技术领域technical field
本发明涉及一类可交联的噻吩并[3，4-b]噻吩共轭聚合物及其制备方法与应用。The invention relates to a class of crosslinkable thieno[3,4-b]thiophene conjugated polymers, a preparation method and application thereof.
背景技术Background technique
聚合物太阳能电池由于其造价低廉、重量轻、易于实现大面积柔性器件的制备等优点，在能源危机问题日益加剧的今天引起了研究者们的广泛兴趣，并在众多科研工作者的努力下，高效率的聚合物材料不断出现，最高能量转化效率已经达到7-8％。(1)Chen，H.Y.；Hou，J.H.；Zhang，S.Q.；Liang，Y.Y.；Yang，G.W.；Yang，Y.；Yu，L.P.；Wu，Y.；Li，G.Nature photonics.2009，3，649；(2)Samuel C.Price；Andrew C.Stuart；Yang.L.Q.；Zhou.H.X.；You.W.JACS.2011，133，4625。(3)Lijun Huo，Shaoqing Zhang，Xia Guo，Feng Xu，Yongfang Li，and Jianhui Hou Angew.Chem.Int.Ed.2011，50，9697-9702；(4)Samuel C.Price，Andrew C.Stuart，Liqiang Yang，Huaxing Zhou，Wei You，J.Am.Chem.Soc.2011，133，4625-4631；(5)Ta-Ya Chu，Jianping Lu，Serge Beaupre，Yanguang Zhang，Jean-Remi Pouliot，Salem Wakim，Jiayun Zhou，Mario Leclerc，Zhao Li，Jianfu Ding，Ye Tao，J.Am.Chem.Soc.2011，133，4250-4253；(6)Yongye Liang，Zheng Xu，Jiangbin Xia，Szu-Ting Tsai，Yue Wu，Gang Li，Claire Ray，Luping Yu，Adv.Mater.2010，22，E135-E138；(7)Zhicai He，Chengmei Zhong，Xun Huang，Wai-Yeung Wong，Hongbin Wu，Liwei Chen，Shijian Su，Yong Cao，DOI：10.1002/adma.201103006；(8)Ming-Shin Su，Chih-Yin Kuo，Mao-Chuan Yuan，U-Ser Jeng，Chun-Jen Su，Kung-Hwa Wei Adv.Mater.2011，23，3315-3319；(9)Chad M.Amb，Song Chen，Kenneth R.Graham，Jegadesan Subbiah，Cephas E.Small，Franky So，John R.Reynolds，J.Am.Chem.Soc.2011，133，10062-10065；(10)Huaxing Zhou，Liqiang Yang，Andrew C.Stuart，Samuel C.Price，Shubin Liu，Wei You，Angew.Chem.Int.Ed.2011，50，2995-2998.)让人们看到有机太阳能电池可商业化应用的前景。Due to its low cost, light weight, and easy preparation of large-area flexible devices, polymer solar cells have aroused widespread interest among researchers in today's increasingly aggravated energy crisis, and with the efforts of many scientific researchers, High-efficiency polymer materials continue to emerge, and the highest energy conversion efficiency has reached 7-8%. (1) Chen, H.Y.; Hou, J.H.; Zhang, S.Q.; Liang, Y.Y.; (2) Samuel C. Price; Andrew C. Stuart; Yang. L. Q.; Zhou. H. X.; (3) Lijun Huo, Shaoqing Zhang, Xia Guo, Feng Xu, Yongfang Li, and Jianhui Hou Angew. Chem. Int. Ed. 2011, 50, 9697-9702; (4) Samuel C. Price, Andrew C. Stuart, Liqiang Yang, Huaxing Zhou, Wei You, J.Am.Chem.Soc.2011, 133, 4625-4631; (5) Ta-Ya Chu, Jianping Lu, Serge Beaupre, Yangguang Zhang, Jean-Remi Pouliot, Salem Wakim, Jiayun Zhou, Mario Leclerc, Zhao Li, Jianfu Ding, Ye Tao, J.Am.Chem.Soc.2011, 133, 4250-4253; (6) Yongye Liang, Zheng Xu, Jiangbin Xia, Szu-Ting Tsai, Yue Wu , Gang Li, Claire Ray, Luping Yu, Adv. Mater.2010, 22, E135-E138; (7) Zhicai He, Chengmei Zhong, Xun Huang, Wai-Yeung Wong, Hongbin Wu, Liwei Chen, Shijian Su, Yong Cao , DOI: 10.1002/adma.201103006; (8) Ming-Shin Su, Chih-Yin Kuo, Mao-Chuan Yuan, U-Ser Jeng, Chun-Jen Su, Kung-Hwa Wei Adv.Mater.2011, 23, 3315 -3319; (9) Chad M. Amb, Song Chen, Kenneth R. Graham, Jegadesan Subbiah, Cephas E. Small, Franky So, John R. Reynolds, J. Am. Chem. Soc. 2011, 133, 10062-10065 ; (10) Huaxing Zhou, Liqiang Yang, Andrew C.Stuart, Samuel C.Price, Shubin Liu, Wei You, Angew.Chem.Int.Ed.2011, 50, 2995-2998.) Let people see organic solar cells Prospects for commercial application.
虽然上述报道的材料都有较高的能量转换效率，但这些材料存在两类问题。一是所成膜不具有抗溶剂性，现有的共轭聚合物给体材料和富勒烯及其衍生物受体材料都易溶于邻二氯苯、三氯甲烷等有机溶剂，当制备多层膜时，下层膜会被上层溶液的溶剂所溶解，因此无法制备多层结构器件。二是器件的热稳定性能差，主要原因是共混膜中聚合物和富勒烯及其衍生物倾向于各自分离，因此所形成的纳米微相分离结构是热不稳定的，它将在器件的操作过程中逐渐的变化，从而导致器件性能的降低。Although the materials reported above all have high energy conversion efficiencies, there are two types of problems with these materials. One is that the formed film does not have solvent resistance. The existing conjugated polymer donor materials and fullerene and its derivative acceptor materials are easily soluble in organic solvents such as o-dichlorobenzene and chloroform. When preparing In the case of a multilayer film, the lower film will be dissolved by the solvent of the upper layer solution, so it is impossible to prepare a multilayer structure device. The second is that the thermal stability of the device is poor. The main reason is that the polymer, fullerene and its derivatives in the blend film tend to separate separately, so the formed nano-microphase separation structure is thermally unstable, and it will be in the device. Gradual changes during operation, resulting in degraded device performance.
发明内容Contents of the invention
本发明的目的之一是提供一类含带交联基团的噻吩并[3，4-b]噻吩的共轭聚合物及其制备方法。One of the objects of the present invention is to provide a conjugated polymer containing thieno[3,4-b]thiophene with crosslinking groups and a preparation method thereof.
本发明所提供的含带交联基团的噻吩并[3，4-b]噻吩的共轭聚合物，其结构式如式I所示：The conjugated polymer containing thieno[3,4-b]thiophene with a crosslinking group provided by the present invention has a structural formula as shown in formula I:
(式I)(Formula I)
式I中，R1是在紫外光照或加热或加入引发剂下可交联的官能团(官能团是决定有机化合物的化学性质的原子或原子团)，R2可以是与R1相同的官能团，也可以是与R1不同的不可交联的取代基；In formula I, R1 is a crosslinkable functional group under ultraviolet light or heating or adding an initiator (functional group is an atom or atomic group that determines the chemical properties of an organic compound), R2 can be the same functional group as R1 , or is a non-crosslinkable substituent different fromR ;
Ar1、Ar2是相同的或不相同的具有共轭特征的单元；Ar1 and Ar2 are the same or different units with conjugation characteristics;
X1、X2可以是相同的或不相同的下述基团中的任意一种：H，F，Cl，Br，氰基和酯基；X1 and X2 can be any one of the following groups that are the same or different: H, F, Cl, Br, cyano and ester;
a/(a+b)是0-1的任意值且a/(a+b)不为0；a/(a+b) is any value from 0-1 and a/(a+b) is not 0;
n代表聚合物主链单元的重复个数，其数值是大于等于4的自然数。n represents the repeating number of polymer main chain units, and its value is a natural number greater than or equal to 4.
其中，所述可交联的官能团选自下述结构中的任意一种：Wherein, the crosslinkable functional group is selected from any one of the following structures:
k为0-16之间的任一自然数。k is any natural number between 0-16.
所述不可交联的取代基为C1-C18的烷基、C1-C18烷氧基或C1-C18的砜基。The non-crosslinkable substituent is a C1 -C18 alkyl group, a C1 -C18 alkoxy group or a C1 -C18 sulfone group.
所述具有共轭特征的单元是被烷基或烷氧基取代下述基团中的任意一种：苯、噻吩、萘、蒽、芴、三苯胺、吩噻嗪、吡咯、噻唑、吡啶、联吡啶、喹啉、呋喃、联苯、噻吩并[3，2-b]噻吩、噻吩并[3，4-b]噻吩、噻吩并[2，3-b]噻吩、双噻吩并[3，2-b：2’，3’-d]噻吩、咔唑、吲哚、4H-环丙基[2，1-b：3，4-b’]双噻吩、4，8-双烷氧基苯唑[1，2-b：4，5-b’]双噻吩、4，4’-双烷基双噻吩并[3，2-b：2’，3’-d]噻咯、苯并[1，2-b：4，5-b’]二噻吩。The unit with conjugation characteristics is any one of the following groups substituted by alkyl or alkoxy groups: benzene, thiophene, naphthalene, anthracene, fluorene, triphenylamine, phenothiazine, pyrrole, thiazole, pyridine, Bipyridine, quinoline, furan, biphenyl, thieno[3,2-b]thiophene, thieno[3,4-b]thiophene, thieno[2,3-b]thiophene, bisthieno[3, 2-b: 2',3'-d]thiophene, carbazole, indole, 4H-cyclopropyl[2,1-b:3,4-b']bisthiophene, 4,8-dialkoxy Benzo[1,2-b:4,5-b']bisthiophene, 4,4'-dialkylbisthieno[3,2-b:2',3'-d]silole, benzo [1,2-b:4,5-b']dithiophene.
作为取代基的烷基具体可为：甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、2-甲基丁基、3-甲基丁基、1-乙基丁基、2-乙基丁基、1-丙基丁基、戊基、异戊基、 2-甲基戊基、3-甲基戊基、4-甲基戊基、1-乙基戊基、2-乙基戊基、3-乙基戊基、己基、异己基、2-甲基己基、3-甲基己基、4-甲基己基、5-甲基己基、2-乙基己基、庚基、异庚基、辛基、异辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基和十八烷基中的任意一种。The alkyl group as the substituent can specifically be: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, 1- Ethylbutyl, 2-ethylbutyl, 1-propylbutyl, pentyl, isopentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethyl Amylpentyl, 2-ethylpentyl, 3-ethylpentyl, hexyl, isohexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2-ethyl ylhexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl Any one of alkyl, heptadecyl and octadecyl.
作为取代基的烷氧基具体可为：甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、叔丁氧基、2-甲基丁氧基、3-甲基丁氧基、1-乙基丁氧基、2-乙基丁氧基、1-丙基丁氧基、戊氧基、异戊氧基、2-甲基戊氧基、3-甲基戊氧基、4-甲基戊氧基、1-乙基戊氧基、2-乙基戊氧基、3-乙基戊氧基、己氧基、异己氧基、2-甲基己氧基、3-甲基己氧基、4-甲基己氧基、5-甲基己氧基、2-乙基己氧基、庚氧基、异庚氧基、辛氧基、异辛氧基、壬氧基、癸氧基、十一烷氧基、十二烷氧基、十三烷氧基、十四烷氧基、十五烷氧基、十六烷氧基、十七烷氧基和十八烷氧基中的任意一种。The alkoxy group as a substituent can specifically be: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, 2-methylbutoxy, 3-methylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1-propylbutoxy, pentyloxy, isopentyloxy, 2-methylpentyloxy, 3 -Methylpentyloxy, 4-methylpentyloxy, 1-ethylpentyloxy, 2-ethylpentyloxy, 3-ethylpentyloxy, hexyloxy, isohexyloxy, 2-methylpentyloxy Hexyloxy, 3-methylhexyloxy, 4-methylhexyloxy, 5-methylhexyloxy, 2-ethylhexyloxy, heptyloxy, isoheptyloxy, octyloxy, Isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, decadecyloxy Any one of heptalkoxy and octadecyloxy.
优选的，本发明含带交联基团的噻吩并[3，4-b]噻吩共轭聚合物可为式II结构的聚合物，Preferably, the thieno[3,4-b]thiophene conjugated polymer containing crosslinking groups in the present invention can be a polymer with a structure of formula II,
(式II)(Formula II)
其中，R是C1-C18的烷基；p和q均为1-18的自然数；a/(a+b)是0-1的任意值且a/(a+b)不为0；n是大于等于4的自然数。Wherein, R is an alkyl group of C1 -C18 ; p and q are both natural numbers of 1-18; a/(a+b) is any value of 0-1 and a/(a+b) is not 0; n is a natural number greater than or equal to 4.
式II所示聚合物的制备方法，包括下述步骤：将式III所示4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸烷基酯、式IV所示4，6-二溴噻吩并[3，4-b]噻吩)-2-羧酸溴代烷基酯和式V所示4，8-二(烷氧基)苯并[1，2-b：4，5-b’]二噻吩-2，6-二(三甲基锡)在四三苯基膦钯催化下进行反应，得到式II所示的共轭聚合物。The preparation method of the polymer shown in formula II comprises the following steps: 4,6-dibromothieno[3,4-b]thiophene-2-carboxylate shown in formula III, 4 shown in formula IV , 6-dibromothieno[3,4-b]thiophene)-2-carboxylic acid bromoalkyl ester and 4,8-bis(alkoxy)benzo[1,2-b shown in formula V: 4,5-b']dithiophene-2,6-bis(trimethyltin) is reacted under the catalysis of tetrakistriphenylphosphine palladium to obtain the conjugated polymer represented by formula II.
(式III) (式IV) (式V)(Formula III) (Formula IV) (Formula V)
式III中p的定义同式II，式IV中q的定义同式II，式V中R的定义同式II。The definition of p in formula III is the same as that of formula II, the definition of q in formula IV is the same as that of formula II, and the definition of R in formula V is the same as that of formula II.
这里所用到的4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸烷基酯是由如下步骤制备得 到的：将1-烷基醇与4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸混合，并加入1，3-二环己基二亚胺和二甲氨基吡啶，无水二氯甲烷作溶剂，氮气保护，搅拌反应5-24小时后得到4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸酯。The 4,6-dibromothieno[3,4-b]thiophene-2-carboxylic acid alkyl ester used here is prepared by the following steps: 1-alkyl alcohol and 4,6-dibromothiophene Mix [3,4-b]thiophene-2-carboxylic acid, add 1,3-dicyclohexyldiimine and dimethylaminopyridine, anhydrous dichloromethane as solvent, nitrogen protection, stirring reaction 5-24 4,6-Dibromothieno[3,4-b]thiophene-2-carboxylate was obtained after 1 hour.
4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸溴代烷基酯是由如下步骤制备得到的：4,6-dibromothieno[3,4-b]thiophene-2-carboxylic acid bromoalkyl ester is prepared by the following steps:
1)烷基二醇、氢溴酸与甲苯混合后，在100-200℃下搅拌反应10-48小时后得到溴代醇；1) Alkyl glycol, hydrobromic acid and toluene are mixed, stirred and reacted at 100-200° C. for 10-48 hours to obtain bromohydrin;
2)将溴代醇与4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸混合，并加入1，3-二环己基二亚胺和二甲氨基吡啶，无水二氯甲烷作溶剂，氮气保护，搅拌反应5-24小时后得到4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸溴代烷基酯。2) Mix bromoalcohol with 4,6-dibromothieno[3,4-b]thiophene-2-carboxylic acid, add 1,3-dicyclohexyldiimine and dimethylaminopyridine, anhydrous Dichloromethane is used as a solvent, under nitrogen protection, and the reaction is stirred for 5-24 hours to obtain bromoalkyl 4,6-dibromothieno[3,4-b]thiophene-2-carboxylate.
本发明的目的之二是提供此类含带交联基团的噻吩并[3，4-b]噻吩共轭聚合物在制备光电器件中的应用，尤其是在制备聚合物太阳电池领域的应用。The second object of the present invention is to provide the application of this type of thieno[3,4-b]thiophene conjugated polymer containing crosslinking groups in the preparation of optoelectronic devices, especially the application in the field of preparation of polymer solar cells .
本发明的含带交联基团的噻吩并[3，4-b]噻吩共轭聚合物材料，不仅是一种良好的电子给体材料，而且可以提高薄膜的抗溶剂性，使采用溶液加工的方法制备多层结构光伏器件成为可能。The thieno[3,4-b]thiophene conjugated polymer material containing crosslinking groups of the present invention is not only a good electron donor material, but also can improve the solvent resistance of the film, making it possible to use solution processing It is possible to fabricate multilayer structure photovoltaic devices by the method.
当将本发明聚合物用于制备多层结构聚合物太阳电池时，可在第一层旋涂本发明聚合物，并用紫外或加热或加入引发剂等方式引发交联，交联后的薄膜具有较强的抗溶剂性，然后在第一层薄膜上再旋涂第二层可交联的或不可交联的材料，若是可交联的材料，则还可继续旋涂第三层。按此方法就能实现多层结构的构筑。When the polymer of the present invention is used to prepare a multilayer structure polymer solar cell, the polymer of the present invention can be spin-coated on the first layer, and crosslinking is initiated by means of ultraviolet or heating or adding an initiator, and the crosslinked film has Strong solvent resistance, then spin-coat the second layer of cross-linkable or non-cross-linkable material on the first layer of film, if it is cross-linkable material, you can continue to spin-coat the third layer. In this way, the construction of a multi-layer structure can be realized.
本发明制备的可交联聚合物，其在交联后可使共轭聚合物复合膜中给受体的微相分离结构有效冻结，从而提高了器件的热稳定性。同时交联结构还大大提高了薄膜的抗溶剂性，使通过溶液加工的方法制备多层结构器件成为可能。The cross-linkable polymer prepared by the invention can effectively freeze the microphase separation structure of the donor and acceptor in the conjugated polymer composite film after cross-linking, thereby improving the thermal stability of the device. At the same time, the cross-linked structure also greatly improves the solvent resistance of the film, making it possible to prepare multilayer structure devices by solution processing.
附图说明Description of drawings
图1为实施例1中聚合物制成的薄膜未经紫外交联，浸没于邻二氯苯溶剂中5分钟后的紫外可见光吸收光谱图。Fig. 1 is the ultraviolet-visible light absorption spectrogram of the film made of the polymer in Example 1 without ultraviolet crosslinking, immersed in o-dichlorobenzene solvent for 5 minutes.
图2为实施例1中聚合物制成的薄膜先经紫外交联5分钟后，再浸没于邻二氯苯溶剂中5分钟后的紫外可见光吸收光谱图。Fig. 2 is the ultraviolet-visible light absorption spectrum of the film made of the polymer in Example 1 after being subjected to ultraviolet cross-linking for 5 minutes, and then immersed in o-dichlorobenzene solvent for 5 minutes.
图3为实施例1中聚合物制成的薄膜先经紫外交联10分钟后，再浸没于邻二氯苯溶剂中5分钟后的紫外可见光吸收光谱图。Fig. 3 is the ultraviolet-visible light absorption spectrum of the film made of the polymer in Example 1 after being subjected to ultraviolet cross-linking for 10 minutes, and then immersed in o-dichlorobenzene solvent for 5 minutes.
图4为实施例1中聚合物制成的薄膜先经紫外交联20分钟后，再浸没于邻二氯苯溶剂中5分钟后的紫外可见光吸收光谱图。Fig. 4 is the ultraviolet-visible light absorption spectrum of the film made of the polymer in Example 1 after being subjected to ultraviolet cross-linking for 20 minutes, and then immersed in o-dichlorobenzene solvent for 5 minutes.
图5为实施例1中聚合物制备的光伏器件(紫外光照交联5分钟，退火90分钟)所测得的电流-电压曲线。Fig. 5 is the measured current-voltage curve of the photovoltaic device (crosslinked by ultraviolet light for 5 minutes and annealed for 90 minutes) prepared from the polymer in Example 1.
图6为实施例1中聚合物制备的光伏器件(未紫外光照交联，退火90分钟)所测 得的电流-电压曲线。Fig. 6 is the measured current-voltage curve of the photovoltaic device (not crosslinked by ultraviolet light, annealed for 90 minutes) prepared by the polymer in Example 1.
图7为实施例1中聚合物制备的光伏器件(未紫外光照交联，未退火)所测得的电流-电压曲线。Fig. 7 is the measured current-voltage curve of the photovoltaic device (not cross-linked by ultraviolet light, not annealed) prepared from the polymer in Example 1.
具体实施方式Detailed ways
下面通过具体实施例对本发明进行说明，但本发明并不局限于此。The present invention will be described below through specific examples, but the present invention is not limited thereto.
下述实施例中所述实验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。The experimental methods described in the following examples, unless otherwise specified, are conventional methods; the reagents and materials, unless otherwise specified, can be obtained from commercial sources.
实施例1、制备式1结构的共轭聚合物1Embodiment 1, prepare the conjugated polymer 1 of formula 1 structure
式1结构的共轭聚合物1是烷基链末端带溴交联基团的噻吩并[3，4-b]噻吩和不带溴交联基团的噻吩并[3，4-b]噻吩和[4，8-二(异辛氧基)苯并[1，2-b：4，5-b’]二噻吩的三元共聚物，其具体反应式如下：The conjugated polymer 1 of formula 1 is thieno[3,4-b]thiophene with bromine crosslinking group at the end of the alkyl chain and thieno[3,4-b]thiophene without bromine crosslinking group And [4,8-two (isooctyloxy) benzo [1,2-b:4,5-b '] terpolymer of dithiophene, its specific reaction formula is as follows:
式1Formula 1
具体制备方法如下：The specific preparation method is as follows:
步骤1)1，8-辛二醇0.1mol与氢溴酸0.18mol混合，甲苯作溶剂，110℃下搅拌反应36小时，萃取，并减压蒸馏得到无色液体便是8-溴-1-辛醇。Step 1) Mix 0.1mol of 1,8-octanediol with 0.18mol of hydrobromic acid, use toluene as solvent, stir and react at 110°C for 36 hours, extract, and distill under reduced pressure to obtain a colorless liquid which is 8-bromo-1- octanol.
步骤2)8-溴-1-辛醇12mmol，4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸3mmol，1，3-二环己基碳二亚胺3.6mmol与二甲氨基吡啶1.05mmol混合，无水二氯甲烷作溶剂，氮 气保护，搅拌反应过夜，萃取，用层析柱提纯得到4，6-二溴噻吩并[3，4-b]噻吩)-2-羧酸-8-溴辛酯。Step 2) 8-bromo-1-octanol 12mmol, 4,6-dibromothieno[3,4-b]thiophene-2-carboxylic acid 3mmol, 1,3-dicyclohexylcarbodiimide 3.6mmol and Dimethylaminopyridine 1.05mmol mixed, anhydrous dichloromethane as solvent, nitrogen protection, stirring and reacting overnight, extraction, purification with chromatographic column to obtain 4,6-dibromothieno[3,4-b]thiophene)-2 -8-Bromooctyl carboxylate.
步骤3)1-辛醇12mmol，4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸3mmol，1，3-二环己基碳二亚胺3.6mmol与二甲氨基吡啶1.05mmol混合，无水二氯甲烷作溶剂，氮气保护，搅拌反应过夜，萃取，用层析柱提纯得到4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸辛酯。Step 3) 1-octanol 12mmol, 4,6-dibromothieno[3,4-b]thiophene-2-carboxylic acid 3mmol, 1,3-dicyclohexylcarbodiimide 3.6mmol and dimethylaminopyridine 1.05mmol mixed, anhydrous dichloromethane as solvent, nitrogen protection, stirred overnight, extracted, and purified by chromatography column to obtain octyl 4,6-dibromothieno[3,4-b]thiophene-2-carboxylate.
步骤4)4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸-8-溴辛酯0.25mmol，4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸辛酯0.25mmol，4，8-二(异辛氧基)苯并[1，2-b：4，5-b’]二噻吩-2，6-二(三甲基锡)0.5mmol，甲苯10ml，N，N-二甲基甲酰胺2ml，四三苯基膦钯30mg，在烧瓶中混合均匀，氮气保护，升温至110℃，反应15.5小时。将聚合物溶液冷却至室温，慢慢倾倒入甲醇(50mL)中，沉析出的固体聚合物在索氏提取器内依次用甲醇、正己烷来洗脱。最后用三氯甲烷溶解后沉析到甲醇中，过滤，真空干燥1天得到共轭聚合物1。Step 4) 0.25 mmol of 4,6-dibromothieno[3,4-b]thiophene-2-carboxylate-8-bromooctyl, 4,6-dibromothieno[3,4-b]thiophene- 2-octyl carboxylate 0.25mmol, 4,8-bis(isooctyloxy)benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin) 0.5 Mmol, 10ml of toluene, 2ml of N,N-dimethylformamide, and 30mg of tetrakistriphenylphosphine palladium were mixed uniformly in a flask, protected by nitrogen, heated to 110°C, and reacted for 15.5 hours. The polymer solution was cooled to room temperature, slowly poured into methanol (50 mL), and the precipitated solid polymer was sequentially eluted with methanol and n-hexane in a Soxhlet extractor. Finally, it was dissolved in chloroform, precipitated into methanol, filtered, and vacuum-dried for 1 day to obtain conjugated polymer 1.
结构确证图谱：Structural confirmation map:
1H NMR((δ/ppm，400MHz，CDCl3)：7.50-8.10(br，4H)，6.52-7.16(br，2H)，4.42(br，4H)，4.02(br，8H)，3.47(t，2H)，0.70-2.49(br，88H).1 H NMR ((δ/ppm, 400MHz, CDCl3 ): 7.50-8.10(br, 4H), 6.52-7.16(br, 2H), 4.42(br, 4H), 4.02(br, 8H), 3.47(t , 2H), 0.70-2.49 (br, 88H).
GPC：Mn＝22.7k.GPC: Mn=22.7k.
实施例2、制备式2结构的共轭聚合物2Embodiment 2, prepare the conjugated polymer 2 of formula 2 structure
式2结构的共轭聚合物2是烷基链末端带溴交联基团的噻吩并[3，4-b]噻吩和不带溴交联基团的噻吩并[3，4-b]噻吩和[4，8-二(异辛氧基)苯并[1，2-b：4，5-b’]二噻吩的三元共聚物，其具体反应式如下：The conjugated polymer 2 of formula 2 is thieno[3,4-b]thiophene with bromine crosslinking group at the end of the alkyl chain and thieno[3,4-b]thiophene without bromine crosslinking group And [4,8-two (isooctyloxy) benzo [1,2-b:4,5-b '] terpolymer of dithiophene, its specific reaction formula is as follows:
(式2)(Formula 2)
具体制备方法如下：The specific preparation method is as follows:
步骤1)1，8-辛二醇0.1mol与氢溴酸0.18mol混合，甲苯作溶剂，110℃下搅拌反应36小时，萃取，并减压蒸馏得到无色液体便是8-溴-1-辛醇。Step 1) Mix 0.1mol of 1,8-octanediol with 0.18mol of hydrobromic acid, use toluene as solvent, stir and react at 110°C for 36 hours, extract, and distill under reduced pressure to obtain a colorless liquid which is 8-bromo-1- octanol.
步骤2)8-溴-1-辛醇12mmol，4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸3mmol，1，3-二环己基碳二亚胺3.6mmol与二甲氨基吡啶1.05mmol混合，无水二氯甲烷作溶剂，氮气保护，搅拌反应过夜，萃取，用层析柱提纯得到4，6-二溴噻吩并[3，4-b]噻吩)-2-羧酸-8-溴辛酯。Step 2) 8-bromo-1-octanol 12mmol, 4,6-dibromothieno[3,4-b]thiophene-2-carboxylic acid 3mmol, 1,3-dicyclohexylcarbodiimide 3.6mmol and Dimethylaminopyridine 1.05mmol mixed, anhydrous dichloromethane as solvent, nitrogen protection, stirring and reacting overnight, extraction, purification with chromatographic column to obtain 4,6-dibromothieno[3,4-b]thiophene)-2 -8-Bromooctyl carboxylate.
步骤3)1-辛醇12mmol，4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸3mmol，1，3-二环己基碳二亚胺3.6mmol与二甲氨基吡啶1.05mmol混合，无水二氯甲烷作溶剂，氮气保护，搅拌反应过夜，萃取，用层析柱提纯得到4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸辛酯。Step 3) 1-octanol 12mmol, 4,6-dibromothieno[3,4-b]thiophene-2-carboxylic acid 3mmol, 1,3-dicyclohexylcarbodiimide 3.6mmol and dimethylaminopyridine 1.05mmol mixed, anhydrous dichloromethane as solvent, nitrogen protection, stirred overnight, extracted, and purified by chromatography column to obtain octyl 4,6-dibromothieno[3,4-b]thiophene-2-carboxylate.
步骤4)4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸-8-溴辛酯0.375mmol，4，6-二溴噻吩并[3，4-b]噻吩-2-羧酸辛酯0.25mmol，4，8-二(异辛氧基)苯并[1，2-b：4，5-b’]二噻吩-2，6-二(三甲基锡)0.5mmol，甲苯10ml，N，N-二甲基甲酰胺2ml，四三苯基膦钯30mg，在烧瓶中混合均匀，氮气保护，升温至110℃，反应15.5小时。将聚合物溶液冷却至室温，慢慢倾倒入甲醇(50mL)中，沉析出的固体聚合物在索氏提取器内依次用甲醇、正己烷来洗脱。最后用三氯甲烷溶解后沉析到甲醇中，过滤，真空干燥1天得到共轭聚合物2。Step 4) 0.375 mmol of 4,6-dibromothieno[3,4-b]thiophene-2-carboxylate-8-bromooctyl, 4,6-dibromothieno[3,4-b]thiophene- 2-octyl carboxylate 0.25mmol, 4,8-bis(isooctyloxy)benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin) 0.5 Mmol, 10ml of toluene, 2ml of N,N-dimethylformamide, and 30mg of tetrakistriphenylphosphine palladium were mixed uniformly in a flask, protected by nitrogen, heated to 110°C, and reacted for 15.5 hours. The polymer solution was cooled to room temperature, slowly poured into methanol (50 mL), and the precipitated solid polymer was sequentially eluted with methanol and n-hexane in a Soxhlet extractor. Finally, it was dissolved in chloroform, precipitated into methanol, filtered, and vacuum-dried for 1 day to obtain conjugated polymer 2.
结构确证图谱：Structural confirmation map:
1H NMR((δ/ppm，400MHz，CDCl3)：7.50-8.10(br，4H)，6.52-7.16(br，2H)，4.42(br，4H)，4.02(br，8H)，3.47(t，1H)，0.70-2.49(br，89H).1H NMR ((δ/ppm, 400MHz, CDCl3): 7.50-8.10(br, 4H), 6.52-7.16(br, 2H), 4.42(br, 4H), 4.02(br, 8H), 3.47(t, 1H ), 0.70-2.49 (br, 89H).
GPC：Mn＝25.3k.GPC: Mn=25.3k.
实施例3、实施例1制备的共轭聚合物1的抗溶剂性实验The solvent resistance experiment of the conjugated polymer 1 prepared by embodiment 3, embodiment 1
步骤1)制备10mm×10mm的载玻片4片，依次用洗洁精水、二次水、丙酮、乙醇 各洗两遍，烘干。Step 1) Prepare 4 glass slides of 10mm×10mm, wash them twice with detergent water, secondary water, acetone, and ethanol successively, and dry them.
步骤2)将载玻片用紫外臭氧处理20分钟，将50微升聚(3，4-乙撑二氧基噻吩)(PEDOT:PSS)的溶液旋涂至载玻片表面。Step 2) The glass slide was treated with ultraviolet ozone for 20 minutes, and 50 microliters of poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) solution was spin-coated on the surface of the glass slide.
步骤3)在聚(3，4-乙撑二氧基噻吩)(PEDOT:PSS)的薄膜上旋涂20微升的10mg/ml实施例1制备的共轭聚合物1的溶液。Step 3) Spin-coat 20 microliters of a 10 mg/ml solution of conjugated polymer 1 prepared in Example 1 on a film of poly(3,4-ethylenedioxythiophene) (PEDOT:PSS).
步骤4)将四个涂有薄膜的载玻片置于紫外灯254nm的波长下，并分别照射0、5、10、20分钟，并测薄膜吸收。Step 4) Put the four slides coated with the film under the wavelength of 254nm of ultraviolet lamp, and irradiate them for 0, 5, 10, 20 minutes respectively, and measure the absorption of the film.
步骤5)将载玻片浸没于邻二氯苯溶剂中5分钟，取出，用丙酮冲洗30秒，晾干，测薄膜吸收。Step 5) Immerse the glass slide in the o-dichlorobenzene solvent for 5 minutes, take it out, rinse it with acetone for 30 seconds, dry it in the air, and measure the absorption of the film.
由实施例3所述测得的薄膜吸收可见光吸收光谱如图1-4所示，通过计算可以得出：未交联的聚合物薄膜经邻二氯苯溶剂浸没后，薄膜最大吸光度是浸没前最大吸光度的13.3％，说明载玻片上的聚合物薄膜大部分已被邻二氯苯溶剂所溶解。紫外交联5分钟的聚合物薄膜经溶剂浸没后薄膜最大吸光度是浸没前最大吸光度的70.0％，紫外交联10分钟的聚合物薄膜经溶剂浸没后薄膜最大吸光度是浸没前最大吸光度的80.0％，紫外交联20分钟的聚合物薄膜经溶剂浸没后薄膜最大吸光度是浸没前最大吸光度的85.3％，说明交联后载玻片上的聚合物薄膜大部分未被邻二氯苯溶剂溶解，从而说明交联的聚合物薄膜的抗溶剂性要强于未交联的聚合物薄膜的抗溶剂性。The film absorption visible light absorption spectrum measured by the embodiment 3 is shown in Fig. 1-4, can draw by calculation: after the uncrosslinked polymer film is immersed in o-dichlorobenzene solvent, the film maximum absorbance is before immersion 13.3% of the maximum absorbance indicates that most of the polymer film on the glass slide has been dissolved by o-dichlorobenzene solvent. The maximum absorbance of the polymer film after UV crosslinking for 5 minutes is 70.0% of the maximum absorbance before immersion, and the maximum absorbance of the polymer film after 10 minutes of UV crosslinking is 80.0% of the maximum absorbance before immersion. The maximum absorbance of the polymer film after ultraviolet crosslinking for 20 minutes after immersion in the solvent is 85.3% of the maximum absorbance before immersion, indicating that most of the polymer film on the glass slide is not dissolved by the o-dichlorobenzene solvent after crosslinking. The solvent resistance of the linked polymer film is stronger than that of the uncrosslinked polymer film.
实施例4、由实施例1的共轭聚合物1所制备的太阳能电池的热稳定性实验Embodiment 4, the thermal stability experiment of the solar cell prepared by the conjugated polymer 1 of embodiment 1
将5mg共轭聚合物1(实施例1制备)与7.5mg[6，6]-苯基-C60-丁酸甲酯(简称PCBM)混合，加入0.5ml邻二氯苯溶解，通过旋涂方式在经聚(3，4-乙撑二氧基噻吩)(PEDOT:PSS)修饰过的导电玻璃上制备出一层约150nm厚的薄膜，将甩完膜的片子分成A、B、C三批。A，在紫外灯254nm波长下照射5分钟，后110℃下退火90分钟；B，不紫外照射，110℃下退火90分钟；C，不紫外照射，不退火。然后通过真空蒸镀的方式用钙和铝在聚合物上制备金属电极，得到太阳能电池。图5-7分别是上述三批器件的电流-电压曲线，从图中可以得出，相较于C批器件，A，B批器件的短路电流都下降了，且B批器件的短路电流下降更多。至于开路电压，B批器件的开路电压未变化，而A批器件的开路电压有所提高。Mix 5 mg of conjugated polymer 1 (prepared in Example 1) with 7.5 mg of [6,6]-phenyl-C60 -butyric acid methyl ester (PCBM for short), add 0.5 ml of o-dichlorobenzene to dissolve, and spin-coat The method is to prepare a layer of about 150nm thick film on the conductive glass modified by poly(3,4-ethylenedioxythiophene) (PEDOT:PSS), divide the flakes after throwing the film into A, B, and C three batch. A, irradiated by a UV lamp at a wavelength of 254nm for 5 minutes, and then annealed at 110°C for 90 minutes; B, no ultraviolet irradiation, annealed at 110°C for 90 minutes; C, no ultraviolet irradiation, no annealing. Then, calcium and aluminum are used to prepare metal electrodes on the polymer by vacuum evaporation to obtain a solar cell. Figures 5-7 are the current-voltage curves of the above three batches of devices. It can be concluded from the figure that compared with the devices of batch C, the short-circuit current of the devices of batch A and batch B has decreased, and the short-circuit current of the devices of batch B has decreased. More. As for the open circuit voltage, the open circuit voltage of the batch B device was unchanged, while that of the batch A device was increased.
通过模拟太阳光(AM 1.5，100Mw/cm2)测得A，B，C三批器件的能量转换效率，计算得出，相较于C批器件效率相，A批器件效率平均下降了14.2％，而B批器件效率则平均下降了34.8％。从计算结果可得出，交联后的活性层薄膜的热稳定性要强于未交联的活性层薄膜的热稳定性。By simulating sunlight (AM 1.5, 100Mw/cm2 ), the energy conversion efficiencies of devices A, B, and C were measured, and it was calculated that compared with the efficiency of devices in batch C, the efficiency of devices in batch A decreased by an average of 14.2% , while the B batch device efficiency dropped by an average of 34.8%. It can be concluded from the calculation results that the thermal stability of the crosslinked active layer film is stronger than that of the uncrosslinked active layer film.
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