CN110358059A - 一种含poss磷光聚合物材料的制备方法 - Google Patents

一种含poss磷光聚合物材料的制备方法 Download PDF

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CN110358059A
CN110358059A CN201910662081.4A CN201910662081A CN110358059A CN 110358059 A CN110358059 A CN 110358059A CN 201910662081 A CN201910662081 A CN 201910662081A CN 110358059 A CN110358059 A CN 110358059A
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林美娟
陈龙杰
凌启淡
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Fujian Normal University
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Abstract

本发明涉及一种含POSS磷光聚合物材料的制备方法。首先制备含二溴的磷光铱配合物单体和POSS单体，再与二溴咔唑单体、9‑(1‑辛基壬基)咔唑‑2,7‑双(硼酸频哪醇酯)在四三苯基膦钯催化剂作用下通过Suzuki缩聚反应得到含POSS磷光聚合物材料。纳米POSS单元键入到共轭聚合物中获得的一种有机无机杂化聚合物磷光材料具有良好的溶解性、成膜性、热稳定性和发光性能，可用于电致发光、光致发光、电存储信息、化学与生物传感器等领域。

Description

一种含POSS磷光聚合物材料的制备方法
技术领域
本发明涉及发光技术领域，具体是涉及一种含POSS磷光聚合物材料的制备方法。
背景技术
近年来，有机/无机杂化技术和纳米技术是制备先进功能材料的重要技术，也是电致发光材料改性最有效的技术方法。多面体低聚倍半硅氧烷(Polyhedral OligomericSilsesquioxane，简称POSS)作为笼状纳米尺寸的无机材料可以提供无机材料物理性能上的各种优势，又可以在纳米尺寸上对材料进行改性，被认为是在OLED领域最有应用潜力的材料。在电致发光材料中，咔唑拥有良好的光化学稳定性、空穴传输性能、三重态能级比较高等优点，成为目前常用的蓝光主体材料。近年来，研究表明通过POSS的引入能提高咔唑材料的发光性能、热稳定性能等。Qifang Li课题组(Tetrahedron,2014,70:2478)研究了在咔唑以及芴/咔唑聚合物中引入POSS的电致发光材料，研究表明由于POSS核心的隔离作用，每一个发光基团都以独立的个体存在，避免了因分子间相互作用而出现的低的荧光效率和发射峰变宽现象，使材料具有高的发光性能和发光纯度；POSS增加了电子电流密度，降低了空穴电流密度，从而有利于电荷的平衡，导致更高的亮度和电流效率。2009年，GhassanE.Jabbour课题组(Soft Matter,2009,5:3002)报道了以带有7个咔唑基和一个Ir(ppy)2(acac)配合物的POSS星状大分子化合物为发光材料，通过喷墨打印的方式所制得器件发光亮度达到10000cd/m2，外量子效率达到2.5％。同年，该课题组又报道了(Adv.Funct.Mater.,2009,19:2623)在POSS核上带有7个咔唑基和一个发不同光色的铱配合物所形成的系列红、绿、蓝光的POSS星状化合物，并以其为发光材料，通过旋涂的方式所得器件单色光的外量子效率达到5％～9％；以红、绿、蓝三种POSS化合物混合制成的白光器件，其外量子效率可达8％，功率效率为8.1lm/W。
本发明发现，通过Suzuki缩聚反应将具有空穴传输咔唑基团、发光铱配合物与无机纳米POSS结合起来，通过引入POSS单元来提高聚合物材料的稳定性能、发光性能、溶解性能和成膜性能，可用于电致发光、光致发光、电存储信息、化学与生物传感器等领域。
发明内容
本发明的目的之一在于提供一种含POSS磷光聚合物材料，可用于电致发光、光致发光、电存储信息、化学与生物传感器等领域。本发明的目的之二在于提供一种含POSS磷光聚合物材料的制备方法。
为实现本发明的目的，本发明首先制备含二溴的磷光铱配合物单体和POSS单体，再与二溴咔唑单体、9-(1-辛基壬基)咔唑-2,7-双(硼酸频哪醇酯)通过Suzuki缩聚反应制得含POSS磷光聚合物材料。
采用的技术方案是：
一种含POSS磷光聚合物材料的制备方法，包括以下制备步骤：
(1)铱配合物单体的制备
通过IrCl3或其水合物与2-(4-溴苯基)苯并噻唑在乙二醇单乙醚和水的混合溶剂中加热回流制备氯桥联铱二聚体，然后与2-吡啶甲酸在无水碳酸钠作用下在乙二醇单乙醚溶剂中加热回流反应制备铱配合物单体。
(2)POSS单体的制备
在三乙胺作用下三硅醇苯基POSS与溴丙基三氯硅烷反应得到溴丙基苯基POSS，然后与3,6-二溴咔唑在碱性条件下反应制备POSS单体。
(3)含POSS磷光聚合物材料的制备
在圆底烧瓶中按单体摩尔比加入9-(1-辛基壬基)咔唑-2,7-双(硼酸频哪醇酯)单体、2,7-二溴-9-(1-辛基壬基)-9H-咔唑单体、铱配合物单体与POSS单体，再加入适量的四三苯基膦钯催化剂和四正丁基碘化铵相转移剂，充氮除氧，而后注入预先充分除氧的甲苯和2M碳酸钾水溶液，在110℃氮气氛下磁力搅拌回流聚合反应48小时后，依次用苯硼酸和溴苯为封端剂进行封端反应各8小时，冷却到室温，用甲醇沉析，过滤收集固体，依次用甲醇和丙酮索提除去小分子和齐聚物，收集氯仿索提的聚合物溶液，浓缩至适当浓度后用甲醇沉析，收集最终所得絮状固体，真空干燥12小时，得到含POSS磷光聚合物材料。
所述的铱配合物单体的结构式为：
所述的POSS单体的结构式为：
所述的含POSS磷光聚合物材料具有如下的结构式：
其中x＝0.0005～0.05，y＝0.0005～0.03，数均分子量为5000～20000。
所述的9-(1-辛基壬基)咔唑-2,7-双(硼酸频哪醇酯)单体摩尔数与2,7-二溴-9-(1-辛基壬基)-9H-咔唑、铱配合物、POSS三种含溴单体的总摩尔数之比为1:1。
所述的9-(1-辛基壬基)咔唑-2,7-双(硼酸频哪醇酯)单体与铱配合物单体的摩尔数比为100:0.1～10。
所述的9-(1-辛基壬基)咔唑-2,7-双(硼酸频哪醇酯)单体与POSS单体的摩尔数比为100:0.1～6。
本发明具有如下优点：
1.聚合物中通过引入POSS，利用POSS的笼形多面体结构所具有的隔离和稀释作用，来抑制发光基团的聚集，从而提高材料的发光性能。
2.将纳米POSS基团垂挂接入刚性聚咔唑链上，可以有效地避免因刚性主链的堆叠而导致聚合物溶解性下降，获得的聚合物材料具有优良的溶解性和成膜性，能有效地提高OLED器件的性能。
3.可以充分发挥POSS纳米以及有机/无机杂化特性，从而提高发光材料的热稳定性、发光颜色稳定性。
附图说明
图1是本发明所述的一种含POSS磷光聚合物材料的结构式。
图2实施例1所制备的含POSS磷光聚合物材料薄膜在365nm激发下的荧光发射光谱。
图3是实施例2所制备的含POSS磷光聚合物材料的红外谱图。
图4是实施例2所制备的含POSS磷光聚合物材料薄膜在365nm激发下的荧光发射光谱。
图5是实施例2所制备的含POSS磷光聚合物材料薄膜和对照样薄膜的扫描电镜图片，其中a图是对照样，b图实施例2样品。
具体实施方式
下面通过具体实施例对本发明作进一步的说明，但这些具体实施方案不以任何方式限制本发明的保护范围。
实施例1
制备方法：
(1)2-(4-溴苯基)苯并噻唑合成
在圆底烧瓶中加入5g 2-氨基苯硫醇、7.4g对溴苯甲醛、7g焦亚硫酸钠，抽真空，充氮气，注入体积比为3:1的除过氧的N,N-二甲基甲酰胺和水的混合溶剂。100℃反应12小时后冷却至室温，将反应物倒入蒸馏水中，抽滤，滤饼用乙醇重结晶，得到白色固体产物，产率75％。
1H NMR(400MHz,CDCl3)δ8.07(ddd,J＝8.2,1.2,0.6Hz,1H),7.96(d,J＝8.7Hz,2H),7.90(d,J＝8.0Hz,1H),7.63(d,J＝8.7Hz,2H),7.51(d,J＝7.1Hz,1H),7.39(s,1H)。
(2)2-(4-溴苯基)苯并噻唑氯桥联二聚体的合成
在圆底烧瓶中加入1.0g 2-(4-溴苯基)苯并噻唑、0.5g三水合三氯化铱、60mL乙二醇单乙醚和20mL水，抽真空，通氮气，氮气下加热至110℃回流反应24h。反应结束后冷却至室温，用乙酸乙酯和饱和食盐水进行萃取，蒸干溶剂得到橙黄色固体，60℃真空干燥48小时，产率46％。
(3)铱配合物单体的制备
在圆底烧瓶中加入0.5g 2-(4-溴苯基)苯并噻唑氯桥联二聚体、0.1g 2-吡啶甲酸、60mg无水碳酸钠和60mL乙二醇单乙醚，抽真空，通氮气，在氮气下120℃回流24小时。反应结束后冷却至室温，用乙酸乙酯和饱和食盐水进行萃取，蒸干溶剂得到黄色固体，用二氯甲烷/石油醚体积比(2:1)作为淋洗剂进行柱层析纯化，得到铱配合物单体。产率为50％。
所制备的铱配合物单体，具有如下的结构：
1H NMR(400MHz,CDCl3)δ8.47(ddd,J＝8.4,1.3,0.6Hz,1H),8.18(ddd,J＝7.8,1.5,0.8Hz,1H),7.97-7.81(m,3H),7.63(d,J＝8.3Hz,1H),7.59-7.39(m,4H),7.36-7.16(m,3H),7.11(dd,J＝8.2,1.9Hz,1H),6.97(ddd,J＝8.5,7.2,1.2Hz,1H),6.69(d,J＝1.8Hz,1H),6.33(d,J＝1.8Hz,1H),6.06-5.99(m,1H)。
所制备的铱配合物单体在365nm激发下的荧光发射峰位于540nm和580nm，为黄光发光。
2、POSS单体的制备
合成路线：
参考文献(New J.Chem.,2013,37,735)，在圆底烧瓶中加入2.8g三硅醇苯基POSS、50mL干燥四氢呋喃和5mL的三乙胺，抽真空，通入氮气，搅拌30分钟充分混合，冰浴氮气氛下将溶于干燥四氢呋喃中的1g溴丙基三氯硅烷缓慢滴加到烧瓶中，搅拌反应12h，过滤去除沉淀，旋蒸去除溶剂，用甲醇沉析，过滤，干燥，得到白色固体溴丙基苯基POSS。
在圆底烧瓶中加入0.325g 3,6-二溴咔唑和5mL二甲基亚砜，溶解后滴加5mL 10％的NaOH溶液，常温下搅拌20min，缓慢滴加10mL溶有0.863g溴丙基苯基POSS的二甲基亚砜溶液，升温至40℃反应5小时。反应结束后用稀盐酸调节PH至中性，过滤，用乙醇重结晶后得到白色絮状固体。产率78％。
1H NMR(400MHz,CDCl3)δ8.03(s,7H),7.81–7.71(m,14H),7.52–7.32(m,14H),3.60–3.48(m,2H),2.97(s,2H),2.90(d,J＝0.5Hz,2H),2.06–1.91(m,2H),1.64(s,2H),1.06–0.94(m,2H)。
3、含POSS磷光聚合物材料的制备
在圆底烧瓶中加入660mg(1mmol)9-(1-辛基壬基)咔唑-2,7-双(硼酸频哪醇酯)单体(M1)、556.5mg(0.9885mmol)2,7-二溴-9-(1-辛基壬基)-9H-咔唑单体(M2)、1.35mg(0.0015mmol)铱配合物单体(M3)、13mg(0.01mmol)POSS单体(M4)，再加入25mg四三苯基膦钯催化剂、50mg四正丁基碘化铵，充氮除氧，而后注入预先充分除氧的10mL 2M K2CO3溶液和20mL甲苯，氮气氛下110℃下磁力搅拌回流反应48小时，而后加入溶有220mg苯硼酸的甲苯溶液继续反应8小时，再加入0.2mL溴苯继续进行封端反应8小时后，冷却到室温，将反应液缓慢滴入到甲醇中沉析，过滤收集固体，依次用甲醇和丙酮索提除去小分子和齐聚物，再用三氯甲烷索提收集聚合物溶液，浓缩至适当浓度后用甲醇沉析，收集最终所得絮状固体，真空干燥12小时，得到含POSS磷光聚合物材料。
本实施例制备的含POSS磷光聚合物材料数均分子量Mn＝1.1×104，PDI＝1.8。
本实施例制备的含POSS磷光聚合物材料薄膜在365nm波长激发下的荧光发射光谱如图2，可看出主要发射主体咔唑位于426nm和449nm附近的蓝光特征峰，客体铱配合物位于585nm附近黄色磷光发射较弱，聚合物的发光为蓝光。
实施例2
铱配合物单体的制备、POSS单体的制备同实施例1。
含POSS磷光聚合物材料的制备的实验条件和实验步骤同实施例1。本实施例包含实例1、实例2、实例3和不含POSS单体对照例，其中9-(1-辛基壬基)咔唑-2,7-双(硼酸频哪醇酯)单体(M1)、2,7-二溴-9-(1-辛基壬基)-9H-咔唑单体(M2)、铱配合物单体(M3)和POSS单体(M4)的投料量如表1所示。
表1单体投料量
M1(mmol) M2(mmol) M3(mmol) M4(mmol)
实例1 1 0.93 0.03 0.04
实例2 1 0.95 0.03 0.02
实例3 1 0.965 0.03 0.005
对照例 1 0.97 0.03 0
实施例2所制备的含POSS磷光聚合物材料薄膜测其在365nm波长激发下荧光发射，并与不含POSS的对照例比较，结果如图4所示，可看出含POSS聚合物主要呈现位于580nm处客体铱配合物黄光发射，位于430nm附近主体咔唑的蓝光发射较弱，聚合物的发光为黄光。
与不含POSS的对照例相比，含POSS的聚合物材料从主体向客体的能量转移更加充分，发光性能更好。
通过热失重测试，结果表明，实例1、2、3所制备的聚合物固体粉末在氮气氛中在失重5％时的温度为401℃，不含POSS的聚合物固体粉末对应的热失重温度为354℃，说明POSS的加入使聚合物热稳定性明显提升。
图5是实例1所制备的含POSS磷光聚合物材料薄膜扫描电镜图，并与不含POSS的对照样比较，表明含POSS聚合物薄膜表面更加平整，成膜性更好。
实施例3
含POSS磷光聚合物材料电致发光性能
将实施例2所制备的含POSS磷光聚合物材料作为发光层进行发光器件的制备，器件结构：ITO/PEDOT:PSS(30nm)/发光层(40nm)/TPBI(37nm)/Al(100nm)，进行电致发光性能的测试，并与不含POSS的对照样比较，结果如表2所示。由表2可见，所有聚合物的启亮电压在5V左右，与不含POSS对照样比较，加入POSS后的聚合物在流明效率，功率效率及外量子效率均有一定的提高，说明POSS的适量加入有利于OLED性能的提高。
表2电致发光性能

Claims (7)

1.一种含POSS磷光聚合物材料的制备方法，其特征在于
(1)铱配合物单体的制备
通过IrCl3或其水合物与2-(4-溴苯基)苯并噻唑在乙二醇单乙醚和水的混合溶剂中加热回流制备氯桥联铱二聚体，然后与2-吡啶甲酸在无水碳酸钠作用下在乙二醇单乙醚溶剂中加热回流反应制备得到铱配合物单体；
(2)POSS单体的制备
在三乙胺作用下三硅醇苯基POSS与溴丙基三氯硅烷反应得到溴丙基苯基POSS，然后与3,6-二溴咔唑在碱性条件下反应制备得到POSS单体；
(3)含POSS磷光聚合物材料的制备
在圆底烧瓶中按单体摩尔比加入9-(1-辛基壬基)咔唑-2,7-双(硼酸频哪醇酯)单体、2,7-二溴-9-(1-辛基壬基)-9H-咔唑单体、铱配合物单体与POSS单体，再加入适量的四三苯基膦钯催化剂和四正丁基碘化铵相转移剂，充氮除氧，而后注入预先充分除氧的甲苯和2M碳酸钾水溶液，在110℃氮气氛下磁力搅拌回流聚合反应48小时后，依次用苯硼酸和溴苯为封端剂进行封端反应各8小时，冷却到室温，用甲醇沉析，过滤收集固体，依次用甲醇和丙酮索提除去小分子和齐聚物，收集氯仿索提的聚合物溶液，浓缩至适当浓度后用甲醇沉析，收集最终所得絮状固体，真空干燥12小时，得到含POSS磷光聚合物材料。
2.根据权利要求1所述的一种含POSS磷光聚合物材料的制备方法，其特征在于所述的含POSS磷光聚合物，具有如下的结构式：
其中x＝0.0005～0.05，y＝0.0005～0.03，数均分子量为5000～20000。
3.根据权利要求1所述的一种含POSS磷光聚合物材料的制备方法，其特征在于所述的铱配合物单体的结构式为：
4.根据权利要求1所述的一种含POSS磷光聚合物材料的制备方法，其特征在于所述的POSS单体的结构式为：
5.根据权利要求1所述的一种含POSS磷光聚合物材料的制备方法，其特征在于所述的9-(1-辛基壬基)咔唑-2,7-双(硼酸频哪醇酯)单体摩尔数与2,7-二溴-9-(1-辛基壬基)-9H-咔唑单体、铱配合物单体、POSS单体的总摩尔数之比为1:1。
6.根据权利要求1所述的一种含POSS磷光聚合物材料的制备方法，其特征在于所述的9-(1-辛基壬基)咔唑-双(硼酸频哪醇酯)单体与铱配合物单体的摩尔比为100:0.1～10。
7.根据权利要求1所述的一种含POSS磷光聚合物材料的制备方法，其特征在于，所述的9-(1-辛基壬基)咔唑-2,7-双(硼酸频哪醇酯)单体与POSS单体的摩尔比为100:0.1～6。
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