CN108503839A - 多功能网状聚合物与薄膜、制备方法及该薄膜在电致变色或电控荧光方面的应用 - Google Patents
多功能网状聚合物与薄膜、制备方法及该薄膜在电致变色或电控荧光方面的应用 Download PDFInfo
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Abstract
多功能网状聚合物与薄膜、制备方法及该薄膜在电致变色和电控荧光方面的应用,属于功能高分子材料领域。首先是利用异氰酸丙基三乙氧基硅烷分别与苯胺四聚体和9,9'‑双(4‑氨基苯基)芴反应得到的两种可水解交联的功能性硅氧烷单体A和B,将单体的混合物配成适当浓度的溶液,通过滴涂的方式将两种单体转移到经过亲水处理的氧化铟锡导电玻璃基底上,再经过循环伏安法使两种单体在酸性条件下发生水解交联而得到多功能网状聚合物薄膜。两单体水解交联形成的三维网状聚合物具有较好的尺寸稳定性和抗氧化分解作用,本发明充分体现了简单高效的绿色化学理念,同时聚合物具有电致变色、电控荧光双重性质,具有广阔的应用前景。
Description
技术领域
本发明属于功能高分子材料技术领域,具体涉及一种以两种分别含苯胺齐聚物和荧光基团的硅氧烷单体制备的多功能网状聚合物与薄膜、制备方法及该聚合物薄膜在电致变色或电控荧光方面应用。
技术背景
近年来电致变色聚合物逐渐广泛的应用于智能窗户、低能量显示器、汽车自调光后视镜、智能可穿戴设备等多个领域。在常见的电致变色聚合物中,聚苯胺由于其具有氧化还原开关电位低、电活性高、多色转换特性以及易于通过化学和电化学聚合方法合成等优点,被认为是一种具有重要研究价值的材料。然而,由于大的共轭结构及强的氢键作用,使得聚苯胺不溶不熔、加工性差,因而限制了其在电致变色方面的应用。随着研究的不断深入,科研工作者发现含苯胺齐聚物的聚合物在保留聚苯胺电致变色性能的同时,有着良好的溶解性、可加工性以及可设计性。因此,设计合成含有苯胺齐聚物链段的聚合物作为电致变色材料成为研究热点。
电控荧光聚合物是一种荧光性质可随输入电信号发生相应变化的智能高分子。近来,通过引入荧光基团设计并合成了一系列含苯胺齐聚物的荧光聚合物,利用苯胺齐聚物和荧光基团之间的相互作用,通过改变施加的电压实现材料荧光性质有效调节。相比于其它的调控方法(光、温度、pH、离子强度等),电调控具有无法比拟的优势,如响应的快速性、可逆性和局部性等。而且电控荧光材料在智能显示、光电信息转换、生物信息存储及化学传感等领域显示出比其它荧光材料更为突出的应用前景。迄今为止,共聚和/或后聚合官能化是制备含荧光聚苯胺的聚合物的主要策略。
本发明旨在合成两种分别含苯胺齐聚物及荧光基团的可水解交联的硅氧烷单体,在循环伏安法扫描过程中,经过水解交联形成的多功能网状聚合物薄膜。利用苯胺齐聚物的电化学活性及与荧光基团之间的相互作用,使聚合物材料具有电致变色和电控荧光的双重性质。利用氧化铟锡导电玻璃基底的亲水化处理,聚合物薄膜能够与基底之间产生键合作用,有效地提高聚合物材料电致变色与电控荧光的循环稳定性。
发明内容
本发明提供了由两种可水解交联硅氧烷单体制备的多功能网状聚合物与薄膜、制备方法及该薄膜在电致变色或电控荧光方面应用。
本发明所述的多功能网状聚合物,其分子结构式如下所示:
其中:n为正整数
本发明进一步提供了多功能网状聚合物(Ⅰ)薄膜的制备方法以及该薄膜在电致变色和电控荧光方面的应用。
首先是利用异氰酸丙基三乙氧基硅烷分别与苯胺四聚体和9,9'-双(4-氨基苯基)芴反应得到的两种可水解交联的功能性硅氧烷单体A和B,将单体A和单体B的混合物配成适当浓度的溶液,通过滴涂的方式将两种单体转移到经过亲水处理的氧化铟锡导电玻璃(ITO)基底上,再经过循环伏安法使两种单体在酸性条件下发生水解交联而得到多功能网状聚合物薄膜两单体水解交联形成的三维网状聚合物具有较好的尺寸稳定性和抗氧化分解作用;另外聚合物能够与氧化铟锌玻璃表面的羟基发生反应,提高了聚合物与基底的之间的粘附力,进一步增强了聚合物材料在电化学过程中的稳定性。9,9'-双(4-氨基苯基)芴的引入旨在使聚合物具有荧光性能。苯胺齐聚物的引入旨在使聚合物在保持电致变色性能的同时,通过醌式结构对荧光的淬灭作用实现电控荧光的特性。本发明充分体现了简单高效的绿色化学理念,同时聚合物具有电致变色、电控荧光双重性质,具有广阔的应用前景。
本发明所述多功能网状聚合物薄膜的制备方法,其步骤如下:
(1)将等摩尔数的异氰酸丙基三乙氧基硅烷和苯胺四聚体加入到二甲基乙酰胺中,反应体系的固含量的质量百分比为10%~20%,在氮气气氛、室温下反应1~2小时得到功能性硅氧烷单体A溶液;
单体A的结构式如下所示:
A:
(2)将等摩尔数的异氰酸丙基三乙氧基硅烷和9,9'-双(4-氨基苯基)芴加入到二甲基乙酰胺中,反应体系的固含量的质量百分比为10%~20%,在氮气气氛、70~90℃下反应2~3小时得功能性硅氧烷单体B溶液;
单体B的结构式如下所示:
B:
(3)将功能性硅氧烷单体A溶液与功能性硅氧烷单体B溶液按照摩尔比1:4的比例混合,再用二甲基乙酰胺将浓度调整为0.20~0.30g/mL,室温氮气保护下搅拌0.3~2小时得到两种单体的混合溶液;将1.2cm×5.5cm的ITO基底(用于制备电致变色和电控荧光的工作电极)在二氯甲烷、丙酮、蒸馏水、无水乙醇中分别超声清洗2~3次,每次3~5分钟,再置于烘箱中干燥;然后将上述ITO基底在体积比为4~6:1:1的去离子水、质量分数25%的氨水、质量分数30%过氧化氢的溶液中在70~90℃下浸泡0.3~2小时,将ITO基底取出用蒸馏水冲洗干净并用氮气气流吹干,得到亲水化处理的ITO基底;将上述两种单体的混合溶液滴涂在亲水化处理的ITO基底上,在真空烘箱中于30~50℃下干燥1~3小时;以1.0M盐酸为电解质溶液,以上述干燥处理后的ITO基底为工作电极,铂丝为对电极,Ag/AgCl为参比电极组成三电极体系,在-0.2~0.8V范围内,以100mV/s的扫速扫描50~80圈,从而得到均一的多功能网状聚合物薄膜。
附图说明(以下结果均来自于实施例1):
图1:本发明合成的功能性硅氧烷单体A(上图)与B(下图)的核磁谱图;
图2:本发明合成的功能性硅氧烷单体A与B混合物薄膜/ITO水解交联过程的循环伏安曲线;
图3:本发明合成的功能性硅氧烷单体A与B混合物薄膜/ITO水解前(插图)后(大图)扫描电镜图;
图4:本发明合成的多功能网状聚合物薄膜/ITO在不同扫速下的循环伏安谱图;
图5:本发明合成的多功能网状聚合物薄膜/ITO的电化学阻抗测试谱图;
图6:本发明合成的多功能网状聚合物薄膜/ITO电致变色性能曲线(在不同电压下的紫外-可见光谱图谱);
图7:本发明合成的多功能网状聚合物薄膜/ITO的电致变色性能曲线(在0~0.8V电压下,循环周期为30s时测试的700nm波长下的第1~10圈和第291~300圈的紫外-可见光谱图);
图8:本发明合成的多功能网状聚合物薄膜/ITO的电控荧光性能曲线(在0~1V电压下的荧光发射图谱);
图9:本发明合成的多功能网状聚合物薄膜/ITO的电控荧光性能曲线(在激发波长为320nm、发射波长为484nm、电压范围为0-1.0V、循环周期为30s时的时间模式荧光图谱)。
图1中单体A的核磁谱图及各信号峰所对应的基团,1H NMR(d6-DMSO,ppm),δ=8.09(s,-CONH-),δ=7.73-7.50(m,-NH-),δ=7.28-6.68(m,Ar-H),δ=6.02(m,-CONH-),δ=3.74(m,-O-CH2-),δ=3.03(m,-CH2-next to urea group),δ=1.46(m,-CH2-),δ=1.14(m,-CH3),δ=0.54(m,-CH2-Si-(-O-)3)。
图1中单体B的核磁谱图及各信号峰所对应的基团,1H NMR(d6-DMSO,ppm):δ=8.35(s,-CONH-),δ=7.89(d,Ar-H),δ=7.42-7.19(m,Ar-H),δ=6.95(d,Ar-H),δ=6.09(m,-CONH-),δ=3.75(m,-O-CH2-),δ=3.02(m,-CH2-next to urea group),δ=1.44(m,-CH2-),δ=1.14(m,-CH3),δ=0.53(m,-CH2-Si-(-O-)3)。
如图2、3所示,A、B混合单体薄膜/ITO在100mV/s扫速下的循环伏安扫描,该测试在三电极体系下,以1.0M盐酸溶液为电解质溶液。在循环伏安过程中,电流峰值不断增大,说明水解过程逐步进行,扫描50圈后,薄膜的循环伏安曲线趋于稳定,说明该水解过程已经进行完全。在扫描电镜图中,右上角为单体A、B混合物薄膜在循环伏安之前电镜图像,形貌平整均一,只有一些少量的微小粒子。由图可见,在50圈循环伏安之后,薄膜由于水解过程中分子的聚合以及小分子的脱去,微观上显示为多孔结构。
如图4为多功能网状聚合物薄膜/ITO在不同扫速下的循环伏安图,扫速分别为10mV/s、20mV/s、30mV/s、40mV/s、50mV/s,图中显示有一对氧化还原峰,电位为0.53V/0.33V,分别对应于苯胺四聚体的氧化还原态之间的转换。
如图5所示,为多功能网状聚合物薄膜/ITO的电化学阻抗谱图。ITO基底上修饰的聚合物薄膜阻抗为74500Ω,相比于其他的类似聚合物,该阻抗值较大。
如图6所示的多功能网状聚合物/ITO在不同电压下的紫外-可见光谱图谱,首先在聚合物/ITO电极上施加恒定电压(-0.2V,0V,0.2V,0.4V,0.6V,0.8V,1.0V)300s,显示电流稳定在某一数值,使聚合物中的苯胺四聚体完全氧化或还原。将该电极置于紫外-可见光谱仪中,在280~800nm的波长范围内测试其透过率。插图显示的分别是0V、0.4V、0.8V时的ITO工作电极颜色由灰色到绿色,再到深蓝色的颜色转变。
如图7所示,多功能网状聚合物/ITO在700nm波长,在0~0.8V的电压范围内,循环周期为30s时的第1~10圈和第291~300圈的紫外-可见光谱图。将着色时间定义为聚合物从漂白态到着色态达到颜色变化的90%所需的时间,将褪色时间定义为聚合物从着色态到漂白态达到颜色变化的90%所需的时间。由图可见在第1~10圈时,工作电极的着色时间和褪色时间分别为9.9s和9.3s,着色效率为79cm2/C。在第291~300圈时,工作电极的着色时间和褪色时间分别为10.4s和10.5s,着色效率为66cm2/C。
如图8所示为多功能网状聚合物薄膜/ITO在0~1.0V电压下的荧光图谱。给工作电极通特定电压300s后测试的荧光发射光谱,其中激发波长为320nm,发射波长为484nm。由图可见随着电压的增加,荧光强度逐渐降低。当电压加到最高值1.0V时,荧光强度为原始荧光值60%。这是由于随着电压的增加,更多的苯胺四聚体由还原态转化为氧化态,随着苯胺四聚体中醌式结构的增加,荧光猝灭效应逐渐增强。
如图9所示为激发波长为320nm发射波长为484nm,施加电压为0~1.0V,电压循环周期为30s时的时间模式下多功能网状聚合物薄膜/ITO的荧光光谱。由于施加电压的时间较短,工作电极的荧光值比图8的荧光值要弱一些。其中荧光ON态和OFF态的转换时间分别为4.2s和2.4s。
具体实施方式
实施例1
将单体异氰酸丙基三乙氧基硅烷0.9895g(4mmol)与苯胺四聚体1.4657g(4mmol)溶解于10mL二甲基乙酰胺中,在氮气气氛、室温下电磁搅拌1小时,得溶液A1。将单体异氰酸丙基三乙氧基硅烷3.9579g(16mmol)与单体9,9'-双(4-氨基苯基)芴5.5749g(16mmol)溶解于30mL二甲基乙酰胺中,在氮气气氛、80℃下电磁搅拌2小时,得溶液B1。
将溶液A1与溶液B1完全混合并室温氮气保护下搅拌1小时得溶液C1,再用二甲基乙酰胺将浓度调整为0.20g/mL。将1.2cm×5.5cm ITO基底(用于制备电致变色和电控荧光工作电极)在二氯甲烷、丙酮、蒸馏水、无水乙醇中分别超声清洗2次,每次3分钟,再置于烘箱中干燥;然后将上述ITO基底在体积比为5:1:1的去离子水、质量分数25%的氨水、质量分数30%过氧化氢的溶液中在80℃下浸泡1小时,将ITO基底取出用蒸馏水冲洗干净并用氮气气流吹干,得到亲水化处理的ITO基底。用滴涂的方式将适量的溶液C1转移到亲水的ITO基底上。将滴涂均匀的ITO基底置于真空烘箱中,并在40℃下保持1小时。以1.0M盐酸为电解质溶液,以上述干燥处理后的ITO基底为工作电极、铂丝为对电极、Ag/AgCl为参比电极的形成三电极体系下,在循环伏安模式中,-0.2~0.8V范围内,以100mV/s的扫速扫描50圈,得到均一的多功能网状聚合物薄膜。
实施例2
将单体异氰酸丙基三乙氧基硅烷0.7421g(3mmol)与苯胺四聚体1.0993g(3mmol)溶解于5mL二甲基乙酰胺中,在氮气气氛、室温下电磁搅拌1小时,得溶液A2。将单体异氰酸丙基三乙氧基硅烷2.9684g(12mmol)与单体2-氨基芴2.1747g(12mmol)溶解于15mL二甲基乙酰胺中,在氮气气氛、80℃下电磁搅拌2小时,得溶液B2。
将溶液A2与溶液B2完全混合并室温氮气保护下搅拌1小时得溶液C2,再用二甲基乙酰胺将浓度调整为0.20g/mL。将1.2cm×5.5cm ITO基底(用于制备电致变色和电控荧光工作电极)在二氯甲烷、丙酮、蒸馏水、无水乙醇中分别超声清洗2次,每次3分钟,再置于烘箱中干燥;然后将上述ITO基底在体积比为5:1:1的去离子水、质量分数25%的氨水、质量分数30%过氧化氢的溶液中在80℃下浸泡1小时,将ITO基底取出用蒸馏水冲洗干净并用氮气气流吹干,得到亲水化处理的ITO基底。用滴涂的方式将适量的溶液C2转移到亲水的ITO基底上。将滴涂均匀的ITO基底置于真空烘箱中,并在40℃下保持1小时。以1.0M盐酸为电解质溶液,以上述干燥处理后的ITO基底为工作电极、铂丝为对电极、Ag/AgCl为参比电极的形成三电极体系下,在循环伏安模式中,-0.2~0.8V范围内,以100mV/s的扫速扫描50圈,得到均一的多功能网状聚合物薄膜。
实施例3
将单体异氰酸丙基三乙氧基硅烷0.4947g(2mmol)与苯胺四聚体0.7320g(2mmol)溶解于5mL二甲基乙酰胺中,在氮气气氛、室温下电磁搅拌1小时,得溶液A3。将单体异氰酸丙基三乙氧基硅烷1.9789g(8mmol)与单体1-氨基蒽1.5459g(8mmol)溶解于15mL二甲基乙酰胺中,在氮气气氛、80℃下电磁搅拌1小时,得溶液B3。
将溶液A3与溶液B3完全混合并室温氮气保护下搅拌0.5小时得溶液C3,再用二甲基乙酰胺将浓度调整为0.20g/mL。将1.2cm×5.5cm ITO基底(用于制备电致变色和电控荧光工作电极)在二氯甲烷、丙酮、蒸馏水、无水乙醇中分别超声清洗2次,每次3分钟,再置于烘箱中干燥;然后将上述ITO基底在体积比为5:1:1的去离子水、质量分数25%的氨水、质量分数30%过氧化氢的溶液中在80℃下浸泡1小时,将ITO基底取出用蒸馏水冲洗干净并用氮气气流吹干,得到亲水化处理的ITO基底。用滴涂的方式将适量的溶液C3转移到亲水的ITO基底上。将滴涂均匀的ITO基底置于真空烘箱中,并在45℃下保持1小时。以1.0M盐酸为电解质溶液,以上述干燥处理后的ITO基底为工作电极、铂丝为对电极、Ag/AgCl为参比电极的形成三电极体系下,在循环伏安模式中,0~1.0V范围内,以100mV/s的扫速扫描60圈,得到均一的多功能网状聚合物薄膜。
实施例4
将单体异氰酸丙基三乙氧基硅烷0.4947g(2mmol)与单体还原态苯胺四聚体0.7320g(2mmol)溶解于5mL二甲基乙酰胺中,在氮气气氛、室温下电磁搅拌1小时,得溶液A4。将单体异氰酸丙基三乙氧基硅烷1.9789g(8mmol)与单体2-氨基-9,9-二甲基芴1.6743g(8mmol)溶解于10mL二甲基乙酰胺中,在氮气气氛、80℃电磁下搅拌1小时,得溶液B4。
将溶液A4与溶液B4完全混合并室温氮气保护下搅拌1小时,再用二甲基乙酰胺将浓度调整为0.20g/mL得溶液C4。将1.2cm×5.5cm ITO基底(用于制备电致变色和电控荧光工作电极)在二氯甲烷、丙酮、蒸馏水、无水乙醇中分别超声清洗2次,每次3分钟,再置于烘箱中干燥;然后将上述ITO基底在体积比为5:1:1的去离子水、质量分数25%的氨水、质量分数30%过氧化氢的溶液中在80℃下浸泡1小时,将ITO基底取出用蒸馏水冲洗干净并用氮气气流吹干,得到亲水化处理的ITO基底。用滴涂的方式将适量的溶液C4转移到亲水的ITO基底上。将滴涂均匀的ITO基底置于真空烘箱中,并在40℃下保持1.5小时。取出样品后,以1.0M盐酸为电解质溶液,以上述干燥处理后的ITO基底为工作电极、铂丝为对电极、Ag/AgCl为参比电极的形成三电极体系下,在循环伏安模式中,0~1.0V范围内,以100mV/s的扫速扫描80圈,得到均一的多功能网状聚合物薄膜。
以下为实施例2~4所需要的单体,均可以购买得到。
Claims (6)
1.一种多功能网状聚合物,其结构式如下所示:
其中:n为正整数
2.一种多功能网状聚合物薄膜的制备方法,其步骤如下:
(1)将等摩尔数的异氰酸丙基三乙氧基硅烷和苯胺四聚体加入到二甲基乙酰胺中,反应体系的固含量的质量百分比为10%~20%,在氮气气氛、室温下反应1~2小时得到功能性硅氧烷单体A溶液;
单体A的结构式如下所示,
(2)将等摩尔数的异氰酸丙基三乙氧基硅烷和9,9'-双(4-氨基苯基)芴加入到二甲基乙酰胺中,反应体系的固含量的质量百分比为10%~20%,在氮气气氛、70~90℃下反应2~3小时得功能性硅氧烷单体B溶液;
单体B的结构式如下所示,
(3)将功能性硅氧烷单体A溶液与功能性硅氧烷单体B溶液按照摩尔比1:4的比例混合,再用二甲基乙酰胺将浓度调整为0.20~0.30g/mL,室温氮气保护下搅拌0.3~2小时得到两种单体的混合溶液;将两种单体的混合溶液滴涂在亲水化处理后的ITO基底上,在真空烘箱中于30~50℃下干燥1~3小时;以1.0M盐酸为电解质溶液,以上述干燥处理后的ITO基底为工作电极,铂丝为对电极,Ag/AgCl为参比电极组成三电极体系,在-0.2~0.8V范围内,以100mV/s的扫速扫描50~80圈,从而得到均一的多功能网状聚合物薄膜。
3.如权利要求2所述的一种多功能网状聚合物薄膜的制备方法,其特征在于:步骤(3)中是将ITO基底在二氯甲烷、丙酮、蒸馏水、无水乙醇中分别超声清洗2~3次,每次3~5分钟,再置于烘箱中干燥;然后将上述ITO基底在体积比为4~6:1:1的去离子水、质量分数25%的氨水、质量分数30%过氧化氢的溶液中在70~90℃下浸泡0.3~2小时,将ITO基底取出用蒸馏水冲洗干净并用氮气气流吹干,得到亲水化处理的ITO基底。
4.如权利要求2所述的一种多功能网状聚合物薄膜的制备方法,其特征在于:将步骤(2)中的9,9'-双(4-氨基苯基)芴更换为2-氨基芴、1-氨基蒽或2-氨基-9,9-二甲基芴。
5.一种多功能网状聚合物薄膜,其特征在于:是由权利要求2~4任何一项所述的方法制备得到。
6.权利要求5所述的多功能网状聚合物薄膜在电致变色或电控荧光方面的应用。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109762347A (zh) * | 2019-01-24 | 2019-05-17 | 吉林大学 | 一种通过共价键键合的多功能网状杂化薄膜材料及其在电化学领域的应用 |
CN111320756A (zh) * | 2020-03-05 | 2020-06-23 | 吉林大学 | 电活性聚硅氧烷、其薄膜制备方法及该薄膜在颜色/荧光双指示的超级电容器中的应用 |
CN111995778A (zh) * | 2019-05-27 | 2020-11-27 | 江西理工大学 | 一种PS-b-P4VP共聚物薄膜及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102604074A (zh) * | 2012-02-28 | 2012-07-25 | 吉林大学 | 电活性荧光聚合物、制备方法及用于检测氧化或还原性物质 |
CN106633074A (zh) * | 2016-12-27 | 2017-05-10 | 哈尔滨工业大学 | 一种具有电致变色性能的聚硅氧烷及其制备方法 |
CN107759789A (zh) * | 2017-10-27 | 2018-03-06 | 黑龙江大学 | 一种具有电致变色性能的聚倍半硅氧烷及其制备方法和应用 |
-
2018
- 2018-03-23 CN CN201810246918.2A patent/CN108503839B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102604074A (zh) * | 2012-02-28 | 2012-07-25 | 吉林大学 | 电活性荧光聚合物、制备方法及用于检测氧化或还原性物质 |
CN106633074A (zh) * | 2016-12-27 | 2017-05-10 | 哈尔滨工业大学 | 一种具有电致变色性能的聚硅氧烷及其制备方法 |
CN107759789A (zh) * | 2017-10-27 | 2018-03-06 | 黑龙江大学 | 一种具有电致变色性能的聚倍半硅氧烷及其制备方法和应用 |
Non-Patent Citations (2)
Title |
---|
DANMING CHAO,ET AL.: "Synthesis and properties of multifunctional poly(amic acid) with oligoaniline and fluorene groups", 《COLLOID AND POLYMER SCIENCE》 * |
尹明莹: "苯胺基电致变色聚合物的设计合成及性质研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109762347A (zh) * | 2019-01-24 | 2019-05-17 | 吉林大学 | 一种通过共价键键合的多功能网状杂化薄膜材料及其在电化学领域的应用 |
CN109762347B (zh) * | 2019-01-24 | 2020-12-01 | 吉林大学 | 一种通过共价键键合的多功能网状杂化薄膜材料及其在电化学领域的应用 |
CN111995778A (zh) * | 2019-05-27 | 2020-11-27 | 江西理工大学 | 一种PS-b-P4VP共聚物薄膜及其制备方法 |
CN111320756A (zh) * | 2020-03-05 | 2020-06-23 | 吉林大学 | 电活性聚硅氧烷、其薄膜制备方法及该薄膜在颜色/荧光双指示的超级电容器中的应用 |
CN111320756B (zh) * | 2020-03-05 | 2021-07-27 | 吉林大学 | 电活性聚硅氧烷、其薄膜制备方法及该薄膜在颜色/荧光双指示的超级电容器中的应用 |
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