CN102834430B - 含噻吩并噻二唑单元卟啉共聚物、其制备方法和应用 - Google Patents
含噻吩并噻二唑单元卟啉共聚物、其制备方法和应用 Download PDFInfo
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- CN102834430B CN102834430B CN201080066000.1A CN201080066000A CN102834430B CN 102834430 B CN102834430 B CN 102834430B CN 201080066000 A CN201080066000 A CN 201080066000A CN 102834430 B CN102834430 B CN 102834430B
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- porphyrin
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- C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- C—CHEMISTRY; METALLURGY
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Abstract
公开一种含噻吩并噻二唑单元卟啉共聚物及其制备方法和用途。其具有结构式(I),式中:R1,R2,R3,R4为相同或不相同的C1-C32烷基;n为1-100的整数。该共聚物包含芴单元,噻吩并噻二唑单元以及卟啉单元,增大共聚物的骨架电子云密度,使得共聚物的带隙变窄,从而加宽共聚物的光谱响应范围,提高光电转换效率。
Description
技术领域
本发明属于有机材料技术领域,具体涉及一种含噻吩并噻二唑单元卟啉共聚物、其制备方法和应用。
背景技术
当今世界经济主要是建立在以化石能源,如煤炭、石油和天然气等基础之上的经济。然而,这些不可再生的化石能源都在不断的枯竭。进入21世纪以来,全球性的能源问题以及随之而来的环境污染和气候变暖等问题日益凸现和逐渐加剧。由于太阳能具有分布普遍和广阔,资源数量多,无污染,清洁,安全以及获取方便等突出优点,被认为是最有希望的可再生能源之一。
为充分利用太阳光照射的能量,人们不断开发出能够吸收太阳光的新型材料,其中无机半导体材料获得较为广泛的发展和应用,例如目前用于地面的硅晶电池,然而由于其生产工艺复杂、成本高,使其应用受到限制。为了降低成本,拓展应用范围,长期以来人们一直在寻找新型的替代的有机光电材料。
近年来,越来越多的研究集中在有机太阳能电池等光电器件上应用的有机光电材料。有机太阳能电池是一种新型的太阳能电池,有机太阳能电池将太阳光能转化成电能,相对于无机半导体材料来源有限、价格昂贵、有毒、制备工艺复杂、成本太高等而言,它具有无机太阳能电池无法比拟的一些优点,如材料来源广泛、结构多样性和可调控性、成本低廉、安全环保、制作工艺简单、产品重量轻、可大面积柔性制备等等,可以广泛应用在建筑、照明和发电等多种领域,具有重要的发展和应用前景。因此,国内外众多的研究机构和企业等都给予了相当的关注和投入。然而,到目前为止,有机太阳能电池的光电转换效率比无机太阳能电池还是要低很多。因此,开发新型的有机光电材料对于提高有机太阳能电池及其它半导体器件的效率具有重要意义。
发明内容
有鉴于此,提供一种光谱响应宽、光电转换效率高的含噻吩并噻二唑单元卟啉共聚物,以及一种含噻吩并噻二唑单元卟啉共聚物制备方法。
本发明实施例还提供上述含噻吩并噻二唑单元卟啉共聚物在有机光电材料、太阳能电池器件、有机场效应晶体管、有机电致发光器件、有机光存储器件或有机激光器件中的应用。
一种含噻吩并噻二唑单元卟啉共聚物,其具有如下所示的结构式:
式中:R1、R2、R3、R4为相同或不相同的C1-C32的烷基;n为1-100的整数。
一种含噻吩并噻二唑单元卟啉共聚物制备方法,其包括如下步骤:
分别提供如下结构式表示的化合物A、B、C、D,
在含有催化剂、氧化剂和有机溶剂的体系中,将化合物A、B、C进行缩聚氧化反应,生成5,15-二(9,9-二烷基芴)卟啉;
在含有催化剂和有机溶剂的体系中,将5,15-二(9,9-二烷基芴)卟啉进行溴化取代反应,生成5,15-二溴-10,20-二(9,9-二烷基芴)卟啉;
在催化剂和有机溶剂存在的条件下,将5,15-二溴-10,20-二(9,9-二烷基芴)卟啉与化合物D进行Suzuki耦合反应,获得如下结构式(1)表示的共聚物:
结构式(1)中的n为1-100的整数。
以及,上述含噻吩并噻二唑单元卟啉共聚物在有机光电材料、太阳能电池器件、有机场效应晶体管、有机电致发光器件、有机光存储器件或有机激光器件中的应用。
在上述含噻吩并噻二唑单元卟啉共聚物中,所含的芴具有优异的光稳定性和热稳定性,并具有易修饰的结构,例如通过引入烷基,来提高材料的溶解性能,有利于成膜加工。该共聚物还具有低的能隙,可以增大共聚物的骨架电子云的密度,使得共聚物的带隙变窄,从而加宽共聚物的光谱响应范围。卟啉结构能使共聚物具有较高的电荷转移和能量转移反应的量子效率,具有良好的电子缓冲性和光电磁性,良好的刚柔性、较好热稳定性和环境稳定性。共聚物中的噻吩并[3,4-c][1,2,5]噻二唑具有优良的平面结构,也有利于降低带隙,提高光电转换效率。在上述含噻吩并噻二唑单元卟啉共聚物制备方法中,采用较简单的合成路线,从而减少工艺流程,降低制造成本。该共聚物可适用于有机光电材料、太阳能电池器件、有机场效应晶体管、有机电致发光器件、有机光存储器件或有机激光器件中,不仅能提高其光电转换效率,而且能减轻太阳能电池器件的质量,且便于大批量的制备。
附图说明
下面将结合附图及实施例对本发明作进一步说明,附图中:
图1显示本发明实施例的含噻吩并噻二唑单元卟啉共聚物的结构式;
图2是本发明实施例的含噻吩并噻二唑单元卟啉共聚物制备方法流程图;
图3是采用本发明实施例的含噻吩并噻二唑单元卟啉共聚物的太阳能电池器件结构示意图;
图4是采用本发明实施例的含噻吩并噻二唑单元卟啉共聚物的有机电致发光器件的结构示意图;
图5是采用本发明实施例的含噻吩并噻二唑单元卟啉共聚物的有机场效应晶体管的结构示意图。
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,以下结合附图及实施例,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仅用以解释本发明,并不用于限定本发明。
请参阅图1,显示本发明实施例的含噻吩并噻二唑单元卟啉共聚物的结构式,具有如下所示的结构式(I):
式中:R1、R2、R3、R4为相同或不相同的C1-C32的烷基;n为1-100的整数。
在一个优选的实施例中,含噻吩并噻二唑单元卟啉共聚物的每个单元中具有两个相同的含烷基芴基团,也即,例如R1、R3为相同的C1-C32的烷基,R2、R4为相同的C1-C32的烷基,或者换句话说,R1、R4为相同的C1-C32的烷基,R2、R3为相同的C1-C32的烷基,这种较为对称的结构便于制备,产率较高。进一步,R1、R2为相同的C8-C32的烷基,以及/或者R3、R4为相同的C8-C32的烷基,这样即在共聚物中引入长链烷基,以提高材料的溶解性能,提高共聚物的成膜加工性能。更优选地,R1、R2、R3、R4为C8-C32的烷基。n优选为10-50的整数。上述烷基可以是直链烷基、支链烷基或环状烷基。
在上述结构式(1)表示的共聚物中,包括芴或其衍生物、卟啉结构和含噻吩并噻二唑单元。其中,芴或其衍生物具有优异的光热稳定性和成膜性,共聚物还通过引入含噻吩并噻二唑单元来增大共聚物的骨架电子云的密度,使得共聚物的带隙变窄,光谱吸收范围加宽。卟啉结构能使共聚物具有较高的电荷转移和能量转移反应的量子效率,具有良好的电子缓冲性和光电磁性,良好的刚柔性、较好热稳定性和环境稳定性。共聚物中的噻吩并[3,4-c][1,2,5]噻二唑具有优良的平面结构,是含有一个五元环和六元环骨架的受体单元,具有分子内电荷转移性质和优异的电化学还原性质。噻吩并噻二唑单元的S...N作用力使得聚合物聚集态结构有序化,从而对降低带隙有利,因此本实施例将噻吩并噻二唑单元作为受体单元引入到光电材料中以调节带宽和还原电势。在光伏材料中将能进一步降低带隙的受体单元噻吩并[3,4-c][1,2,5]噻二唑引入到给电子的芴卟啉单元中形成的具有电子给体-受体结构单元的材料,并同时具有高的空穴迁移率和宽的太阳光吸收光谱范围,提高光电转换效率。
由此,上述含噻吩并噻二唑单元卟啉共聚物具有较宽的光谱响应范围,波段大约在280-780nm,基本涵盖可见光波段,还具有较好的热稳定性和环境稳定性,表现出较好的光电性能,而且利用芴单元、噻吩并噻二唑单元及卟啉单元三者的协同作用,提高光电转换效率。在本实施例的共聚物中,R1、R2、R3、R4选自C1-C32的烷基,通过引入烷基链以提高材料的溶解性能,有利于成膜加工,扩大其应用范围。
请参阅图2,上述含噻吩并噻二唑单元卟啉共聚物的制备方法包括如下步骤:
S10,分别提供如下结构式表示的化合物A、B、C、D,
其中R1、R2、R3、R4为相同或不相同的C1-C32的烷基;
S20,在含有催化剂、氧化剂和有机溶剂的体系中,将化合物A、B、C进行缩聚氧化反应,生成5,15-二(9,9-二烷基芴)卟啉;
S30,在含有催化剂和有机溶剂的体系中,将5,15-二(9,9-二烷基芴)卟啉进行溴化取代反应,生成5,15-二溴-10,20-二(9,9-二烷基芴)卟啉;
S40,在催化剂和有机溶剂存在的条件下,将5,15-二溴-10,20-二(9,9-二烷基芴)卟啉与化合物D进行Suzuki耦合反应,获得如下结构式(1)表示的共聚物:
结构式(1)中的n为1-100的整数。
在步骤S01中,化合物A、B、C、D可直接从市场上购得或者通过现有的合成方法制备。其中,与上述含噻吩并噻二唑单元卟啉共聚物的描述基本相同,R1、R2、R3、R4采用上面描述的结构形式,在此不再赘述。n优选为10-50的整数。
本实施例中,化合物A、B、C、D分别制备而得,具体如下:
1、化合物A和B的制备
以化合物A为例,其制备包括以下步骤:
第一步,由2-溴芴与溴烷在催化剂、有机溶剂条件下进行取代反应,制得9,9-二烷基-2-溴芴。催化剂为四丁基溴化铵或者苄基三乙基氯化铵等,有机溶剂为甲苯、二甲亚砜或四氢呋喃等。对应地,溴烷分别是烷基为R1、R2的溴烷。如下所示,分两个反应步骤,即步骤i和ii,用两种溴烷(当R1、R2相同时为同一种)分别进行取代反应,其反应路线如下:
9,9-二烷基-2-溴芴的详细制备过程可参考文献:《高分子》(Macromolecules),2002,35,3474。
第二步,在含有烷基锂、二甲基甲酰胺和有机溶剂体系中进行溴基醛化的反应,其反应路线如下:
在一些具体的实施例中,烷基锂为C2-C4的烷基锂,本实施例采用正丁基锂,有机溶剂可为四氢呋喃、四氯化碳或氯仿等,详细制备过程可参考文献:《高分子》(Macromolecules),2006,39,456。
在制备化合物B时,各步骤基本相同,不同在于两种溴烷的烷基分别替换为R3、R4。
2、化合物C的制备
在含有甲醛、催化剂和吡咯的体系中进行缩合反应,制得化合物C,其反应式如下所示:
其中,催化剂可以为三氟乙酸,也可以为三氟化硼二甲基氧基络合物(BF3·(CH3)2O),吡咯既是有机溶剂又是反应物。二吡咯甲烷即化合物C的制备详细步骤可参考文献:《四面体》(Tetrahedron),1994,39,11427。
3、化合物D的制备
在正丁基锂、有机溶剂存在的条件下进行的如下取代反应:
其中正丁基锂可以替换以其它烷基锂,例如但不限于C2-C4的烷基锂,有机溶剂可为四氢呋喃、四氯化碳或氯仿等,优选为四氢呋喃。具体实施过程如下:在反应器中加入9,10-二溴噻吩并[3,4-c][1,2,5]噻二唑,加入有机溶剂,在-20到-78℃条件下注入正丁基锂,继续搅拌反应1-12h,在-20到-78℃条件下注入2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,室温下搅拌过夜(例如12-14小时)。加入饱和氯化钠水溶液终止反应,用氯仿萃取,无水硫酸钠干燥,抽虑后将滤液收集并旋蒸掉溶剂。最后将粗产物用石油醚/乙酸乙酯(15/1)为淋洗液进行硅胶柱层析分离,得到产物,即化合物D。
在步骤S02中,催化剂可采用有机酸,例如但不限于三氟乙酸或丙酸等,氧化剂可采用二氯二氰基苯醌或其类似物,并不限于此,有机溶剂可采用二氯甲烷、四氢呋喃、四氯化碳、氯仿或乙腈等。其反应式如下所示:
具体实施步骤如下:在无水无氧条件下,将化合物A、B、C(例如按照A/B/C的摩尔比例1/1/2称取),溶解于二氯甲烷等有机溶剂中,通入氮气,加入三氟乙酸作催化剂,20-100℃下搅拌1-24小时,然后加入两个摩尔当量(即为反应计量比的两倍)的二氯二氰基苯醌(DDQ),继续搅拌1-60分钟,然后加入三乙胺淬灭反应。接着进行如下提纯:浓缩溶剂,过滤,收集滤液并旋干溶剂,用二氯甲烷在硅胶柱上快速淋洗,旋干溶剂,用乙醚/甲醇重结晶到产物,即芴基卟啉化合物,产率约在70%以上。
在本发明实施例中涉及的无氧条件可以是在氮气、二氧化碳或惰性气体等保护气氛条件下,例如可以为100%的氮气、氩气、二氧化碳等环境,无氧条件的获得方法也可以包括各种方法,但是优选的是通过油泵抽真空,再通入氮气,如此反复3-4次,再一直通入氮气使反应体系处于氮气的保护下,同时在向反应体系加入反应物的时候,保持该保护气体气氛。
步骤S03,在含有催化剂和有机溶剂的体系中,将步骤S02生成的芴基卟啉化合物进行溴化取代反应,生成二溴取代的芴基卟啉化合物。有机溶剂可以是但不限于氯仿、四氢呋喃、二甲基甲酰胺(DMF)、四氯化碳、二氯甲烷或乙腈等,并加入N-溴代丁二酰亚胺(NBS)、Br2、HBr或PBr3等作为溴源,优选为NBS。
步骤S03具体实施过程如下:在无水无氧条件下,将5,15-二(9,9-二烷基芴)卟啉溶解于有机溶剂中,加入适量吡啶,将反应物降到0℃,加入适量N-溴代丁二酰亚胺,搅拌后,混合物恢复到20-40℃,然后继续搅拌1-48小时,加入丙酮终止反应,除去溶剂,用乙醚/甲醇进行重结晶得到产物,产率约在80%以上。本实施例各步骤所涉及的有机溶剂都可以是弱极性或极性非质子性有机溶剂或其混合溶剂,并不限于各步骤中所列举的具体有机溶剂。
步骤S03中涉及的反应式如下所示:
步骤S04中,催化剂可以为有机钯催化剂,其用量为化合物D的摩尔用量的0.05-20%。有机钯催化剂例如可以是但不限于Pd2(dba)3/P(o-Tol)3、Pd(PPh3)4或Pd(PPh3)2Cl2。另外,催化剂也可以是有机钯和有机膦配体的混合物,两者为按照摩尔配比为1∶2-20混合。有机溶剂为弱极性或极性非质子性有机溶剂或其混合溶剂,例如可以是但不限于氯仿、二氯甲烷、乙二醇二甲醚、二甲基亚砜(DMSO)、四氢呋喃(THF)、甲苯、二甲苯或其类似化合物,优选为甲苯。有机溶剂的用量足量,以使各反应物溶解并充分反应。步骤S04进行的反应式如下所示:
步骤S04的具体实施过程如下:在无氧条件下,将化合物D、5,15-二溴-10,20-二(9,9-二烷基芴)卟啉按照摩尔比1∶1.5~1.5∶1加入到有机溶剂中,抽真空除氧并充入氮气,然后加入催化剂,加热到50-120℃,反应12-80小时,冷却后将反应液加入到二乙基二硫代氨基甲酸钠的水溶液中,然后将混合液加热到60-80℃搅拌过夜(约12-14小时)。在反应液加入到二乙基二硫代氨基甲酸钠的水溶液之前,先滴加到甲醇中进行沉降,抽滤,甲醇洗涤,干燥,用甲苯溶解后再加入到二乙基二硫代氨基甲酸钠的水溶液中。在搅拌过夜后,进行如下提纯:将最后反应体系有机相通过氧化铝的柱层析,氯苯淋洗,减压除去有机溶剂,甲醇沉降,抽滤,所得固体用丙酮索氏提取。甲醇沉降,抽滤。真空泵下抽过夜(例如12-14小时)得到产物。所得共聚物中的聚合度n优选为10-50。在实际制备过程中,可通过对有机溶剂的选择、对反应温度、反应时间、反应物的加入量、催化剂种类和用量进行控制,以获得所想要的聚合度。
在上述方法中,化合物A、B、C、D单体的合成路线比较简单且成熟,从而减少工艺流程,降低制造成本。而且Suzuki耦合反应是一种非常成熟的聚合反应,产率高、条件温和,易于控制,且易通过引入烷基提高产物的溶解性和分子量,以实现可旋涂的聚合物。
本实施例的含噻吩并噻二唑单元卟啉共聚物可作为有机光电材料,应用于各种光电或半导体器件中,例如,可用于太阳能电池器件、有机场效应晶体管、有机电致发光器件、有机光存储器件或有机激光器件等。其中,有机光电材料即采用上述含噻吩并噻二唑单元卟啉共聚物,作为电子给体材料或光电转换材料等。下面以太阳能电池器件、有机场效应晶体管,有机电致发光器件为例进行说明。其它如有机光存储器件,有机非线性材料和有机激光器件与下面类似,都是以本实施例的含噻吩并噻二唑单元卟啉共聚物作为其的光存储材料、激光材料或半导体材料等。
请参阅图3,显示采用上述实施例中含噻吩并噻二唑单元卟啉共聚物的太阳能电池器件,其包括依次层叠的玻璃基层11、透明阳极12、中间辅助层13、活性层14、阴极15,中间辅助层13采用聚乙烯二氧基噻吩:聚苯乙烯-磺酸复合材料(简称为PEDOT:PSS),活性层14包括电子给体材料和电子受体材料,电子给体材料采用上述含噻吩并噻二唑单元卟啉共聚物,电子受体材料可以是[6,6]苯基-C61-丁酸甲酯(简称为PCBM)。透明阳极12可采用氧化铟锡(简称为ITO),优选为方块电阻为10-20Ω/的氧化铟锡。阴极15可采用铝电极。其中,玻璃基层11可作为底层,制作时,先将ITO电极沉积于玻璃基层11,再用氧-等离子喷涂(氧-Plasma)处理工艺,将中间辅助层13形成于ITO电极上,以及将含噻吩并噻二唑单元卟啉共聚物和电子受体材料通过旋涂技术沉积于中间辅助层13上,形成活性层14,然后再通过真空蒸镀技术在活性层14上沉积阴极15,获得上述太阳能电池器件。
如图所示,在光照下,光透过玻璃基层11和ITO电极12,活性层14中的含噻吩并噻二唑单元卟啉共聚物吸收光能,并产生激子,这些激子再迁移到电子给体/受体材料的界面处,并将电子转移给电子受体材料,如PCBM,实现电荷的分离,从而形成自由的载流子,即自由的电子和空穴。这些自由的电子沿电子受体材料向金属阴极传递并被阴极所收集,自由的空穴沿电子给体材料向ITO阳极传递并被阳极所收集,从而形成光电流和光电压,实现光电转换,外接负载16时,可对其进行供电。在此过程中,含噻吩并噻二唑单元卟啉共聚物由于其具有很宽的光谱响应范围,能够更充分地利用光能,以获得更高的光电转换效率,增加太阳能电池器件的产电能力。而且这种有机材料还能减轻太阳能电池器件的质量,并通过旋涂等技术即可制作,便于大批量的制备。
请参阅图4,显示采用上述实施例中的含噻吩并噻二唑单元卟啉共聚物的有机电致发光器件,其包括依次层叠设置的玻璃基层21、透明阳极22、发光层23、缓冲层24、阴极25。透明阳极22可采用氧化铟锡(简称为ITO),优选为方块电阻为10-20Ω/的氧化铟锡。发光层23包含上述实施例中的含噻吩并噻二唑单元卟啉共聚物。缓冲层24可采用LiF等,但不限于此。阴极25可以是但不限于金属Al或Ba等,但不限于此。因而,在一个具体实施例中,有机电致发光器件结构表示为:ITO/含噻吩并噻二唑单元卟啉共聚物/LiF/Al。各层可采用现有方法形成,而含噻吩并噻二唑单元卟啉共聚物可通过旋涂技术形成于ITO上。
请参阅图5,显示采用上述实施例中的含噻吩并噻二唑单元卟啉共聚物的有机场效应晶体管,其包括依次层叠设置的衬底31、绝缘层32、修饰层33、有机半导体层34以及设于有机半导体层34上的源电极35和漏电极36。其中,衬底31可以是但不限于高掺杂的硅片(Si),绝缘层32可以是但不限于微纳米(如450nm)厚的SiO2。有机半导体层34采用上述描述的含噻吩并噻二唑单元卟啉共聚物。源电极35和漏电极36均可采用但不限于金。修饰层33可以是但不限于十八烷基三氯硅烷。衬底31、绝缘层32、修饰层33以及源电极35和漏电极36都可采用现有的方法形成。有机半导体层34可以将上述实施例中的含噻吩并噻二唑单元卟啉共聚物旋涂于由修饰层33修饰的绝缘层32上。
以下通过具体实施例来举例说明含噻吩并噻二唑单元卟啉共聚物、其制备方法以及其性能等方面。
实施例1
本实施例1提供结构如下的10,20-二(9,9-二辛基芴)卟啉-噻吩并[3,4-c][1,2,5]噻二唑共聚物,该聚合物的结构式如第四步骤的反应式的产物所示。上述聚合物的制备步骤如下:
一、5,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基噻吩并[3,4-c][1,2,5]噻二唑的制备,其制备涉及反应式如下所示:
具体过程为:在氮气的保护下,往三口瓶中加入对9,10-二溴噻吩并[3,4-c][1,2,5]噻二唑(9.0g,0.03mol),加入200ml的四氢呋喃溶剂,在-78℃条件下再用注射器慢慢注入正丁基锂(25.2mL,2.5M,0.06mol),继续搅拌反应2h,在-78℃条件下用注射器注入2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷(13mL,0.06mol),室温下搅拌过夜。加入饱和氯化钠水溶液(30ml)终止反应,用氯仿萃取,无水硫酸钠干燥,抽虑后将滤液收集并旋蒸掉溶剂。最后将粗产物用石油醚/乙酸乙酯(15/1)为淋洗液进行硅胶柱层析分离,得到产物,产率92%。
二、10,20-二(9,9-二辛基芴)卟啉的制备
由于R1、R2、R3、R4同为辛基,此步骤采用的原料化合物A和B相同,这样可具有较高产率和产物纯度,涉及反应式如下所示:
具体过程为:搭好无水无氧装置,称取中间体9,9-二辛基-2-醛芴(0.42g,1mmol)与二吡咯甲烷(0.15g,1mmol),溶解于300ml二氯甲烷中,通入氮气30min,注射器加入丙酸1ml,20℃下搅拌24h,然后加入二氯二氰基苯醌(DDQ)(0.91g,4mmol),继续在室温下搅拌30min,然后加入1ml三乙胺淬灭反应,浓缩溶剂,过滤,收集滤液并旋干溶剂,用二氯甲烷在硅胶柱上快速淋洗,旋干溶剂,用乙醚/甲醇重结晶到产物,产率约为75%。
三、5,15-二溴-10,20-二(9,9-二辛基芴)卟啉的制备,此步骤反应式如下所示:
具体过程为:搭好无水无氧装置,称取10,20-二(9,9-二辛基芴)卟啉(0.22g,0.2mmol)溶解于80ml氯仿中,加入1ml吡啶,将反应物降到0℃,加入N-溴代丁二酰亚胺(0.07g,0.4mmol),搅拌72h后,混合物恢复到室温,然后继续搅拌4h,加入5ml丙酮终止反应,除去溶剂,用乙醚/甲醇进行重结晶得到产物,产率86%。
四、10,20-二(9,9-二辛基芴)卟啉-噻吩并[3,4-c][1,2,5]噻二唑共聚物的制备,此步骤涉及反应式如下所示:
具体过程为:在氮气保护下,加入5,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基噻吩并[3,4-c][1,2,5]噻二唑(79mg,0.2mmol)、5,15-二溴-10,20-二(9,9-二辛基芴)卟啉(250mg,0.2mmol)和甲苯溶剂40ml,抽真空除氧并充入氮气,然后加入5mg Pd(PPh3)2Cl2,加热到100℃反应56h。冷却至室温后将混合液滴加到200ml甲醇中进行沉降。抽滤,甲醇洗涤,干燥。然后用甲苯溶解,加入到二乙基二硫代氨基甲酸钠的水溶液中,然后将混合液加热到80℃搅拌过夜。将有机相通过氧化铝的柱层析,氯苯淋洗。减压除去有机溶剂,甲醇沉降。抽滤,所得固体用丙酮索氏提取器提取三天。甲醇沉降,抽滤。真空泵下抽过夜得到产物,产率78%。分子量(Molecular weight)测试结果为:(GPC,THF,R.I):Mn=39600,Mw/Mn=3.52;)
实施例2
本实施例2提供结构如下的10-(9-甲基-9-辛基芴)-20-(9-癸基-9-十六烷基芴)卟啉-噻吩并[3,4-c][1,2,5]噻二唑共聚物,该聚合物的结构式如第四步骤的反应式的产物所示。上述聚合物的制备步骤如下:
一、5,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基噻吩并[3,4-c][1,2,5]噻二唑其制备详见实施例1。
二、10-(9-甲基-9-辛基芴)-20-(9-癸基-9-十六烷基芴)卟啉的制备,此步骤涉及反应式如下所示:
具体过程为:搭好无水无氧装置,称取中间体9-甲基-9-辛基芴(0.32g,1mmol)、9-癸基-9-十六烷基芴(0.56g,1mmol)、二吡咯甲烷(0.30g,2mmol),溶解于250ml二氯甲烷中,通入氮气30min,注射器加入三氟乙酸2ml,100℃下搅拌1h,然后加入二氯二氰基苯醌(DDQ)(1.82g,8mmol),继续在室温下搅拌30min,然后加入2ml吡啶淬灭反应,浓缩溶剂,过滤,收集滤液并旋干溶剂,用二氯甲烷在硅胶柱上快速淋洗,旋干溶剂,用乙醚/甲醇重结晶到产物,产率约为71%。
三、5,15-二溴-10-(9-甲基-9-辛基芴)-20-(9-癸基-9-十六烷基芴)卟啉的制备,此步骤涉及反应式如下所示:
具体过程为:搭好无水无氧装置,称取10-(9-甲基-9-辛基芴)-20-(9-癸基-9-十六烷基芴)卟啉(0.23g,0.2mmol)溶解于80ml氯仿中,加入1ml吡啶,将反应物降到0℃,加入N-溴代丁二酰亚胺(0.07g,0.4mmol),搅拌0.5h后,混合物升温至120℃,然后继续搅拌1h后,加入5ml丙酮终止反应,除去溶剂,用乙醚/甲醇进行重结晶得到产物,产率81%。
四、10-(9-甲基-9-辛基芴)-20-(9-癸基-9-十六烷基芴)卟啉-噻吩并[3,4-c][1,2,5]噻二唑共聚物的制备,此步骤涉及反应式如下所示:
具体过程为:在氮气保护下,加入5,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基噻吩并[3,4-c][1,2,5]噻二唑(79mg,0.2mmol)、5,15-二溴-10-(9-甲基-9-辛基芴)-20-(9-癸基-9-十六烷基芴)卟啉(260mg,0.2mmol)和甲苯溶剂100ml,抽真空除氧并充入氮气,然后加入Pd(OAc)2(2.5mg)/三环己基膦(6.5mg)和2ml 20%(wt)Et3NOH溶液。,加热到120℃反应24h。冷却至室温后将混合液滴加到200ml甲醇中进行沉降。抽滤,甲醇洗涤,干燥。然后用甲苯溶解,加入到二乙基二硫代氨基甲酸钠的水溶液中,然后将混合液加热到80℃搅拌过夜。将有机相通过氧化铝的柱层析,氯苯淋洗。减压除去有机溶剂,甲醇沉降。抽滤,所得固体用丙酮索氏提取三天。甲醇沉降,抽滤。真空泵下抽过夜得到产物,产率76%。分子量(Molecular weight)测试结果为:(GPC,THF,R.I):Mn=42800,Mw/Mn=4.33;)
实施例3
本实施例3提供结构如下的10-(9-甲基-9-三十二烷基基芴)-20-(9,9-二(十六烷基芴))卟啉-噻吩并[3,4-c][1,2,5]噻二唑共聚物,该聚合物的结构式如第四步骤的反应式的产物所示。上述聚合物的制备步骤如下:
一、5,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基噻吩并[3,4-c][1,2,5]噻二唑
其制备详见实施例1。
二、10-(9-甲基-9-三十二烷基基芴)-20-(9,9-二(十六烷基芴))卟啉的制备,此步骤涉及反应式如下所示:
具体过程为:搭好无水无氧装置,称取中间体9-甲基-9-三十二烷基芴(0.66g,1mmol)、9,9-二(十六烷基芴)(0.64g,1mmol)、二吡咯甲烷(0.30g,2mmol),溶解于300ml二氯甲烷中,通入氮气30min,注入三氟乙酸2ml,室温下搅拌3h,然后加入二氯二氰基苯醌(DDQ)(1.82g,8mmol),继续在室温下搅拌30min,然后加入2ml三乙胺淬灭反应,浓缩溶剂,过滤,收集滤液并旋干溶剂,用二氯甲烷在硅胶柱上快速淋洗,旋干溶剂,用乙醚/甲醇重结晶到产物,产率约为85%。
三、5,15-二溴-10-(9-甲基-9-三十二烷基基芴)-20-(9,9-二(十六烷基芴))卟啉的制备,此步骤涉及反应式如下所示:
具体过程为:搭好无水无氧装置,称取10-(9-甲基-9-三十二烷基基芴)-20-(9,9-二(十六烷基芴))卟啉(0.31g,0.2mmol)溶解于100ml氯仿中,加入1ml吡啶,将反应物降到0℃,加入N-溴代丁二酰亚胺(0.07g,0.4mmol),搅拌0.5h后,混合物升温至30℃,然后继续搅拌48h,加入5ml丙酮终止反应,除去溶剂,用乙醚/甲醇进行重结晶得到产物,产率82%。
四、10-(9-甲基-9-三十二烷基基芴)-20-(9,9-二(十六烷基芴))卟啉-噻吩并[3,4-c][1,2,5]噻二唑共聚物的制备,此步骤涉及反应式如下所示:
具体过程为:在氮气保护下,加入5,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基噻吩并[3,4-c][1,2,5]噻二唑(79mg,0.2mmol)、5,15-二溴-10-(9-甲基-9-三十二烷基基芴)-20-(9,9-二(十六烷基芴))卟啉(343mg,0.2mmol)和甲苯溶剂80ml,抽真空除氧并充入氮气,然后加入8mg Pd(PPh3)4,加热到50℃反应72h。冷却至室温后将混合液滴加到250ml甲醇中进行沉降。抽滤,甲醇洗涤,干燥。然后用甲苯溶解,加入到二乙基二硫代氨基甲酸钠的水溶液中,然后将混合液加热到80℃搅拌过夜。将有机相通过氧化铝的柱层析,氯苯淋洗。减压除去有机溶剂,甲醇沉降。抽滤,所得固体用丙酮索氏提取三天。甲醇沉降,抽滤。真空泵下抽过夜得到产物,产率76%。分子量(Molecular weight)测试结果为:(GPC,THF,R.I):Mn=38100,Mw/Mn=3.62;)。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
2.如权利要求1所述的含噻吩并噻二唑单元卟啉共聚物,其特征在于,所述含噻吩并噻二唑单元卟啉共聚物的每个单元中具有两个相同的含烷基芴基团。
3.如权利要求1所述的含噻吩并噻二唑单元卟啉共聚物,其特征在于,所述R1、R2、R3、R4为相同的C8-C32的烷基。
4.如权利要求1所述的含噻吩并噻二唑单元卟啉共聚物,其特征在于,所述n为10-50的整数。
5.一种含噻吩并噻二唑单元卟啉共聚物制备方法,其包括如下步骤:
分别提供如下结构式表示的化合物A、B、C、D,
其中,R1、R2、R3、R4为相同或不相同的C1-C32的烷基;
在含有催化剂、氧化剂和有机溶剂的体系中,将化合物A、B、C进行缩聚 氧化反应,生成5,15-二(9,9-二烷基芴)卟啉;
在含有催化剂和有机溶剂的体系中,将5,15-二(9,9-二烷基芴)卟啉进行溴化取代反应,生成5,15-二溴-10,20-二(9,9-二烷基芴)卟啉;
在催化剂和有机溶剂存在的条件下,将5,15-二溴-10,20-二(9,9-二烷基芴)卟啉与化合物D进行Suzuki耦合反应,获得如下结构式(1)表示的共聚物:
结构式(1)中的n为1-100的整数。
6.如权利要求5所述的含噻吩并噻二唑单元卟啉共聚物制备方法,其特征在于,所述缩聚氧化反应过程包括如下步骤:在无水无氧条件下,将化合物A、B、C溶解于有机溶剂中,加入有机酸作催化剂,在20-100℃下搅拌1-24小时,加入二氯二氰基苯醌作氧化剂,继续搅拌反应1-60分钟,加入三乙胺淬灭反应,然后提纯,得到产物。
7.如权利要求5所述的含噻吩并噻二唑单元卟啉共聚物制备方法,其特征在于,所述Suzuki耦合反应过程包括如下步骤:在无氧条件下,将化合物D、5,15-二溴-10,20-二(9,9-二烷基芴)卟啉按照摩尔比1:1.5~1.5:1加入到有机溶剂中,抽真空除氧并充入保护气体,然后加入催化剂,加热到50-120℃,反应12-80小时,冷却后将反应液加入到二乙基二硫代氨基甲酸钠的水溶液中,然后将混合液加热到60-80℃搅拌12-14小时。
8.如权利要求5所述的含噻吩并噻二唑单元卟啉共聚物制备方法,其特征在于,所述R1、R2、R3、R4为相同的C8-C32的烷基,所述n为10-50的整数。
9.如权利要求5所述的含噻吩并噻二唑单元卟啉共聚物制备方法,其特征 在于,所述Suzuki耦合反应采用的催化剂为有机钯或者按照摩尔配比为1:2-20的有机钯和有机膦配体的混合物,所述Suzuki耦合反应采用的催化剂的摩尔用量为化合物D摩尔用量的0.05%-20%,所述有机溶剂为氯仿、二氯甲烷、乙二醇二甲醚、二甲基亚砜、四氢呋喃、甲苯或二甲苯。
10.根据权利要求1-4任一项所述的含噻吩并噻二唑单元卟啉共聚物在太阳能电池器件、有机场效应晶体管、有机电致发光器件、有机光存储器件或有机激光器件中的应用。
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