CN107011923A - 一种碳纳米管掺杂的聚合物分散液晶膜的制备方法 - Google Patents
一种碳纳米管掺杂的聚合物分散液晶膜的制备方法 Download PDFInfo
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Abstract
一种碳纳米管掺杂的聚合物分散液晶膜的制备方法，属于液晶材料应用领域。本发明以向列相液晶、光可聚合单体、光引发剂、玻璃微珠和改性多壁碳纳米管为原料，将所有原料混合超声震荡均匀后夹在两层镀有氧化铟锡的导电塑料薄膜之间，滚轴挤压均匀后形成10微米至30微米的薄层，在液晶/光可聚合单体复合体系的液晶相的清亮点温度以上0.5‑25℃通过3‑15mw/cm2光强的紫外光聚合5‑10min，制备出掺杂改性多壁碳纳米管的聚合物分散液晶膜。改性碳纳米管的掺杂能提高聚合物基体的电导率，从而降低阈值电压、驱动电压。
Description
技术领域
本发明属于液晶应用技术领域，具体涉及一种碳纳米管掺杂的聚合物分散液晶薄膜(Polymer Dispersed Liquid Crystal：PDLC)的聚合分相法，制备的薄膜可以广泛用于液晶显示技术及相关领域。
背景技术
PDLC膜的特征是向列相液晶微滴分散于聚合物基体网络中，制备PDLC膜时，在光或热的条件下，使得液晶和聚合单体的复合体系中聚合单体发生聚合反应，分子量逐步增加，导致其与液晶的相溶性降低，液晶会逐渐从复合体系分离析出。当对PDLC膜不加电时，由于光通过复合体系中液晶微滴的有效折射率和通过聚合物基体的折射率(np)不匹配，导致光线在液晶/聚合物界面产生多次折射、反射，这时PDLC膜会出现强烈的光散射，即不透明状态；当对PDLC膜施加电场时，液晶微滴在电场作用下会沿着电场方向重新进行取向，复合体系中液晶的寻常光折射率(no)和聚合物基体的折射率越匹配，光线就越能直接透过而不发生折射、反射，PDLC膜呈透明状态。
PDLC膜作为一种新型液晶功能显示材料，制备时无需偏振片和对基板进行表面处理，使得PDLC膜具备视角大、显示亮度高，降低了生产成本。此外，因为它是固态膜，能够有效控制液晶泄露和膜厚度问题，利于制作大面积或者弯曲柔性显示器。另外，PDLC膜在智能玻璃、光敏元件及电控开关等领域。
尽管PDLC膜具有优异的性能，但是随着人们对显示材料的要求不断提高，PDLC膜驱动电压高、动态响应慢等缺陷，因此提高PDLC膜的电光特性一直是研究的核心问题，特别是在降低开关电压和改善对比度及响应时间方面。聚合物网络中的液晶微滴重新取向所需的驱动临界电压受液晶和聚合物基质的电导率的影响，液晶微滴和聚合物网络的尺寸和形状影响复合材料的介电性能，因此影响PDLC膜的电光性能。
碳纳米管自发现以来就以其独特的电光机械性能而得到广泛应用。因此掺杂碳纳米管到液晶/聚合物复合体系中能够有效的提高聚合物基体的电导率，但是由于碳纳米管容易团聚缠绕尤其是高浓度时，因此碳纳米管在液晶/聚合物复合体系中的分散性比较差，这会降低PDLC膜的电光性能。通过合成类似液晶结构的分子对碳纳米管进行改性以提高在液晶/聚合物体系中的分散能力，从而改善PDLC膜的电光性能。
发明内容
本发明的目的是提供一种纳米掺杂的聚合物分散液晶(PDLC)膜的制备方法，通过调节碳纳米管掺杂以及改性碳纳米管的质量比来改善PDLC膜的电光性能，从而制备出低驱动电压、高对比度的薄膜材料。
本发明的方法是制备改性的碳纳米管掺杂在液晶/聚合物体系中；选用甲基丙烯酸月桂酯、甲基丙烯酸异冰片酯和聚乙二醇二丙烯酸酯-400为光聚合单体，液晶选用向列相液晶；单体之间聚合形成聚合物网络，将改性碳纳米管引入到液晶/聚合物复合体系中，利用碳纳米管优异的电光性能来提高液晶/聚合物复合体系的电导率，从而提高PDLC膜的电光性能。
一种碳纳米管掺杂的聚合物分散液晶膜的制备方法，其特征在于，所述方法如下：以向列相液晶、光可聚合单体、光引发剂、玻璃微珠和改性碳纳米管为原料，将所有原料混合超声震荡均匀后夹在两层镀有氧化铟锡的导电塑料薄膜之间，滚轴挤压均匀后形成10微米至30微米的薄层，在液晶/光可聚合单体复合体系的液晶相的清亮点温度以上0.5-25℃通过3-15mw/cm2光强的紫外光聚合5-10min，制备出掺杂改性多壁碳纳米管的聚合物分散液晶膜。
其中向列相液晶的含量为原料总质量的40％-55％，光可聚合单体为原料总量的50％-40％，光引发剂的含量为光可聚合单体质量的0.1％-10％，玻璃微珠的含量为原料总质量的0.1％-5％，改性碳纳米管的含量为原料总质量的0.01wt％-0.1wt％。
所述改性碳纳米管的改性方法为化学修饰法，具体步骤如下：
(1)首先，将N-(5-溴戊基)邻苯二甲酰亚胺溶在无水N，N-二甲基甲酰胺中，再逐滴加入到4'-羟基-4-联苯基甲腈和K2CO3的无水DMF溶液中；然后将反应混合物在保护气氛下磁力搅拌一段时间；反应结束后将反应混合物冷却至室温；通过过滤除去残余固体，滤液用乙酸乙酯、CH2Cl2和H2O萃取三次，合并的有机萃取物用无水MgSO4干燥；通过过滤除去残余固体，通过旋转蒸发从滤液中获得粗产物。用甲苯重结晶后，得到N-(5-(4'-氰基联苯-4-氧基)戊基)邻苯二甲酰亚胺为无色结晶；
(2)将水合肼溶在无水乙醇中的溶液滴加到溶有N-(5-(4'-氰基联苯-4-氧基)戊基)邻苯二甲酰亚胺的EtOH溶液中。反应混合物在氮气保护下在回流温度下磁力搅拌一段时间；反应结束后将反应混合物冷却至室温；反应混合物用CH2Cl2和H2O萃取三次；合并的有机相用无水MgSO4干燥；过滤除去残余固体并通过旋转蒸发从滤液中除去溶剂，得到粗产物；纯产物为浅黄色固体通过SiO2，CH2Cl2:MeOH＝4:1的快速柱色谱法获得；
(3)将酸化的MWNT加入SO2Cl2中进行超声分散处理；然后将反应混合物在氮气保护下90℃下磁力搅拌一段时间；反应结束后将反应混合物离心，随后除去上清液；残余固体用真空干燥炉干燥后，将残余固体和5-(4'-氰基联苯-4-氧基)戊胺分散在无水THF和三乙胺溶液中。在氮气保护下，将悬浮液在80℃下磁力搅拌一段小时；通过过滤获得残留固体；残留固体用甲醇洗涤5-8次，直至除去5-(4'-氰基联苯-4-氧)戊胺；通过干燥残留固体获得改性碳纳米管。
所述光可聚合单体是：
A.甲基丙烯酸月桂酯(LMA)、
B.甲基丙烯酸异冰片酯(IBMA)、
C.聚乙二醇二丙烯酸酯-400(PEGDA-400)。
上述光可聚合单体的质量比为：
A/B＝10:15-14:11，(A+B)/C＝6:1-1:6。
所述的清亮点温度是指液晶与单体复合体系从各向同性体转化为各向异性体时的温度。
本发明的关键在于改性碳纳米管在液晶/聚合物复合体系中的分散性；控制碳纳米管掺杂含量、调节可光聚合单体的配比和液晶的含量。
本发明的优点在于：改性碳纳米管在液晶/聚合物复合体系的分散性得到提升。通过调节碳纳米管的含量、光可聚合单体是甲基丙烯酸月桂酯(LMA)、甲基丙烯酸异冰片酯(IBMA)和聚乙二醇二丙烯酸酯-400(PEGDA-400)的质量比，制备出低驱动电压、高对比度的PDLC膜。这是因为碳纳米管掺杂会大幅度提高聚合物基体的电导率，从而降低PDLC膜的驱动电压，改性碳纳米管在液晶/聚合物复合体系中的分散性得到提高，这也降低了碳纳米管对液晶指向矢取向的影响从而降低对对比度的影响。
附图说明
图1是本发明所用的光可聚合单体和光引发剂安息香双甲醚(Irgacure 651)的分子式。
图2(a)是实例1制备的聚合物分散液晶膜的聚合物网络的扫描电镜照片，
图2(b)是实例2制备的聚合物分散液晶膜的聚合物网络的扫描照片，
图2(c)是实例3制备的聚合物分散液晶膜的聚合物网络的扫描照片。
图3是实例1/2/3制备的聚合物分散液晶膜的电压-透过率曲线。
具体实施方式
下面结合实施例对本发明作进一步详细说明。
实施例1
一种碳纳米管掺杂的聚合物分散液晶膜的制备方法，首先采用化学修饰方法对碳纳米管进行改性，具体步骤如下：
(1)首先，将N-(5-溴戊基)邻苯二甲酰亚胺溶在无水N，N-二甲基甲酰胺中，再逐滴加入到4'-羟基-4-联苯基甲腈和K2CO3的无水DMF溶液中。然后将反应混合物在保护气氛下100℃下磁力搅拌10小时。反应结束后将反应混合物冷却至室温。通过过滤除去残余固体，滤液用乙酸乙酯、CH2Cl2和H2O萃取三次，合并的有机萃取物用无水MgSO4干燥。通过过滤除去残余固体，通过旋转蒸发从滤液中获得粗产物。用甲苯重结晶后，得到N-(5-(4'-氰基联苯-4-氧基)戊基)邻苯二甲酰亚胺为无色结晶(7.18g，75％)。
(2)将水合肼溶在无水乙醇中的溶液滴加到溶有N-(5-(4'-氰基联苯-4-氧基)戊基)邻苯二甲酰亚胺的EtOH溶液中。反应混合物在氮气保护下在回流温度下磁力搅拌2.5小时。反应结束后将反应混合物冷却至室温。反应混合物用CH2Cl2和H2O萃取三次。合并的有机相用无水MgSO4干燥。过滤除去残余固体并通过旋转蒸发从滤液中除去溶剂，得到粗产物。纯产物通过快速柱色谱法(SiO2，CH2Cl2:MeOH＝4:1)获得，为浅黄色固体(3.12g，76％)。
(3)将100mg酸化的MWNT加入20mL SO2Cl2中进行超声分散处理。然后将反应混合物在氮气保护下90℃下磁力搅拌24小时。反应结束后将反应混合物离心(25min，7000rpm)，随后除去上清液。残余固体用真空干燥炉干燥2小时后，将残余固体和5-(4'-氰基联苯-4-氧基)戊胺分散在无水THF(20mL)和三乙胺(5mL)溶液中。在氮气保护下，将悬浮液在80℃下磁力搅拌72小时。通过过滤获得残留固体。固体用甲醇洗涤5-8次，直至除去5-(4'-氰基联苯-4-氧)戊胺。通过干燥残留固体24小时获得改性碳纳米管。
选用的光可聚合单体是(a)甲基丙烯酸月桂酯(LMA)、(b)甲基丙烯酸异冰片酯(IBMA)和(c)聚乙二醇二丙烯酸酯-400(PEGDA-400)，所用的单体质量百分比为：a/b/c＝30/52/18wt％。向列相液晶SLC1717(TNI＝365.2K，no＝1.519，ne＝1.720，石家庄诚志永华液晶有限公司)，所用混配单体与液晶的质量比为：混配单体/SLC1717＝48/48wt％。加入改性多壁碳纳米管为液晶和单体总质量的0.01wt％，加入光引发剂安息香双甲醚(Irgacure651)为单体总质量的1.99％，纳米微珠的含量约为液晶和单体总质量的2％。加热的条件下，使得液晶、可光聚合单体、改性多壁碳纳米管、光引发剂和纳米微珠复合体系达到清亮点形成各向同性的液体。通过漩涡震荡仪将体系混合均匀后，将其涂覆于两片镀有氧化铟锡(ITO)的透明玻璃之间，用滚轴压匀至20微米左右。在室温下用365nm紫外光辐照计照射(紫外光强度是6mW/cm2)10分钟，制成PDLC膜，其阈值电压、驱动电压、对比度都因多壁碳纳米管的掺杂而有较大的变化。
实施例2
一种碳纳米管掺杂的聚合物分散液晶膜的制备方法，选用的光可聚合单体是(a)甲基丙烯酸月桂酯(LMA)、(b)甲基丙烯酸异冰片酯(IBMA)和(c)聚乙二醇二丙烯酸酯-400(PEGDA-400)，所用的单体质量百分比为：a/b/c＝30/52/18wt％。向列相液晶SLC1717(TNI＝365.2K，no＝1.519，ne＝1.720，石家庄诚志永华液晶有限公司)，所用混配单体与液晶的质量比为：混配单体/SLC1717＝48/48wt％。加入改性多壁碳纳米管为液晶和单体总质量的0.02wt％，加入光引发剂安息香双甲醚(Irgacure 651)为单体总质量的1.98％，纳米微珠的含量约为液晶和单体总质量的2％。加热的条件下，使得液晶、可光聚合单体、改性多壁碳纳米管、光引发剂和纳米微珠复合体系达到清亮点形成各向同性的液体。通过漩涡震荡仪将体系混合均匀后，将其涂覆于两片镀有氧化铟锡(ITO)的透明玻璃之间，用滚轴压匀至20微米左右。在室温下用365nm紫外光辐照计照射(紫外光强度是6mW/cm2)10分钟，制成PDLC膜，其阈值电压、驱动电压、对比度都因多壁碳纳米管的掺杂而有较大的变化。
实施例3
一种碳纳米管掺杂的聚合物分散液晶膜的制备方法，选用的光可聚合单体是(a)甲基丙烯酸月桂酯(LMA)、(b)甲基丙烯酸异冰片酯(IBMA)和(c)聚乙二醇二丙烯酸酯-400(PEGDA-400)，所用的单体质量百分比为：a/b/c＝30/52/18wt％。向列相液晶SLC1717(TNI＝365.2K，no＝1.519，ne＝1.720，石家庄诚志永华液晶有限公司)，所用混配单体与液晶的质量比为：混配单体/SLC1717＝48/48wt％。加入改性多壁碳纳米管为液晶和单体总质量的0.05wt％，加入光引发剂安息香双甲醚(Irgacure 651)为单体总质量的1.95％，纳米微珠的含量约为液晶和单体总质量的2％。加热的条件下，使得液晶、可光聚合单体、改性多壁碳纳米管、光引发剂和纳米微珠复合体系达到清亮点形成各向同性的液体。通过漩涡震荡仪将体系混合均匀后，将其涂覆于两片镀有氧化铟锡(ITO)的透明玻璃之间，用滚轴压匀至20微米左右。在室温下用365nm紫外光辐照计照射(紫外光强度是6mW/cm2)10分钟，制成PDLC膜，其阈值电压、驱动电压、对比度都因多壁碳纳米管的掺杂而有较大的变化。
Claims (3)
1.一种碳纳米管掺杂的聚合物分散液晶膜的制备方法，其特征在于，所述方法如下：以向列相液晶、光可聚合单体、光引发剂、玻璃微珠和改性碳纳米管为原料，将所有原料混合超声震荡均匀后夹在两层镀有氧化铟锡的导电塑料薄膜之间，滚轴挤压均匀后形成10微米至30微米的薄层，在液晶/光可聚合单体复合体系的液晶相的清亮点温度以上0.5-25℃通过3-15mw/cm2光强的紫外光聚合5-10min，制备出掺杂改性多壁碳纳米管的聚合物分散液晶膜。
2.如权利要求1所述碳纳米管掺杂的聚合物分散液晶膜的制备方法，其特征在于将向列相液晶的含量为原料总质量的40％-55％，光可聚合单体为原料总量的50％-40％，光引发剂的含量为光可聚合单体质量的0.1％-10％，玻璃微珠的含量为原料总质量的0.1％-5％，改性碳纳米管的含量为原料总质量的0.01wt％-0.1wt％。
3.如权利要求1或2所述碳纳米管掺杂的聚合物分散液晶膜的制备方法，其特征在于光可聚合单体是：
A.甲基丙烯酸月桂酯
B.甲基丙烯酸异冰片酯
C.聚乙二醇二丙烯酸酯-400
上述光可聚合单体的质量比为：
A/B＝10:15-14:11，(A+B)/C＝6:1-1:6。
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