CN115433346B - 基于菲醌α-二胺的钯类催化剂及其制备方法和应用 - Google Patents
基于菲醌α-二胺的钯类催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种基于菲醌α‑二胺的钯催化剂,其结构式如下:式中,R为甲基、苯基的一种;R1为烷基、烷氧基、氯原子或氟原子的一种官能团取代。本发明所述的催化剂以菲醌α‑二胺为配体中心,其具有制备原料来源广,价格便宜,结构简单易修饰,给电子能力强,等诸多优点,能够有效调节催化剂的电子和位阻效应;采用不同空间位阻取代基团进行优化获得的钯催化剂,能够实现聚合物PDD‑4的分子量和收率的协同调节,获得高品质的聚合物材料;在有机太阳能电池等光电材料的制备中有着良好的商业应用前景。
Description
技术领域
本发明属于光电材料催化剂技术领域,具体涉及菲醌α-二胺钯类催化剂制备及其在光电给体聚合物材料中的应用。
背景技术
有机太阳能电池(OSC)作为一种新型薄膜光伏技术,因具有质轻、柔性、大面积低成本制备、光伏材料高度可调等诸多现有光伏技术无法比拟优点,成为新能源领域的研究热点。在现有的光伏技术中,昂贵的制作成本是制约其大规模商业化应用的关键。然而,在有机太阳能电池的实验室研发中,尽管一些聚合物给体材料展现出较高的光电转换效率,但较低的聚合产率阻碍了其商业化应用前景。
在已报道的高性能聚合物给体材料中,基于苯并二噻吩(BDT)单元的聚合物给体材料一直是有机太阳能电池领域的研究热点。目前,通常是采用两种经典钯催化体系来制备该类聚合物给体材料,如聚合物PBnDT-FTAZ,J52,PNTBDT等通常采用Pd2(dba)3/P-(o-Tol)3催化体系制备,而聚合物PTB7-Th[10],PBDBT,PBPD-Th,PM6,D18等通常采用Pd(PPh3)4催化体系获得。理想情况下,基于上述催化体系的Stille交叉偶联缩合方法能够产生规整的D-A交替共聚物,这是因为sp2杂化碳-卤(Br or I)键仅能与芳基碳-锡键(sp2 C-Sn)反应。事实上,在钯催化条件下,通常存在一定程度的反应缺陷(自偶联、端基缺陷、钯金属缺陷等),导致D和A单元共聚时并不完全按照预想的1:1交替排列。尤其是使用不同催化剂时,这种自耦联程度将会呈现出不同状况。说明:即使具有相同主链结构单元的D-A交替共聚物,在使用不同催化剂聚合时很可能会展现出完全不同的的规整度、分子量、分散指数,进而影响对应高性能聚合物部分的产率。
基于此,申请人前期研究发现:采用上述两种经典钯催化剂,对展现出高性能的聚合物PTB7-Th进行制备,经分析两种催化剂制备的聚合物结构的D和A比例均不是按照1:1进行排列,表明两种聚合物结构均存在不同程度的缺陷。此外,以②Pd(PPh3)4为催化剂制备聚合物的分子量几乎是①Pd2(dba)3的两倍,光伏性能也接近于两倍,但产率缺相反(Pd(PPh3)4收集的高效聚合物产率为48%,而Pd2(dba)3可获得87%高的产率)。可以看出,优化聚合物反应条件,不仅可以筛选出高性能的聚合物,同时还可以提升聚合物收率;且传统的两种钯系催化无法有效兼顾良好的聚合物性能和收率。基于此,设计高性能的催化剂是进一步提升聚合物性能和收率的关键。
发明内容
本发明的主要目的在于针对现有催化剂的不足,提供一类基于菲醌α-二胺钯催化剂,该催化剂以原料来源广,价格便宜,结构简单易修饰,热稳定性以及环境稳定性等诸多优点为一体的α-二胺为配体中心,并采用不同空间位阻取代基团来进行优化,具有低成本、高效的优点;可用于高性能聚合物给体材料PDD-4等,实现聚合物PDD-4的分子量和分散度的调节,获得高品质的聚合物材料,在有机太阳能电池具有良好的应用前景。
为实现上述目的,本发明采用的技术方案为:
基于菲醌α-二胺钯催化剂以α-二胺为配体中心,结构式见式I:
式中,R为甲基、苯基;R1为氯原子、氟原子、烷基、烷氧基(C的个数为1~3,下文以甲基或甲氧基为例)。
具体结构如下
上述方案中,所述基于菲醌α-二胺的钯催化剂催化剂为Pd-NHC络合物,其中采用的NHC配体前体的结构式见式II:
式中,R为甲基、苯基的一种;R1为烷基、烷氧基、氯原子或氟原子的一种。
上述方案中,菲醌α-二胺钯催化剂的制备方法,包括如下步骤:在反应容器中加入NHC配体前体、二氯化钯和反应溶剂,在保护气氛下升温至80~90℃,回流反应10~24小时。
上述方案中,所述保护气氛可用氮气、氩气等气氛。
上述方案中,所述反应溶剂可选用甲醇、乙醇等醇类;其与二氯化钯的液固比为8~12ml:1g。
上述方案中,所述NHC配体前体、二氯化钯的摩尔比为1:1~1.2。
上述方案中,所述NHC配体前体的制备方法包括如下步骤:在反应容器中加入9,10-菲醌、4号位取代的2,6-二苯甲基苯胺和氯化锌,加入醋酸为溶剂,100~120℃下搅拌5~12h;冷却至室温后,过滤出固体,将其溶于二氯甲烷,加入草酸钾和水,室温搅拌12-24h;二氯甲烷萃取,二氯甲烷和醋酸重结晶,即得所述NHC配体前体。
上述方案中,所述含4号位取代的2,6-二苯甲基苯胺的结构式见式III;
式中,R为甲基、苯基中的一种。
上述方案中,所述含9,10-菲醌、4号位取代的2,6-二苯甲基苯胺、氯化锌的摩尔比为1:2~2.5:2.5。
上述方案所述基于菲醌α-二胺的钯催化剂作为D-A聚合物催化剂的应用。
进一步地,所述D-A聚合物催化剂为聚合物PDD-4等,具体制备步骤包括如下:将D单元单体、A单元单体、基于菲醌α-二胺的钯催化剂、膦配体、碱金属碳酸钾、四甲基乙二胺(TMEDA)、t-BuCO2H加入有机溶剂中混合均匀,然后在110~150℃和保护气氛下,反应24~72h;其中D单元单体、A单元单体和催化剂的摩尔比为1:1:0.02~0.05。
上述方案中,所述有机溶剂为甲苯、氯苯或邻二甲苯。
上述方案中,所述膦配体可选用P(o-OMePh)3、P(o-tol)3、PPh3等;碱金属碳酸钾可选用碳酸钾,碳酸铯等。
根据上述方案构建出的给体材料的催化体系,获得高度规整,分子量和分散度可控的D-A交替共聚物,用作活性层的给体材料或电子传输材料。
本发明通过合成具有不同基团取代的N-苯环的α-二胺钯催化剂,可通过优化催化剂结构,控制聚合时间、催化剂用量制备出系列聚合物,经对比聚合收率、聚合物品质等筛选出最佳聚合物材料(PDD-4样本)。进一步选取非富勒烯小分子为受体,通过器件优化,制备出基于PDD-4为给体的性能超过16%的有机太阳能电池。
本发明的原理为:骨架空间位阻会影响催化剂的催化活性,选择合适位阻的取代基团可实现对聚合物分子量的调控,进而筛选高效的聚合物材料;本发明所述催化剂以较大体积的菲醌为骨架,并在N原子上引入不同取代基的苯,通过增加骨架和邻位芳基的体积来实现阻碍链转移速率,提升链增速率,抑制结构缺陷,进而获得高度规整度、分子量高的聚合物材料。
与现有技术相比,本发明的有益效果为:
1)本发明涉及的α-二胺分子具有制备原料来源广,价格便宜,结构简单易修饰,骨架空间位阻大且易于调节,给电子能力强,热稳定性以及空气稳定性好等诸多优点,能够有效调节催化剂的电子和位阻效应;
2)本发明所得催化剂可实现对聚合物结构缺陷的有效抑制,可有效调控所得聚合物的分子量和分散度的调控,获得高收率、高品质的聚合物;其在有机太阳能电池具有良好的应用前景。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
实施例1
一种基于菲醌α-二胺的钯催化剂,其合成路线见式IV;
具体制备步骤如下:
1-1)在双颈瓶中加入2-苯甲基苯胺(2.59g,10mmol)和N-氯代丁二酰亚胺(NCS)(2.66g,20mmol),加入三氯甲烷(50ml)和乙酸(50ml)为溶剂,室温下搅拌反应过夜;去离子水猝灭后,用饱和氯化钠和二氯甲烷萃取,有机相用无水Na2SO4干燥后,除去溶剂;用硅胶柱色谱分离提纯,洗脱剂为石油醚,得到化合物2-苯甲基-4-氯苯胺(1.46g,50%);
1-2)在烧瓶中依次加入产物1(4.99g,17mmol)、二苯甲醇(3.44g,19mmol)、氯化锌(0.54g,4mmol)和盐酸(0.49g,13.6mmol),搅拌反应四小时,点板监测反应;反应结束后,蒸馏水猝灭后,用饱和氯化钠和二氯甲烷萃取,有机相用无水Na2SO4干燥后,除去溶剂;用硅胶柱色谱分离提纯,洗脱剂为乙酸乙酯/石油醚,得到化合物2(2.11g,27%);
1-3)在氮气氛围下,将化合物2(460.02mg,1.00mmol),9,10-蒽醌(91.09mg,0.50mmol),氯化锌(170.37mg,1.25mmol)加入双颈烧瓶中,加入5mL的醋酸为溶剂,120℃下搅拌5小时;冷却至室温后,过滤出固体,将其溶于二氯,加入草酸钾和水,室温搅拌12小时;二氯甲烷萃取,二氯和醋酸重结晶;得到化合物3(0.98g,90%);
1-4)将化合物3(1.09g,1.0mmol)、二氯化钯(0.19g,1.1mmol)和甲醇(10mL)加入到双口烧瓶中,在氮气氛围下,升温至80℃,回流反应12小时;在反应混合物冷却至室温后,蒸馏水猝灭后,用饱和氯化钠和二氯甲烷萃取,有机相用无水Na2SO4干燥后,然后减压蒸干溶剂,加入二氯甲烷(5ml)溶解后过滤除去不溶部分;后加入正己烷(20毫升),然后将沉淀过滤、干燥,得到最终产物化合物4(0.76g,60%)。
应用例1
将实施例1所得催化剂产物和传统Pd(PPh3)4催化剂应用于PDD-4的聚合,其聚合路线见式V;
Still聚合反应:在氮气保护下,依次加入A单元单体(0.13g,0.20mmol)和D单元单体(0.19g,0.20mmol),催化剂Pd(PPh3)4(0.01g,0.01mmol)和5mL无水甲苯,110℃反应48h;粗产物用甲醇沉降,随后依次用丙酮、正己烷、二氯甲烷、三氯甲烷进行抽提;旋蒸三氯甲烷,加入甲醇沉降,抽滤得最终宽带隙聚合物产物PDD-4。(Mn=121461;PDI=3.68)
DArP聚合:D单元单体(0.19g,0.20mmol)、A单元单体(0.13g,0.20mmol)、新型菲醌α-二胺钯类催化剂(126.90mg,0.01mmol)、P(o-OMePh)3(4.32mg,0.01mmol)、Cs2CO3(0.16g,0.50mmol)、TMEDA(0.06g,0.5mmol)、t-BuCO2H(1.03mg,0.01mmol)和5mL无水甲苯,110℃反应48h;粗产物用甲醇沉降,随后依次用丙酮、正己烷、二氯甲烷、三氯甲烷进行抽提;旋蒸三氯甲烷,加入甲醇沉降,抽滤得最终宽带隙聚合物产物PDD-4。(Mn=186113;PDI=1.56);
所得聚合物分子量和分散性指数的测试结果见表1。
表1使用Still和DArP方法聚合的聚合物分子量和分散性指数对比
上述结果表明:使用本发明所述菲醌α-二胺钯类催化剂所得聚合物的分子量得到显著提升,PDI指数下降,材料分子量分布更均匀。
本发明通过构建出基于α-二胺分子为配体,引导筛选骨架、基团的设计规律,优化出最高效α-二胺钯催化剂。通过分子工程构建催化体系,获得高品质聚合物材料,实现基于PDD-4给体材料制备电池器件效率超过16%的有机太阳能电池。
上述实施例仅是为了清楚地说明所做的实例,而并非对实施方式的限制。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其他不同形式的变化或者变动,这里无需也无法对所有的实施方式予以穷举,因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。
Claims (8)
1.一类基于菲醌α-二胺的钯类催化剂,其特征在于,以α-二胺为配体中心,结构式见式I:
I;
式中,R为甲基、苯基中的一种;R1为烷基、烷氧基、氯原子、氟原子中的一种。
2.根据权利要求1所述的钯类催化剂,其特征在于,具体结构包括:
。
3.根据权利要求1所述的钯类催化剂,其特征在于,采用的NHC配体前体的结构式见式II:
II;
式中,R为甲基、苯基中的一种;R1为烷基、烷氧基、氯原子、氟原子中的一种。
4.权利要求1~3任一项所述基于菲醌α-二胺的钯类催化剂的制备方法,其特征在于,包括如下步骤:在反应容器中加入NHC配体前体、二氯化钯和反应溶剂,混合均匀后,在80~90℃和保护气氛下,回流反应10~24h。
5.根据权利要求4所述的制备方法,其特征在于,所述NHC配体前体的制备方法包括如下步骤:在反应容器中加入9,10-菲醌、式III化合物和氯化锌,加入醋酸为溶剂,100~120°C下搅拌5~12h;冷却至室温后,过滤出固体,将其溶于二氯甲烷,加入草酸钾和水,室温搅拌12-24h;二氯甲烷萃取,二氯甲烷和醋酸重结晶,即得所述NHC配体前体;
所述式III化合物的结构式见式III;
III;
式中,R为甲基或苯基;R1为烷基、烷氧基、氯原子、氟原子中的一种。
6.权利要求1-3任一项所述基于菲醌α-二胺的钯类催化剂或权利要求4~5任一项所述制备方法制备的基于菲醌α-二胺的钯类催化剂在制备D-A型聚合物领域中的应用,其特征在于,包括如下步骤:将D单元单体、A单元单体、基于菲醌α-二胺的钯类催化剂、膦配体、碱金属碳酸盐、四甲基乙二胺、t-BuCO2H加入有机溶剂中混合均匀,然后在110~150 ℃和保护气氛下,反应24~72 h;其中D单元单体、A单元单体和催化剂的摩尔比为1:1:0.02~0.05。
7.根据权利要求6所述的应用,其特征在于,所述有机溶剂为甲苯、氯苯或邻二甲苯。
8.根据权利要求6所述的应用,其特征在于,所得D-A型聚合物的分子量达18 KDa,分散性指数下降至1.56。
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