CN111116793B - 一种热交联功能化的三苯胺类聚合物及其制备方法与应用 - Google Patents
一种热交联功能化的三苯胺类聚合物及其制备方法与应用 Download PDFInfo
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Abstract
本发明涉及一种热交联功能化的三苯胺类聚合物及其制备方法与应用;所述聚合物结构如式(I)所示,其特点在于将两个苯乙烯基团引入到三苯胺衍生物,通过热聚合反应在电极表面形成稳定的交联聚合物薄膜,该制备方法具有聚合温度低、反应时间短的特点。本发明所制备的聚合物薄膜在不同电压下可实现从透明‑橙色‑蓝色的可逆颜色变化,具有光学对比度高、响应速度快、循环稳定性好等优点,可作为新型电致变色材料应用于智能窗、后视镜、智能眼镜等领域。
Description
技术领域
本发明涉及一种热交联功能化的三苯胺类聚合物及其制备方法,以及将其作为新型电致变色材料的应用。
背景技术
电致变色是指在外加电场作用下,材料在紫外--可见光或近红外区域的光学属性(如透射率、反射率或吸收率)产生稳定可逆变化的现象,在外观上表现为颜色和透明度的可逆变化。电致变色材料及其器件在建筑节能玻璃、汽车防眩目后视镜、汽车或飞机的调光玻璃、静态显示等领域展示了很大的应用前景。通过将电致变色材料应用于窗户以控制进入建筑物内的光线和热量,从而起到夏季保持凉爽和冬季保持温暖的功效,同时起到改善自然光照程度、防窥的目的。大部分科研工作者致力于调节可见光的变化以实现自然受控照明和节能目的,但到达地球的太阳所发出的能量中约有50%来自700nm至2500nm的红外光。因此,为了构建能够减少建筑物能耗的有效智能窗户,允许在可见光和近红外(NIR)光谱范围内进行能量调制的功能性电致变色材料,引起了越来越多的关注。
有机电致变色材料由于具有分子结构可设计、颜色多样性、加工性能好、制造成本低等特点,受到越来越广泛的关注。小分子和离散的低聚物具有出色的光物理和电致变色特性,并且可以通过合成调节其结构和性能来进行选择,但其薄膜的成膜性和稳定性较差。与有机小分子相比,聚合物可以形成非常稳定的薄膜,具有更好的稳定性,但在纯化和溶解性方面的挑战以及缺乏无色透明状态限制了它们的广泛应用。
发明内容
基于上述情况,本发明在三苯胺衍生物引入苯乙烯功能基团,合成一种热交联功能化的三苯胺类聚合物,苯乙烯基基团的存在可以使单体通过热聚合反应,在电极表面形成稳定的交联薄膜,并将其应用于电致变色领域,实现材料中性态的高透过率及高光学对比度的性能。
本发明的技术方案如下:
一种如式(I)所示的热交联功能化的三苯胺类聚合物P(MeO-TPDSt):
本发明所述式(I)所示的热交联功能化的三苯胺类聚合物的制备方法具体按照如下步骤进行:
(1)将二溴联苯、式(Ⅲ)所示的4-甲氧基-N-(4-(4-乙烯基苄氧基)苯基苯胺、钯类催化剂A、Buchwald磷配体A和碱性物质A加入有机溶剂A中,将混合液在氮气氛围下回流24小时,反应结束后,得到反应液A,经后处理得到式(Ⅳ)所示的MeO-TPDSt;所述的二溴联苯、式(Ⅲ)所示的4-甲氧基-N-(4-(4-乙烯基苄氧基)苯基苯胺、碱性物质A、钯类催化剂A和Buchwald磷配体A的投料物质的量之比为1:2~2.5:2~5:0.1~0.2:0.1~1,优选为1:2:4:0.1:0.7;
(2)将式(Ⅳ)所示的MeO-TPDSt溶解于有机溶剂中得到单体溶液,采用旋涂法在预处理的FTO玻璃上制备MeO-TPDSt薄膜,然后在氮气气氛下,在180~240℃下热聚合反应20~50min,得到P(MeO-TPDSt)聚合物薄膜;所述的单体溶液的浓度为30~60mg/mL;
进一步,步骤(1)中,所述的钯类催化剂A为Pd2(dba)3或Pd(OAc)2。
进一步,步骤(1)中,所述的碱性物质A为Cs2CO3、t-BuOK、t-BuONa、LHMDS或K2PO3。
进一步,步骤(1)中,所述的Buchwald磷配体A为BINAP、P(t-Bu)3、P(O-tolyl)3、Xantphos、BrettPHos、RuPhos、XPhos或t-BuXPhos。
进一步,步骤(1)中,所述有机溶剂A为甲苯、二甲苯、1,4二氧六环或叔丁醇。
进一步,步骤(1)中,所述有机溶剂A的体积用量以式(Ⅳ)所示的MeO-TPDSt的质量计为15~20mL/g。
进一步,步骤(1)中,所述反应液A的后处理的方法为:反应结束后,用水淬灭后再加入水和二氯甲烷进行萃取,收集有机相,经无水硫酸镁干燥,进行柱层析分离,以二氯甲烷/石油醚体积比1:1混合液为流动相进行洗脱,收集含目标化合物的洗脱液,减压蒸馏除溶剂并干燥,得到式(Ⅳ)所示的MeO-TPDSt。
进一步,步骤(2)中,旋涂转速为1000~2000rmp/s,时间为30~60s。
进一步,步骤(2)中,所述的预处理过程为:在300-600℃退火25-40分钟后进行紫外线臭氧处理20-40min。
本发明所述的式(Ⅲ)所示的4-甲氧基-N-(4-(4-乙烯基苄氧基)苯基苯胺具体按照如下方法进行制备:
1)将4-乙烯基苄基氯、4-溴苯酚、K2CO3、18冠-6醚和四丁基碘化铵加入无水丙酮中,并加热至回流12~16h,反应结束后,得到反应液C,经后处理得到式(Ⅱ)所示的1-溴-4-(4-乙烯基苄氧基)苯;所述的4-乙烯基苄基氯、4-溴苯酚、K2CO3、18冠-6醚和四丁基碘化铵投料物质的量之比为1:1:1~1.7:0.08~0.12:0.05~0.08,优选为1:1:1.6:0.2:0.05;
2)将式(Ⅱ)所示的1-溴-4-(4-乙烯基苄氧基)苯、对茴香胺、钯类催化剂B、Buchwald磷配体B、碱性物质B加入有机溶剂B中,并将反应混合物在氮气氛围下回流18~24小时,反应结束后,得到反应液D,经后处理得到式(Ⅲ)所示的4-甲氧基-N-(4-(4-乙烯基苄氧基)苯基苯胺;1-溴-4-(4-乙烯基苄氧基)苯、对茴香胺、碱性物质B、钯类催化剂B和Buchwald磷配体B投料物质的量之比为1:1~1.5:
进一步,步骤1)中,所述丙酮的体积用量以式(Ⅱ)所示的1-溴-4-(4-乙烯基苄氧基)苯的质量计为15~20mL/g。
再进一步,步骤1)中,所述反应液C的后处理的方法为:反应结束后,待反应液C冷却至室温,用水淬灭后再加入水和二氯甲烷进行萃取,收集有机相,经无水硫酸镁干燥,进行柱层析分离,以二氯甲烷/石油醚体积比1:1混合液为流动相进行洗脱,收集含目标化合物的洗脱液,减压蒸馏除溶剂并干燥,得到式(Ⅱ)所示的1-溴-4-(4-乙烯基苄氧基)苯。
进一步,步骤2)中,所述的钯类催化剂B为Pd2(dba)3或Pd(OAc)2。
进一步,步骤2)中,所述的碱性物质B为Cs2CO3、t-BuOK、t-BuONa、LHMDS或K2PO3。
进一步,步骤2)中,所述的Buchwald磷配体B为BINAP、P(t-Bu)3、P(O-tolyl)3、Xantphos、BrettPHos、RuPhos、XPhos或t-BuXPhos。
进一步,步骤2)中,所述的有机溶剂B为甲苯、二甲苯、1,4二氧六环或叔丁醇。
进一步,步骤2)中,所述有机溶剂B的体积用量以式(Ⅲ)所示的4-甲氧基-N-(4-(4-乙烯基苄氧基)苯基苯胺的质量计为15~20mL/g。
进一步,步骤2)中,所述反应液D的后处理的方法为:反应结束后,待反应液D冷却至室温,用水淬灭后再加入水和二氯甲烷进行萃取,收集有机相,经无水硫酸镁干燥,进行柱层析分离,以二氯甲烷/石油醚体积比2:1混合液为流动相进行洗脱,收集含目标化合物的洗脱液,减压蒸馏除溶剂并干燥,得到式(Ⅲ)所示的4-甲氧基-N-(4-(4-乙烯基苄氧基)苯基苯胺。本发明所述的P(MeO-TPDSt)聚合物薄膜应用于制备电致变色材料。
本发明通过核磁共振(NMR)、质谱(MS)进行化合物的表征。
本发明采用电化学工作站660E,紫外-可见吸收光谱表征了所得P(MeO-TPDSt)聚合物薄膜的电化学及电致变色性能。本发明制得的P(MeO-TPDSt)聚合物薄膜在不同电压下可实现从透明-橙色-蓝色的可逆颜色变化,在910nm处的光学对比度为85%,响应时间为1s、3.7s,700nm处的光学对比度为46%,响应时间为1.3s、3.2s。
与现有技术相比,本发明的有益效果在于:合成了新颖的热交联功能化的三苯胺类聚合物,该制备方法具有聚合温度低、反应时间短的特点;所制备的聚合物薄膜在不同电压下可实现从透明-橙色-蓝色的可逆颜色变化,具有光学对比度高、响应速率度快、循环稳定性好的优点,可作为新型电致变色材料应用于智能窗、后视镜、智能眼镜等领域。
附图说明
图1:本发明实施例1~3中化合物的合成路线及化学结构;
图2:本发明实施例4中P(MeO-TPDSt)聚合物薄膜的电镜图;
图3:本发明实施例4中P(MeO-TPDSt)聚合物薄膜的循环伏安曲线;
图4:本发明实施例4中P(MeO-TPDSt)聚合物薄膜不同电压下的紫外-可见吸收光谱和颜色变化;
图5:本发明实施例4中P(MeO-TPDSt)聚合物薄膜的在900nm下的光学对比度和响应时间;
图6:本发明实施例4中P(MeO-TPDSt)聚合物薄膜在700nm下的光学对比度和响应时间。
具体实施方式
下面以具体实施例对本发明的技术方案作进一步说明,但本发明的保护范围不限于此。
实施例1 1-溴-4-(4-乙烯基苄氧基)苯的合成
将4-乙烯基苄基氯(2.2g,14.5mmol),4-溴苯酚(2g,14.5mmol),K2CO3(3g,23.4mmol),18-冠-6-醚(0.78g,3mmol)和四丁基碘化铵(0.27g,0.8mmol)分别加入30mL无水丙酮中,并加热至回流16h,反应结束后,得到反应液A,反应结束后,待反应液冷却至室温,加入水淬灭。之后加入饱和食盐水和二氯甲烷进行萃取,收集有机相,经无水硫酸镁干燥后,减压浓缩,进行柱层析分离提纯。以300-400目硅胶为固定相,以二氯甲烷/石油醚体积比1:1混合液为流动相进行洗脱,收集含目标化合物的洗脱液,减压蒸馏除去溶剂并干燥,得到白色粉状的中间产物2 1-溴-4-(4-乙烯基苄氧基)苯化合物2.31g,产率为52.5%。1HNMR(500MHz,CDCl3):δ7.43–7.35(m),7.35(dd,J=5.3,2.9Hz),6.88–6.77(m),6.70(dt,J=21.7,10.9Hz),5.82–5.69(m),5.29–5.22(m),5.00(s);MS(EI):m/z(%):288.0
实施例2 4-甲氧基-N-(4-(4-乙烯基苄氧基)苯基苯胺的合成
将1-溴-4-(4-乙烯基苄氧基)苯(2g,6.92mmol),对茴香胺(1.92g,10.41mmol),KOtBu(2.33g,20.83mmol),Pd(OAc)2(0.233g,0.67mmol),将其取入装有隔膜的100ml两口烧瓶中。加入30mL无水甲苯和三叔丁基膦(0.631g,2.08mmol),并将反应混合物在氮气氛围下回流24小时。待反应液冷却至室温,加入水淬灭。之后加入饱和食盐水和二氯甲烷进行萃取,收集有机相,经无水硫酸镁干燥后,减压浓缩,进行柱层析分离提纯。以300-400目硅胶为固定相,以二氯甲烷/石油醚体积比为2:1混合液为流动相进行洗脱,收集含目标化合物的洗脱液,减压蒸馏除去溶剂并干燥,得到橙色粉状的中间产物2:4-甲氧基-N-(4-(4-乙烯基苄氧基)苯基苯胺1.6g,产率为46%。1H NMR(500MHz,CDCl3)δ10.01(s,2H),9.87(s,1H),5.82–5.73(m,25H),5.27(dd,J=10.8,5.2Hz,24H),5.00(d,J=10.0Hz,41H);MS(EI):m/z(%):331.16。
实施例3MeO-TPDSt的合成
将二溴联苯(1.43g,3.02mmol),产物(Ⅲ)4-甲氧基-N-(4-(4-乙烯基苄氧基)苯基苯胺(2g,6.04mmol),KOtBu(1.36g,12.08mmol),Pd(OAc)2(0.233g,0.67mmol)和P(t-Bu)3(0.631g,2.08mmol)在室温下加入到含有30mL无水甲苯的两口烧瓶中。将反应混合物在氮气氛围下回流24小时。反应结束后,待反应液冷却至室温,加入水淬灭。之后加入饱和食盐水和二氯甲烷进行萃取,收集有机相,经无水硫酸镁干燥后,减压浓缩,进行柱层析分离提纯。以300-400目硅胶为固定相,以二氯甲烷/石油醚体积比1:1混合液为流动相进行洗脱,收集含目标化合物的洗脱液,减压蒸馏除去溶剂并干燥,得到黄色粉状的最终产物:MeO-TPDSt 1.23g,产率为36%。1H NMR(500MHz,DMSO)δ7.51(d,J=8.1Hz,2H),7.47–7.35(m,4H),7.10–6.95(m,6H),6.92(d,J=9.0Hz,2H),6.82(d,J=8.7Hz,2H),6.78–6.67(m,1H),5.85(d,J=17.8Hz,1H),5.28(d,J=11.0Hz,1H),5.07(s,2H),3.75(d,J=4.4Hz,3H);MS(EI):m/z(%):812.36。
实施例4薄膜的热聚合及性能表征
将洗净的FTO玻璃在500℃退火20分钟后进行紫外线臭氧处理,然后将MeO-TPDSt溶解在氯苯中的溶液(50mg/ml)以1500rpm的转速旋涂1分钟。干燥后,使旋涂得到的薄膜在氮气环境下,在200℃下退火30分钟进行热聚合,以获得稳定的交联的电致变色聚合物膜。
将3-甲基咪唑四氟硼酸盐(3.42g,0.1mol/L)溶解在乙腈/二氯甲烷体积比7:3的混合溶剂(100mL)中作为空白溶液,后续所有电化学测试均在空白溶液中进行。
循环伏安、光谱电化学及电致变色测试阶跃电压为0-1.1V,测试结果表明,本发明制得的可热引发聚合的电致变色材料可由透明变为黄色再变为蓝色,有较高的对比度,在910nm处的光学对比度为85%,响应时间为1s、3.7s,700nm处的光学对比度为46%,响应时间为1.3s、3.2s,响应时间较快;可进一步制成电致变色器件,且在不同电压下在可见光和近红外(NIR)光谱范围具有不同的吸收,可作为新型光电功能材料应用于在电致变色等领域。
Claims (10)
2.如权利要求1所述的式(I)所示的热交联功能化的三苯胺类聚合物P(MeO-TPDSt)的制备方法,其特征在于:所述方法按照如下步骤进行:
(1)将二溴联苯、式(Ⅲ)所示的4-甲氧基-N-(4-(4-乙烯基苄氧基)苯基苯胺、钯类催化剂A、Buchwald磷配体A和碱性物质A加入有机溶剂A中,将混合液在氮气氛围下回流24小时,反应结束后,得到反应液A,经后处理得到式(Ⅳ)所示的MeO-TPDSt;所述的二溴联苯、式(Ⅲ)所示的4-甲氧基-N-(4-(4-乙烯基苄氧基)苯基苯胺、碱性物质A、钯类催化剂A和Buchwald磷配体A的投料物质的量之比为1:2~2.5:2~5:0.1~0.2:0.1~1;
(2)将式(Ⅳ)所示的MeO-TPDSt溶解于有机溶剂中得到单体溶液,采用旋涂法在预处理的FTO玻璃上制备MeO-TPDSt薄膜,然后在氮气气氛下,在180~240℃下热聚合反应20~50min,得到P(MeO-TPDSt)聚合物薄膜,即所述三苯胺类聚合物P(MeO-TPDSt);所述的单体溶液的浓度为30~60mg/mL;
3.如权利要求2所述的方法,其特征在于:步骤(1)中,所述的钯类催化剂A为Pd2(dba)3或Pd(OAc)2。
4.如权利要求2所述的方法,其特征在于:步骤(1)中,所述的碱性物质A为Cs2CO3、t-BuOK、t-BuONa、LHMDS或K2PO3。
5.如权利要求2所述的方法,其特征在于:步骤(1)中,所述的Buchwald磷配体A为BINAP、P(t-Bu)3、P(O-tolyl)3、Xantphos、BrettPHos、RuPhos、XPhos或t-BuXPhos。
6.如权利要求2所述的方法,其特征在于:步骤(1)中,所述有机溶剂A为甲苯、二甲苯、1,4-二氧六环或叔丁醇;所述有机溶剂A的体积用量以式(Ⅳ)所示的MeO-TPDSt的质量计为15~20mL/g。
7.如权利要求2所述的方法,其特征在于:步骤(1)中,所述反应液A的后处理的方法为:反应结束后,用水淬灭后再加入水和二氯甲烷进行萃取,收集有机相,经无水硫酸镁干燥,进行柱层析分离,以二氯甲烷/石油醚体积比1:1混合液为流动相进行洗脱,收集含目标化合物的洗脱液,减压蒸馏除溶剂并干燥,得到式(Ⅳ)所示的MeO-TPDSt。
8.如权利要求2所述的方法,其特征在于:步骤(2)中,旋涂转速为1000~2000rmp/s,时间为30~60s。
9.如权利要求2所述的方法,其特征在于:步骤(2)中,所述的预处理过程为:在300-600℃退火25-40分钟后进行紫外线臭氧处理20-40min。
10.一种如权利要求1所述的三苯胺类聚合物P(MeO-TPDSt)应用于制备电致变色材料。
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