB 0.20g、丙酮100mL加入250mL圆底烧瓶中，回流反应24h。反应液经旋蒸除去丙酮得到固体剩余物。剩余物依次经DCM萃取、饱和NaCl水溶液洗涤、无水NaSO4干燥得到粗品，再在乙醇中重结晶得到粗品。以上纯品10.00g、KOH 1.5g在150ml乙醇/水(V/V＝3)中回流2h。反应液经稀盐酸酸化至PH值～2，旋蒸除去大部分乙醇，过滤、真空干燥得到化合物(II-12)(8.86g，90％)。
(3)化合物(III-12)的合成
化合物(II-12)8.00g、1-溴乙醇1.43g、K2CO3 2.58g、催化量KI、DMF 50mL加入100mL圆底烧瓶中，混合液在80℃搅拌24h。反应液经旋蒸除去DMF，剩余物经柱层析分离(洗脱剂：EtOAc/石油醚＝1:3)、真空干燥得化合物(III-12)(7.00g，产率82％)。
(4)化合物(IV-12)的合成
化合物(III-12)5.00g、4-甲醛酰胺基苯甲酸0.85g、DCC 2.11g、DMAP 0.12g、干燥DCM 50mL加入100mL反应瓶中，室温搅拌24h。反应液经过滤除去不溶物，滤液经旋蒸得到剩余物，再经柱层析分离(洗脱剂：EtOAc/石油醚＝2:3)、真空干燥得到化合物(IV-12)(3.26g，产率60％)。
(5)化合物(V-12)的合成
50mL Schlenk瓶经抽真空-充氮气循环两次，然后在充氮气循环中加入化合物(IV-12)3.00g(2.82mmol)和BTC 4.60g(1.55mmol)，再通过注射器依次加入干燥DCM 30mL、三乙胺0.57g(5.62mmol)。反应混合液在氮气保护下于冰盐浴中反应4h。反应液经DCM萃取，再依次经饱和NaHCO3水溶液洗涤、饱和NaCl水溶液洗涤、无水Na2SO4干燥、旋蒸得到粗品。以上粗品经柱层析分离(洗脱剂为DCM)、真空干燥得到单体(V-12)(1.77g，60％)。1H NMR分析结果(图1)表明单体V-12的化学结构正确。
(6)聚合物(VI-12)的合成
10mL Schlenk瓶经抽真空―充氮气循环两次，然后在充氮气循环中加入单体(V-12)300mg和Ni(ClO4)2·6H2O 1.06mg，再通过注射器加入干燥的、除气的DCM 3mL。混合液在氮气保护下于室温搅拌24h。反应液滴入50mL CH3OH/DCM(1/3，V/V)中，过滤得到聚合物粗品，再经溶解―沉淀―过滤循环两次，最后真空干燥得到聚合物(VI-12)(240mg，产率80％)。1H NMR分析结果(图2)表明单体(V-12)成功聚合，聚合物(VI-12)结构正确。GPC分析结果(图3)表明，聚合物(VI-12)数均分子量为8.14×104g/mol，分子量分布指数(PDI)为1.25。
实施例2
一种聚异腈苯乙烯主链/hemiphasmid型液晶基元的SCLCP(VI-4)的制备方法，包括如下步骤：
用1-溴正丁烷代替实施例1中步骤(1)中的1-溴正十二烷，其它同实施例1。单体(V-4)和聚合物(VI-4)的1H NMR结果分别见图4和图5。GPC分析结果(图3)表明，聚合物(VI-4)数均分子量为9.03×104g/mol，PDI为1.19。
实施例3
一种聚异腈苯乙烯主链/hemiphasmid型液晶基元的SCLCP(VI-8)的制备方法，包括如下步骤：
用1-溴正辛烷代替实施例1中步骤(1)中的1-溴正十二烷，其它同实施例1。单体(V-8)和聚合物(VI-8)的1H NMR结果分别见图6和图7。GPC分析结果(图3)表明，聚合物(VI-8)数均分子量为8.21×104g/mol，PDI为1.22。
对上述实施例中的SCLCPs(VI-n)的进行热稳定性分析。
TG分析结果(图8)表明，本发明所述SCLCPs(VI-n)热稳定性较好，其热分解温度(物质分解5％时的温度)分别为367(n＝4)、369(n＝8)和374℃(n＝12)。
对上述实施例中的SCLCPs(VI-n)的室温液晶相结构分析。
室温PLM分析结果(图9(a)-图9(c))表明，本发明所述SCLCPs(VI-n)在室温下具有液晶性质。由室温1D XRD结果(图10)可知，聚合物(VI-4)的低角衍射矢量q之比为1:2:3，因而其形成层状液晶相；聚合物(VI-8)和(VI-12)的低角衍射矢量q之比为因而其形成六方柱状液晶相。
对上述实施例中的SCLCPs(VI-n)的液晶相的热稳定性分析。
变温PLM分析结果表明，本发明所述SCLCPs(VI-n)从室温到350℃呈现双折射性质，形成稳定液晶相。其在350℃的PLM照片见图11(a)-图11(c)。以聚合物(VI-12)为例，我们通过变温1D XRD研究了其柱状液晶相的热稳定性(图12)。聚合物(VI-12)在300℃时的低角衍射q之比为低角衍射强度与室温变化不大(图12和10)。这表明聚合物(VI-12)在高温下依然保持六方柱状液晶相，这与PLM的织构观察结果一致(图9和11)。
综上，本发明所述SCLCPs(VI-n)热稳定性好，可形成层状液晶相和柱状液晶相，液晶相从室温(即低温)至350℃稳定存在，是一类低温和高温都具有稳定液晶相的SCLCPs。这一性质在传统的SCLCPs和MJLCPs中难以具备。本发明所述SCLCPs(VI-n)独特的液晶性质源于其特殊的化学结构：主链为典型的螺旋高分子；侧链液晶基元接枝密度高；主链与侧链液晶基元之间的间隔基短。因而，本发明所述SCLCPs(VI-n)在耐热液晶材料领域有潜在应用。
Claims (5)
1.一种聚异腈苯乙烯主链/hemiphasmid型液晶基元的侧链液晶高分子，具有下式(VI-n)的结构：
其中，n为介于4和12之间的自然数。
2.权利要求1所述的液晶高分子化合物的制备方法，其特征在于，反应方程式如下：
3.根据权利要求2所述的液晶高分子的制备方法，其特征在于，包括如下步骤：
(1)将化合物(I-n)、4'-羟基-4-联苯基羧酸甲酯、碳酸钾、四丁基溴化铵TBAB的混合物在丙酮中回流24h；旋蒸除去丙酮，剩余物经二氯甲烷DCM萃取、饱和NaCl水溶液洗涤、无水NaSO4干燥，旋蒸除去DCM得到粗品，再在乙醇中重结晶两次得到纯品；纯品、KOH在乙醇/H2O(V/V＝3)中回流4h，盐酸酸化，旋蒸除去乙醇，过滤得到化合物(II-n)；
(2)将化合物(II-n)、2-溴乙醇、K2CO3、KI置于N,N-二甲基甲酰胺DMF中于80℃下搅拌24h；旋蒸除去DMF，剩余物再经柱层析分离(洗脱剂：EtOAc/石油醚＝1:3)、真空干燥得到化合物(III-n)；
(3)将化合物(III-n)、4-甲酰胺基苯甲酸、DCC、DMAP在DCM中于室温下搅拌24小时；过滤除去反应液中的不溶物，旋蒸除去滤液中的DCM得到剩余物，剩余物再经柱层析分离(洗脱剂：EtOAc/石油醚＝2:3)，真空干燥得到化合物(IV-n)；
(4)Schlenk反应瓶经抽真空-充氮气循环两次，然后在充氮气循环中加入化合物(IV-n)和三光气(BTC)，再通过注射器加入干燥Et3N和DCM，在冰盐浴下反应4h；反应液经DCM萃取、饱和NaHCO3水溶液洗涤、饱和NaCl水溶液洗涤、无水Na2SO4干燥，旋蒸除去有机相得到粗品；粗品再经柱层析分离(洗脱剂：DCM)、真空干燥得到化合物(V-n)；
(5)Schlenk反应瓶经抽真空―充氮气循环两次，然后在充氮气循环中加入单体(V-n)和Ni(ClO4)2·6H2O，再通过注射器加入干燥的、除气的DCM，室温聚合24h；将反应液滴入CH3OH/DCM(V/V＝3)中，过滤得到粗品，再重复溶解―沉淀―过滤两次，真空干燥得到聚合物(VI-n)。
4.权利要求1的高分子(VI-n)具有层状液晶相和柱状液晶相。
5.权利要求1的高分子(VI-n)在制备耐高温液晶材料领域的应用。
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