CN105001233B - 双s,s‑二氧‑二苯并噻吩并五元环单体及其制备方法与聚合物 - Google Patents
双s,s‑二氧‑二苯并噻吩并五元环单体及其制备方法与聚合物 Download PDFInfo
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- CN105001233B CN105001233B CN201510200637.XA CN201510200637A CN105001233B CN 105001233 B CN105001233 B CN 105001233B CN 201510200637 A CN201510200637 A CN 201510200637A CN 105001233 B CN105001233 B CN 105001233B
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- substituted
- dibenzothiophene
- dioxo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 49
- 239000000178 monomer Substances 0.000 title claims abstract description 29
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 230000005669 field effect Effects 0.000 claims abstract description 9
- -1 bis (S, S-dioxo-dibenzothiophene) pentalene Chemical class 0.000 claims description 105
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- OYFCIEFATSHSKX-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3CC12.[Ge] Chemical class C1=CC=CC=2C3=CC=CC=C3CC12.[Ge] OYFCIEFATSHSKX-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 229920001519 homopolymer Polymers 0.000 abstract description 3
- 238000010129 solution processing Methods 0.000 abstract description 2
- 238000013086 organic photovoltaic Methods 0.000 abstract 1
- 150000003457 sulfones Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 102
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 91
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 5
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- MMCXXZHJBLWHKN-UHFFFAOYSA-N 4-(4-hexylthiophen-2-yl)-2,1,3-benzothiadiazole Chemical compound C(CCCCC)C=1C=C(SC=1)C1=CC=CC2=NSN=C21 MMCXXZHJBLWHKN-UHFFFAOYSA-N 0.000 description 1
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- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- GGWHJTJHSJIICG-UHFFFAOYSA-N tributyl-(4-hexylthiophen-2-yl)stannane Chemical compound CCCCCCC1=CSC([Sn](CCCC)(CCCC)CCCC)=C1 GGWHJTJHSJIICG-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
本发明公开双S,S‑二氧‑二苯并噻吩并五元环单体及其制备方法与聚合物。所述双S,S‑二氧‑二苯并噻吩并五元环中双砜基的存在更加有利于提高分子的电子亲和势,在五元环上引入烷基链可以显著改善单体在有机溶剂中的溶解性,同时也可以避免烷基链的位置对聚合反应带来的位阻影响。较大的共轭平面可以提高聚合物的空穴和电子传输性能。双S,S‑二氧‑二苯并噻吩并五元环单体通过Suzuki、Stille、Yamamoto聚合反应可获得均聚物或共聚物。该系列聚合物在有机溶剂中有良好的溶解性,适合于溶液加工。在有机发光显示、有机光伏电池以及有机场效应管领域有着广泛的应用前景。
Description
技术领域
本发明属于有机光电领域,具体涉及双S,S-二氧-二苯并噻吩并五元环单体及其制备方法与聚合物。
背景技术
有机电致发光二极管的报道最早可追溯至上世纪60年代,Pope等用蒽单晶制备了有机电致发光器件(Pope M.;Kallmann H.P.;Magnante P.Electroluminescence inOrganic Crystals,The Journal of chemical physics,1963,38:2042–2043)。有机太阳能光伏电池材料起步于上世纪90年代,1995年,黑格尔等人第一次使用给受体共混的体异质结结构制作有机聚合物电池材料,器件性能相对于给受体双层结构有了较大幅度的提升。(G.Yu,J.Gao,J.C.Hummelen,F.Wudl,A.J.Heeger,Science 1995,270,178‐180)。有机场效应晶体管方面,1987年,VanSlyke等人将联苯二胺衍生物材料引入到器件中以提高器件的空穴迁移率得到了较好的结果。(Appl.Phys.Lett.,51(12),21Semptember 1987)。2004年,华南理工大学曹镛等人合成了具有电子传输性能的PFN材料,将其引入到器件的界面层中得到了比较好的效果。(Adv.Mater.2004,16No.20,October 18)。因此,开发具有市场吸引力的有机电子产品吸引了世界上众多的研究机构和科研团队的关注和投入。而在这其中,开发新型高效稳定的材料无疑成为关键的一个环节。
双S,S-二氧-二苯并噻吩并五元环是具有诸多优点的缺电子单元,相比于单个的S,S-二氧-二苯并噻吩单元,其缺电子性更强,更加有利于提高材料的电子亲和势和电子迁移率,其中的两个S都达到了最高的化学价态,抗氧化的能力更强;稠环结构增大分子共轭平面,有利于提高材料的电子迁移率,分子内的D-A相互作用也增强了单元的荧光性,聚合物薄膜的荧光量子效率取得了比较理想的结果。单个S,S-二氧-二苯并噻吩单元的溶解性较差,而稠环结构的双S,S-二氧-二苯并噻吩并五元环通过引入烷基链增加了溶解性,同时也可以避免烷基链引入带来的聚合位阻。同时,从化学合成的角度,双S,S-二氧-二苯并噻吩并五元环结构比单个的S,S-二氧-二苯并噻吩单元可修饰的位点多一些,可以在苯环的不同位置引入卤素原子,得到不同结构的聚合单体,从而可以有效调节聚合物的共轭长度,调节聚合物的荧光发射,得到色坐标比较理想的聚合物。对于有机太阳能电池来说,双S,S-二氧-二苯并噻吩并五元环具有较强的吸电性和较好的平面共轭性,可以降低材料的HOMO能级,也有助于电荷的分离和传输,作为电池材料中的A单元,有助于提高器件的开路电压,得到高效的光伏器件。对于有机场效应晶体管来说,双S,S-二氧-二苯并噻吩并五元环均聚物有着较大的应用潜力。从单体本身来看,双砜基的存在使分子的刚性增强,分子结构稳定,同时双S,S-二氧-二苯并噻吩并五元环具有较好的共轭平面,有利于空穴和电子的传输,特别是双S,S-二氧-二苯并噻吩并吡咯的结构更具有双极传输特性。本发明开发了新型稠环结构双S,S-二氧-二苯并噻吩并五元环单体及其制备方法和聚合物。该类聚合物有很好的溶解性,适合于溶液加工;用作发光材料有着较好的荧光光谱和色坐标。由于双砜基的存在,材料的电子迁移率得到增强,稠环结构使其有较好的平面共轭性,其作为电子受体材料和高迁移率有机半导体材料在太阳能电池和有机场效应晶体管方面将会有很大的应用潜力。
发明内容
本发明解决的技术问题在于提供一种双S,S-二氧-二苯并噻吩并五元环单体,并将其引入到共轭聚合物中,合成主链含双S,S-二氧-二苯并噻吩并五元环的聚合物。
本发明的目的在于提供一种基于双S,S-二氧-二苯并噻吩并五元环的聚合物材料,并将其应用于有机电致发光、有机太阳能电池和有机场效应晶体管中。
一类双S,S-二氧-二苯并噻吩并五元环单体,所述单体具有如下化学结构式之一:
式中,X为Br或I原子;R1为碳原子数为1~30的烷基。
一种双S,S-二氧-二苯并噻吩并五元环单体的制备方法,
单体M-1和M-5的制备方法:
1)将双(S,S-二氧-二苯并噻吩)并环戊二烯和双(S,S-二氧-二苯并噻吩)并吡咯分别溶于有机溶剂中,酸性条件下与NBS反应1~10小时,反应结束后,萃取、干燥、提纯,分别得到2,10-二溴代双(S,S-二氧-二苯并噻吩)并环戊二烯(M-1)和5,7-二溴代双(S,S-二氧-二苯并噻吩)并吡咯(M-5);
单体M-2的制备方法:
1)将2,4-二溴-1-甲硫基苯溶于醋酸中,冰浴下加入摩尔当量为1~1.5倍的双氧水,反应4~10小时,反应结束后,萃取、干燥、提纯得到2,4-二溴-1-甲亚磺酰苯;
2)将2,7-二硼酸酯-烷基取代芴和2,4-二溴-1-甲亚磺酰苯按摩尔比1:2~10的比例混合,溶于有机溶剂中,在钯催化剂中、40~100℃下反应8~25小时,反应完毕后,萃取、干燥、提纯,得到2,7-二(5-溴-2-甲亚磺酰苯基)-烷基取代芴;
3)将2,7-二(5-溴-2-甲亚磺酰苯基)-烷基取代芴在三氟甲烷磺酸中反应,同时加入五氧化二磷,反应2~20小时,反应结束后将反应液滴加到水中并抽滤,滤渣晾干后在吡啶中加热回流2~30小时,反应结束后萃取、干燥、提纯,得到3,9-二溴代双(二苯并噻吩)并环戊二烯;
4)将3,9-二溴代双(二苯并噻吩)并环戊二烯溶解于有机溶剂中,加入氧化剂反应2~10小时,反应结束后,萃取、干燥、提纯,得到3,9-二溴代双(S,S-二氧-二苯并噻吩)并环戊二烯(M-2);
单体M-3和M-4的制备方法:
1)将3,6-二甲硫基-2,7-二溴-烷基取代咔唑溶于三氟乙酸中,加入摩尔当量为2~5倍的双氧水,冰浴下反应2~15小时,反应结束后萃取、干燥、提纯得到3,6-二甲亚磺酰基-2,7-二溴-烷基取代咔唑;
2)将3,6-二甲亚磺酰基-2,7-二溴-烷基取代咔唑和3-溴苯硼酸或4-溴苯硼酸按摩尔比1:2~10的比例混合,分别溶于有机溶剂中,在钯催化剂中、50~100℃下反应8~20小时,反应完毕后,萃取、干燥、提纯,分别得到3,6-二甲亚磺酰基-2,7-二(3-溴苯基)-烷基取代咔唑或3,6-二甲亚磺酰基-2,7-二(4-溴苯基)-烷基取代咔唑;
3)将3,6-二甲亚磺酰基-2,7-二(3-溴苯基)-烷基取代咔唑或3,6-二甲亚磺酰基-2,7-二(4-溴苯基)-烷基取代咔唑分别在三氟甲烷磺酸中反应,同时加入五氧化二磷,反应2~20小时,反应结束后将反应液滴加到水中并抽滤,滤渣晾干后在吡啶中加热回流2~30小时,反应结束后萃取、干燥、提纯,分别得到3,9-二溴代双(二苯并噻吩)并吡咯或2,10-二溴代双(二苯并噻吩)并吡咯;
4)将3,9-二溴代双(二苯并噻吩)并吡咯或2,10-二溴代双(二苯并噻吩)并吡咯在有机溶剂中分别溶解,加入氧化剂反应2~10小时。反应结束后,萃取、干燥、提纯,分别得到3,9-二溴代双(S,S-二氧-二苯并噻吩)并吡咯(M-3)或2,10-二溴代双(S,S-二氧-二苯并噻吩)并吡咯(M-4)。
上述方法中,单体M-2、M-3和M-4制备方法中,所述钯催化剂为Pd(PPh3)4、Pd(OAc)2或Pd2(dba)3。
上述方法中,单体M-1、M-2、M-3、M-4和M-5制备方法中,所用溶剂为四氢呋喃、甲苯中任意一种或其混合物。
上述方法中,单体M-2、M-3和M-4制备方法中,所用氧化剂为双氧水、3-氯过氧苯甲酸中任意一种或其混合物。
双S,S-二氧-二苯并噻吩并五元环单体的聚合物,结构式如下,
式中:x,y为单元组分的摩尔分数,满足:0<x≤1,x+y=1,n=1~300;R1为碳原子数为1~30的烷基;
其中,具有如下结构之一:
2,10-取代双(S,S-二氧-二苯并噻吩)并环戊二烯3,9-取代双(S,S-二氧-二苯并噻吩)并环戊二烯。
双S,S-二氧-二苯并噻吩并五元环单体的聚合物,结构式如下,
式中:x,y为单元组分的摩尔分数,满足:0<x≤1,x+y=1,n=1~300;R1为碳原子数为1~30的烷基;
其中,具有如下结构之一:
3,9-取代双(S,S-二氧-二苯并噻吩)并吡咯2,10-取代双(S,S-二氧-二苯并噻吩)并吡咯5,7-取代双(S,S-二氧-二苯并噻吩)并吡咯。
上述聚合物中,Ar为如下结构之一:
2,7-取代芴;
3,6-取代芴;
2,7-取代螺芴;
2,7-取代硅芴;
2,7-取代锗芴;
2,7-取代咔唑;
3,6-取代咔唑;
3,9-取代吲哚咔唑;
2,8-取代吲哚咔唑;
3,9-取代茚芴;
2,8-取代茚芴;
1,4-取代苯;
4,7-取代2,1,3-苯并噻二唑;
4,7-取代-2,1,3-苯并硒二唑;
4,7-二(4-取代苯基)-2,1,3-苯并噻二唑;
4,7-二(4-取代苯基)-2,1,3-苯并硒二唑;
4,7-二(5-取代-4-烷基噻吩-2-基)-2,1,3-苯并噻二唑;
4,7-二(5-取代-4-烷基噻吩-2-基)-2,1,3-苯并硒二唑;
4,7-二(N-(4-取代苯基)-N-(4-烷基苯基)胺基)-2,1,3-苯并噻二唑;
4,7-二(N-(4-取代苯基)-N-(4-烷基苯基)胺基)-2,1,3-苯并硒二唑;
4,7-二(4-(N-(4-取代苯基)-N-(4-烷基苯基)胺基)苯基)-2,1,3-苯并噻二唑;
4,7-二(4-(N-(4-取代苯基)-N-(4-烷基苯基)胺基)苯基)-2,1,3-苯并硒二唑;
3,7-二(N-(4-取代苯基)-N-(4-烷基苯基)胺基)-二苯并噻吩-S,S-二氧;
2,8-二烷基-3,7-二(N-(4-取代苯基)-N-(1-苯基)胺基)-二苯并噻吩-S,S-二氧;
3,7-二(4-(N-(4-取代苯基)-N-(4-烷基苯基)胺基)苯基)-二苯并噻吩-S,S-二氧;
2,8-二烷基-3,7-二(4-(N-(4-取代苯基)-N-(1-苯基)胺基)苯基)-二苯并噻吩-S,S-二氧;
其中,Z1、Z2包括如下组合:Z1=H,Z2=H、或者Z1=H,Z2=F、或者Z1=F,Z2=F;
R2为碳原子数为1~30的烷基、1~30的烷氧基或H原子。
本发明还提供了基于双S,S-二氧-二苯并噻吩并五元环聚合物在有机电致发光器件、有机太阳能电池和有机场效应晶体管中应用。
本发明所具有的优点和效益在于:1)提供了一种简单有效的双S,S-二氧-二苯并噻吩并五元环单体的合成路线,原料价格低廉,有利于规模制备生产;2)烷基的引入极大地改善了单体的溶解性,同时也可以避免位阻效应对聚合带来的影响,不仅得到了高分子量、高含量的含双S,S-二氧-二苯并噻吩并五元环单元共聚物及均聚物,而且其溶液加工性能也显著提高;3)分子内的D-A相互作用也增强了材料的荧光量子效率,化合物活性反应位点多,通过不同位置的卤代反应得到不同结构的单体,从而可以有效调节材料的共轭长度和共轭平面性,得到较好的荧光发射;4)双S,S-二氧-二苯并噻吩并五元环吸电性强,HOMO能级较深,共轭平面性好,用于有机太阳能电池材料中有利于提高器件的开路电压,得到高效的光伏器件;5)材料的共轭平面性好,双砜基基团使材料的电子传输性能增强,用于有机场效应晶体管方面可以得到高效稳定的场效应晶体管。
附图说明
图1为聚合物P1、P2、P3热重分析曲线。
图2为聚合物P1、P4、P7和P8薄膜中的紫外-可见吸收光谱图。
图3为聚合物P1、P4、P7和P8的薄膜光致发光光谱图。
图4为聚合物P4、P6和P8的循环伏安特性曲线图。
图5为聚合物P1、P3和P7的循环伏安特性曲线图。
图6为聚合物P1、P2、P4和P5的电压-电流密度-亮度曲线图。
图7为聚合物P1、P2、P4和P5器件EL光谱曲线图。
具体实施方式
以下通过实施例对S,S-二氧-二苯并噻吩衍生物单体的合成作进一步的说明,但本发明将不限于所列之例。
实施例1
2,10-二溴-双(S,S-二氧-二苯并噻吩)并环戊二烯(M-1)的合成(Ghaemy M.,Barghamadi M.Synthesis and characterization of novel photoactive polyamidederived from substituted fluorene by copper(I)catalyst[J].J.Appl.Polym.Sci.,2009,114(6):3464-3471.)
1)2,7-二溴芴(1)的制备:将芴(16.6g,0.1mol)和铁粉(88mg,1.57mmol)溶于100mL三氯甲烷。冰浴中,缓慢滴加35mL三氯甲烷稀释的液溴(35.2g,0.22mol)。滴加时瓶内温度不超过5℃。反应完毕,过滤、氯仿重结晶,得米黄色固体粉末(26.9g,83%)。MS(APCI):m/z(%):325.0[M+].
2)2,7-二溴-9,9-二正辛基芴(2)的制备:将2,7-二溴芴(9.7g,30mmol)和苄基三乙基氯化铵(0.07g,0.3mmol)溶于90mL二甲基亚砜中,并加入45mL质量分数为50%的氢氧化钠水溶液。室温下剧烈搅拌形成悬浮液。缓慢滴加1-溴正辛烷(12.5g,65mmol),继续搅拌3小时后,用乙酸乙酯萃取。用饱和氯化钠水溶液洗涤有机相,无水硫酸镁干燥。蒸去溶剂,产物用石油醚作洗脱剂柱层析提纯,得白色晶体(14.8g,90%)。MS(APCI):m/z(%):549.4[M+].
3)2,7-二硼酸酯-9,9-二正辛基芴(3)的制备:将2,7-二溴-9,9-二正辛基芴(5.6g,10.22mmol)溶于130mL无水四氢呋喃中。氩气保护下于-78℃时滴加浓度为1.6M正丁基锂的正己烷溶液(20mL,32mmol),在-78℃下反应2小时。随后快速加入2-异丙氧基-4,4,5,5-四甲基-1,3,2-乙二氧基硼酸酯(25mL,123mmol),继续保温反应40分钟。将反应液逐渐升至室温反应36小时。反应结束后将反应液倒入水中,用二氯甲烷萃取、食盐水洗涤、无水硫酸镁干燥。蒸去溶剂,残余物用四氢呋喃/甲醇重结晶,进一步用硅胶柱层析提纯(石油醚:乙酸乙酯=9:1为洗脱剂),得白色固体粉末(4.59g,70%)。MS(APCI):m/z(%):643.5[M+].
4)2,7-二(2-甲亚磺酰苯基)-9,9-二正辛基芴(4)的制备:将30mL浓度为2M的碳酸钾水溶液,2,7-二(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-9,9-二正辛基芴(3.86g,6mmol)和1-溴-2-甲亚磺酰苯(2.9g,13.2mmol)加入到反应瓶中,并加入60mL甲苯,通氮气。反应温度升至90℃时加入350mg四三苯基膦钯和190mg四丁基溴化铵,反应进行24小时。停止反应并冷却到室温,用二氯甲烷萃取1~3次。将有机层旋干之后用200~300目硅胶过层析柱,洗脱剂的极性是石油醚/乙酸乙酯(3:1),最终得到淡黄色液体(3.6g,90%)。MS(APCI):m/z(%):667.5[M+].
5)双(二苯并噻吩)并环戊二烯(5)的制备:将2,7-二(2-甲亚磺酰苯基)-9,9-二正辛基芴(0.8g,1.2mmol)加入到4.2mL三氟甲烷磺酸中,室温条件下搅拌24小时。反应结束后将反应液滴加到冰水中,将混合液抽滤得到淡黄色的固体粉末并晾干。将淡黄色固体粉末溶于100mL吡啶中,氮气下加热回流12小时。停止反应并冷却到室温,萃取并用盐酸中和其中的吡啶。用石油醚过层析柱,并用乙醇重结晶得到白色粉末状晶体(0.46g,64%)。MS(APCI):m/z(%):603.4[M+].
6)双(S,S-二氧-二苯并噻吩)并环戊二烯(6)的制备:将双(二苯并噻吩)并环戊二烯(100mg,0.17mmol)和3-氯过氧苯甲酸(570mg,3.3mmol)溶解于10mL二氯甲烷中并在冰浴条件下反应10小时。反应结束后将反应液倒入冷的10%质量浓度的氢氧化钠水溶液中搅拌30分钟。有机层用水洗(150mL×3),浓缩并过层析柱,洗脱剂极性为二氯甲烷/乙酸乙酯(5:1),产物用乙醇重结晶得到白色片状晶体(100mg,90%)。MS(APCI):m/z(%):667.1[M+].
7)2,10-二溴-双(S,S-二氧-二苯并噻吩)并环戊二烯(M-1)的制备:将双(S,S-二氧-二苯并噻吩)并环戊二烯(0.51g,0.76mmol)溶于6mL三氟乙酸和1mL三氯甲烷的混合溶液中,再将N-溴代丁二酰亚胺(0.55g,3.1mmol)用3mL三氟乙酸和3mL硫酸溶解之后,避光条件下滴加到反应液中,避光条件下反应2小时。将反应液倒入水中并用二氯甲烷萃取,用洗脱剂石油醚/二氯甲烷(1:5)过层析柱,产物用乙醇/四氢呋喃重结晶得到白色颗粒状晶体(0.5g,80%)。1H-NMR(600MHz,CDCl3,δ)8.17(s,2H),7.99(d,2H),7.80(d,2H),7.76(d,2H),7.72(d,2H)2.11(t,4H),1.06(m,20H),0.77(t,6H),0.58(s,4H).13C-NMR(150MHz,CDCl3,δ)157.70,141.72,138.89,137.46,135.94,131.28,130.54,125.63,124.40,123.10,115.94,114.57,56.67,40.41,31.70,29.84,29.12,29.08,23.80,22.52,14.04.MS(APCI):m/z(%):824.8[M+].
实施例2
3,9-二溴-双(S,S-二氧-二苯并噻吩)并环戊二烯(M-2)的合成(KameneckaT.M.,JiangR.,SongX.et al.Preparation of phenylaminopyrimidine derivatives andanalogs as protein kinase inhibitors:PCT Int.Appl.WO 2009032861A1[P].2009-03-12.)
1)2,4-二溴茴香硫醚(7)的制备:将2,4-二溴氟苯(1.0g,4.0mmol),甲硫醇钠(0.33g,4.8mmol)和三乙胺(0.52mL,4.0mmol)溶于装有3mL N,N-二甲基乙酰胺的密闭试管中,加热到100℃反应12小时。反应结束后,将反应液冷却到室温,乙酸乙酯萃取,卤水洗涤,无水硫酸镁干燥,过硅胶层析柱(乙酸乙酯/正己烷),得到油状液体(0.65g,58%)。MS(APCI):m/z(%):283.0[M+].
2)2,4-二溴-1-甲亚磺酰苯(8)的制备:将2,4-二溴茴香硫醚(2.82g,10mmol)溶于100mL醋酸中,冰浴条件下加入浓度为30%的双氧水(1.4mL,12mmol),室温反应8小时。停止反应后,萃取、干燥,将有机相浓缩得到油状液体(2.09g,70%),无需进一步纯化即可使用。MS(APCI):m/z(%):298.9[M+].
3)2,7-二(5-溴-2-甲亚磺酰苯基)-9,9-二正辛基芴(9)的制备:将30mL浓度为2M的碳酸钾水溶液,2,7-二(4,4,5,5-四甲基-1,3-二氧-2-硼烷基)-9,9-二正辛基芴(3.86g,6mmol)和2,4-二溴甲亚磺酰苯(3.93g,13.2mmol)加入到反应瓶中,加入60mL甲苯,通氮气。反应温度升至90℃时加入350mg四三苯基膦钯和190mg四丁基溴化铵,反应24小时。停止反应并冷却到室温,用二氯甲烷萃取1~3次。将有机层旋干之后用200~300目硅胶过层析柱,洗脱剂的极性是石油醚/乙酸乙酯(3:1),最终得到油状液体(3.95g,80%)。MS(APCI):m/z(%):825.8[M+].
4)3,9-二溴-双(二苯并噻吩)并环戊二烯(10)的制备:将2,7-二(5-溴-2-甲亚磺酰苯基)-9,9-二正辛基芴(0.99g,1.2mmol)加入到4.2mL三氟甲烷磺酸中,室温条件下反应24小时。反应结束后将反应液滴加到冰水中,抽滤得到滤渣粉末并晾干。将淡黄色固体粉末溶于100mL吡啶中,氮气下加热回流12小时。停止反应并冷却到室温,萃取并用盐酸中和其中的吡啶。用石油醚过层析柱,并用乙醇重结晶得到粉末固体(0.32g,35%)。元素分析:C41H44Br2S2理论值:C 64.73%,H 5.83%,S 8.43%;实测值:C65.24%,H 5.53%,S8.11%.
5)3,9-二溴-双(S,S-二氧-二苯并噻吩)并环戊二烯(M-2)的制备:将3,9-二溴-双(二苯并噻吩)并环戊二烯(152mg,0.2mmol)和3-氯过氧苯甲酸(690mg,4mmol)溶解于10mL二氯甲烷中并在冰浴条件下反应10小时。反应结束后将反应液倒入10%质量浓度的氢氧化钠水溶液中搅拌30分钟。有机层用水洗(150mL×3),浓缩并过层析柱,洗脱剂极性为二氯甲烷/乙酸乙酯(5:1),产物用乙醇重结晶得到粉末固体(148mg,90%)。1H-NMR(600MHz,CDCl3,δ)8.15(s,2H),7.98(d,2H),7.78(m,4H),7.73(d,2H)2.12(t,4H),1.04(m,20H),0.76(t,6H),0.59(s,4H).
实施例3
3,9-二溴-双(S,S-二氧-二苯并噻吩)并吡咯(M-3)的合成(Kerszulis J.A.,AmbC.M.,Dyer A.L.,et al.Follow the yellow brick road:structuraloptimization ofvibrant yellow-to-transmissive electrochromic conjugated polymers[J].Macromolecules,2014,47(16):5462-5469.Chen Y,Liu C,Tian H,et al.NovelConjugated Polymers Based on Dithieno[3,2-b:6,7-b]carbazole for SolutionProcessed Thin-Film Transistors[J].Macromol.Rapid Comm.,2012,33(20):1759-1764.)
1)4,4’-二溴-2-硝基联苯(11)的制备:将4,4’-二溴联苯(20.0g,64.1mmol)溶于200mL乙酸,将100mL乙酸稀释的发烟硝酸(31mL)滴加到反应液中。滴毕将反应瓶封口并在100℃回流反应1~2小时。停止反应并且冷却到室温,将反应液倒入到冰水中搅拌抽滤得到淡黄色固体状物质,再分别用水、饱和亚硫酸氢钠水溶液、水、冷的乙醇按顺序分别洗涤,将滤渣干燥得到淡黄色粉末固体(15g,65.5%)。MS(APCI):m/z(%):358.0[M+].
2)2,7-二溴咔唑(12)的制备:将4,4’-二溴-2-硝基联苯(17.85g,50mmol)和三苯基膦(32.75g,125mmol)溶于300mL的N,N-二甲基乙酰胺中,氩气气氛中回流过夜反应。停止反应并且冷却到室温,用二氯甲烷萃取并水洗4~5次,干燥后用200~300目硅胶柱层析提纯(石油醚/二氯甲烷=2:1),用乙醇重结晶得到白色固体(12g,73.8%)。MS(APCI):m/z(%):326.0[M+].
3)2,7-二溴-N-(2-癸基十四烷基)咔唑(13)的制备:将2,7-二溴咔唑(32.5g,100mmol)和氢氧化钾(28g,500mmol)溶于200mL二甲基亚砜中,氮气下加热到60℃,缓慢加入2-癸基十四烷基-4-甲苯磺酸酯(76.35g,150mmol),反应8小时。停止反应并且冷却到室温,将反应液倒入水中用二氯甲烷萃取,用柱层析法纯化,以200~300目硅胶为固定相,石油醚为洗脱剂,得到白色蜡状固体(60g,91%)。MS(APCI):m/z(%):662.6[M+].
4)3,6-二甲硫基-2,7-二溴-N-(2-癸基十四烷基)咔唑(14)的制备:将二甲硫醚(0.67mL,9.2mmol)和1.7mL三氟甲磺酸酐溶于20mL干燥二氯甲烷中,降温至-40℃反应15分钟。之后缓慢滴加用二氯甲烷稀释的2,7-二溴-N-(2-癸基十四烷基)咔唑(2.91g,4.4mmol)溶液。滴毕将温度升高到-20℃反应2小时。将反应液浓缩并用20mL乙腈溶解,在0℃下反应,此时加入三乙胺(6.2mL,44mmol)。再将反应液缓慢升至室温,过夜反应。将反应液浓缩,过层析柱,洗脱剂极性为石油醚/二氯甲烷(5:1),得到粉末固体(1.59g,48%)。MS(APCI):m/z(%):754.8[M+].
5)3,6-二甲亚磺酰基-2,7-二溴-N-(2-癸基十四烷基)咔唑(15)的制备:将3,6-二甲硫基-2,7-二溴-N-(2-癸基十四烷基)咔唑(7.54g,10mmol)用乙腈溶解,在冰浴条件下搅拌,此时加入双氧水(0.68g,20mmol)反应8小时。反应结束后将反应液萃取,浓缩,得到粗产物(6.29g,80%)。MS(APCI):m/z(%):786.8[M+].
6)3,6-二甲亚磺酰基-2,7-二(3-溴苯基)-N-(2-癸基十四烷基)咔唑(16)的制备:将30mL浓度为2M的碳酸钾水溶液,间溴苯硼酸(3.5g,12.5mmol)和3,6-二甲亚磺酰基-2,7-二溴-N-(2-癸基十四烷基)咔唑(3.93g,5mmol)加入到反应瓶中,加入100mL甲苯,通氮气。反应温度升至90℃时加入350mg四三苯基膦钯和190mg四丁基溴化铵,反应24小时。停止反应并冷却到室温,用二氯甲烷萃取1~3次。将有机层旋干之后用200~300目硅胶过层析柱,洗脱剂的极性是石油醚/乙酸乙酯(3:1),得到产物(2.34g,50%)。MS(APCI):m/z(%):939.0[M+].
7)3,9-二溴-双(二苯并噻吩)并吡咯(17)的制备:将3,6-二甲亚磺酰基-2,7-二(3-溴苯基)-N-(2-癸基十四烷基)咔唑(1.88g,2mmol)加入到4.2mL三氟甲烷磺酸中,室温下反应24小时。反应结束后将反应液滴加到冰水中,抽滤得到滤渣并晾干。将滤渣溶于50mL吡啶中,氮气下加热回流8小时。停止反应并冷却到室温,萃取并用盐酸处理,用石油醚进行柱层析,乙醇重结晶得到粉末固体(0.53g,30%)。元素分析:C48H59Br2NS2理论值:C65.97%,H 6.80%,N 1.60%,S 7.34%;实测值:C 65.59%,H 6.89%,N 1.67%,S7.22%.
8)3,9-二溴-双(S,S-二氧-二苯并噻吩)并吡咯(M-3)的制备:将3,9-二溴-双(二苯并噻吩)并吡咯(1.3g,1.5mmol)和3-氯过氧苯甲酸(5.16g,30mmol)溶于200mL二氯甲烷中,冰浴条件下反应10小时。反应结束后将反应液倒入10%质量浓度的氢氧化钠水溶液中搅拌30分钟。有机层用水洗(150mL×3),浓缩并过层析柱,洗脱剂极性为二氯甲烷/乙酸乙酯(5:1),用乙醇重结晶得到粉末固体(844mg,60%)。元素分析:C50H67Br2NO2S2理论值:C61.47%,H6.34%,N 1.49%,S 6.84%;实测值:C 61.98%,H 5.97%,N 1.72%,S7.14%.
实施例4
2,10-二溴-双(S,S-二氧-二苯并噻吩)并吡咯(M-4)的合成
1)3,6-二甲亚磺酰基-2,7-二(4-溴苯基)-N-(2-癸基十四烷基)咔唑(18)的制备:将30mL浓度为2M的碳酸钾水溶液,对溴苯硼酸(3.5g,12.5mmol)和3,6-二甲亚磺酰基-2,7-二溴-N-(2-癸基十四烷基)咔唑(3.93g,5mmol)加入到反应瓶中,加入100mL甲苯,通氮气。反应温度升至90℃时加入350mg四三苯基膦钯和190mg四丁基溴化铵,反应24小时。停止反应并冷却到室温,用二氯甲烷萃取2~3次。将有机层旋干之后用200~300目硅胶过层析柱,洗脱剂的极性是石油醚/乙酸乙酯(3:1),得到产物(2.71g,58%)。MS(APCI):m/z(%):939.0[M+].
2)2,10-二溴-双(二苯并噻吩)并吡咯(19)的制备:将3,6-二甲亚磺酰基-2,7-二(4-溴苯基)-N-(2-癸基十四烷基)咔唑(1.88g,2mmol)加入到4.2mL三氟甲烷磺酸中,室温下反应24小时。反应结束后将反应液滴加到冰水中,抽滤得到滤渣并晾干。将滤渣溶于50mL吡啶中,氮气下加热回流8小时。停止反应并冷却到室温,萃取并用盐酸中和其中的吡啶。用石油醚过层析柱,并用乙醇重结晶得到粉末固体(1.31g,75%)。元素分析:C50H67Br2NO2S2理论值:C 65.97%,H 6.80%,N 1.60%,S 7.34%;实测值:C 66.56%,H 6.47%,N 1.33%,S 7.65%.
3)2,10-二溴-双(S,S-二氧-二苯并噻吩)并吡咯(M-4)的制备:将2,10-二溴-双(二苯并噻吩)并吡咯(1.3g,1.5mmol)和3-氯过氧苯甲酸(5.16g,30mmol)溶于200mL二氯甲烷中,冰浴下搅拌10小时。反应结束后将反应液倒入10%质量浓度的氢氧化钠水溶液中搅拌30分钟。有机层用水洗(150mL×3),浓缩并过层析柱,洗脱剂极性为二氯甲烷/乙酸乙酯(5:1),用乙醇重结晶得到粉末固体(1.13g,80%)。元素分析:C50H67Br2NO2S2理论值:C61.47%,H6.34%,N 1.49%,S 6.84%;实测值:C 61.77%,H 6.01%,N 1.81%,S6.59%.
实施例5
5,7-二溴-双(S,S-二氧-二苯并噻吩)并吡咯(M-5)的合成(Kerszulis J.A.,AmbC.M.,Dyer A.L.,et al.Follow the yellow brick road:structuraloptimization ofvibrant yellow-to-transmissive electrochromic conjugated polymers[J].Macromolecules,2014,47(16):5462-5469.)
1)2,7-二硼酸酯-N-(2-癸基十四烷基)咔唑(20)的制备:将2,7-二溴-N-(2-癸基十四烷基)咔唑(13.2g,20mmol)溶于120mL绝干四氢呋喃中,室温溶解后放入-80℃低温反应器中,氩气下缓慢滴加浓度为2.4M的正丁基锂的正己烷溶液(25mL,60mmol),保温反应2小时,之后快速加入2-异丙基-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(16.3mL,80mmol),保温反应40分钟之后在室温下过夜反应。停止反应将反应液倒入水中淬灭,将反应液浓缩并用二氯甲烷萃取,用柱层析法纯化处理,以200~300目硅胶为固定相,洗脱剂为石油醚/二氯甲烷(2:1),得到淡黄色透明粘稠液体(9.8g,65%)。MS(APCI):m/z(%):756.8[M+].
2)2,7-二(2-甲亚磺酰苯基)-N-(2-癸基十四烷基)咔唑(21)的制备:将2,7-二硼酸酯-N-(2-癸基十四烷基)咔唑(20g,26.5mmol),1-溴-2-甲亚磺酰苯(14.5g,66mmol),四丁基溴化铵(0.84g,2.6mmol)和130mL浓度为2M的碳酸钾水溶液加入到500mL的三口圆底烧瓶中,并加入300mL甲苯充分溶解,氩气条件下加热回流搅拌,温度稳定在90℃时加入四(三苯基膦)钯(1.5g,1.3mmol),密封好反应瓶,加热回流过夜反应。之后停止反应并且冷却到室温,用水洗反应液2~3次,之后将反应液浓缩过层析柱,硅胶200~300目,洗脱剂为石油醚/乙酸乙酯(3:1),最终得到淡黄色油状液体,产物有(16.5g,80%)。MS(APCI):m/z(%):781.2[M+].
3)双(二苯并噻吩)并吡咯(22)的制备:将2,7-二(2-甲亚磺酰苯基)-N-(2-癸基十四烷基)咔唑(5g,6.4mmol)溶于9mL的三氟甲烷磺酸中反应,同时反应瓶密封,反应8小时。停止反应将反应液滴加到冰水中,抽滤得到滤渣并晾干。将滤渣溶于100mL吡啶中,氩气下加热回流8小时。停止反应并且冷却到室温,盐酸中和并用二氯甲烷萃取,干燥后用200~300目硅胶柱层析(石油醚/二氯甲烷=5:1),用乙醇重结晶得到黄色粉末固体(2.6g,56%)。MS(APCI):m/z(%):716.5[M+].元素分析:C48H61NS2,理论值:C 80.50%,H 8.59%,N1.96%,S 8.96%;实测值:C 80.85%,H 8.23%,N 2.10%,S 8.75%。
4)双(S,S-二氧-二苯并噻吩)并吡咯(23)的制备:将双(二苯并噻吩)并吡咯(1.5g,2.1mmol)和间氯过氧苯甲酸(7.2g,42mmol)用二氯甲烷溶解,冰浴下过夜反应。反应结束后,将反应液倒入饱和氢氧化钠水溶液中,二氯甲烷萃取,干燥,200~300目硅胶过层析柱(二氯甲烷),四氢呋喃重结晶得到白色固体(1.3g,81%)。元素分析:C48H61NO4S2,理论值:C 73.90%,H7.88%,N 1.80%,S 8.22%;实测值:C 74.21%,H 7.65%,N 1.91%,S8.10%。
5)5,7-二溴-双(S,S-二氧-二苯并噻吩)并吡咯(M-5)的制备:将双(S,S-二氧-二苯并噻吩)并吡咯(100mg,0.13mmol)冰浴条件下加入到10mL三氯甲烷和5ml三氟乙酸的混合溶液中溶解,再将N-溴代丁二酰亚胺(91.3mg,0.51mmol)用5mL三氟乙酸和2mL硫酸溶解,避光条件下缓慢滴加到反应液中,过夜反应。反应停止后将反应液倒入水中,二氯甲烷萃取,200~300目硅胶过层析柱(二氯甲烷),乙醇重结晶得到白色固体(73mg,80%)。1H-NMR(600MHz,CDCl3,δ)9.10(d,2H),8.49(s,2H),7.95(d,2H),7.72(t,2H),7.61(t,2H),5.18(d,2H),1.79(m,1H),1.32-0.93(m,34H),0.91-0.72(m,10H),0.60(m,2H).
实施例6
4,7-二(5-溴-(4-己基噻吩)-2-基)-2,1,3-苯并噻二唑(M-6)的制备(Zhuang XX,Lei X L,Sun X X.The New Synthesis of Organic Light-Emitting Material BHBTMonomer by Stille Coupling[C].Advanced Materials Research.2013,602:1261-1264.)
1)4,7-二溴-2,1,3-苯并噻二唑(24)的制备:氮气保护下,将3-己基噻吩(8.4g,50mmol)溶于100mL干燥的四氢呋喃中,用液氮/乙醇降温至-30℃,滴加浓度为2.5M正丁基锂(22mL,55mmol),然后在-30℃下反应2小时,再滴加SnBu3Cl,继续在-30℃反应30分钟。将反应液倒入亚硫酸氢钠溶液,用***萃取,水洗有机层后,用硫酸钠干燥,减压下除去溶剂,用中性Al2O3柱层析(石油醚),得到无色透明的油状液体。无需进一步精制,直接用于下一步反应。MS(APCI):m/z(%):294.9[M+].
2)4,7-二(4-己基噻吩-2-基)-2,1,3-苯并噻二唑(25)的制备:将4g 4,7-二溴-2,1,3-苯并噻二唑,13.6g三丁基-(4-己基噻吩-2-基)锡烷,200mg PdCl2(PPh3)2溶于100mL的THF,在氮气保护下回流6小时,然后减压除去溶剂,将得到的红色固体以硅胶为载体,用混合溶剂CH2Cl2/石油醚(1:1)柱层析。最后用无水乙醇重结晶得到橙红色针状晶体,产率:85%。元素分析:C26H32N2S3理论值:C 66.62%,H 6.88%,N 5.98%,S 20.52%;实测值:C67.07%,H 6.66%,N 5.77%,S 20.40%.
3)4,7-二(5-溴-(4-己基噻吩)-2-基)-2,1,3-苯并噻二唑(M-6)的制备:将2.34g4,7-二(4-己基噻吩-2-基)-2,1,3-苯并噻二唑加入150mL的THF中,待固体全部溶解后,加入2.14g NBS,然后室温搅拌过夜,加水后,用***萃取,无水硫酸镁干燥,减压蒸除溶剂后得到红色固体,用硅胶做载体,石油醚为洗脱液用柱层析进一步提纯得到红色固体(M-6)。1H-NMR(600MHz,CDCl3,δ)7.76(s,2H),7.72(s,2H),2.63(t,4H),1.66(m,4H),1.34(m,12H),0.88(t,6H).
实施例7
聚(9,9-二正辛基芴-co-2,10-双S,S-二氧-二苯并噻吩并环戊二烯)(P1)的制备
将2,7-二(4,4,5,5-四甲基-1,3-二氧-2-硼烷基)-9,9-二正辛基芴(321mg,0.5mmol),2,7-二溴-9,9-二正辛基芴(269mg,0.49mmol)和2,10-二溴-双(S,S-二氧-二苯并噻吩)并环戊二烯(8.2mg,0.01mmol)加入到10mL甲苯中,同时加入10mg四(三苯基膦)钯和1mL四乙基羟氨,温度稳定在80℃反应30小时,之后加入1mL溴苯封端并反应8小时,之后将反应停止冷却到室温,沉析到甲醇中,过滤之后索氏提取(先后用甲醇,丙酮和正己烷),之后将聚合物用甲苯溶解过层析柱,再次沉析到甲醇中过滤,得到纤维状聚合物(270mg,70%)。1H-NMR(600MHz,CDCl3,δ)7.48-7.85(br,Ar H),1.95-2.31(m,CH2),0.93-1.30(m,CH2),0.72-0.91(m,CH2).元素分析:[(C29H40)0.99(C41H44O4S2)0.01]理论值:C 89.42%,H10.24%,S0.16%实测值:C 89.23%,H 10.46%,S 0.23%.
实施例8
聚(9,9-二正辛基芴-co-2,10-双S,S-二氧-二苯并噻吩并环戊二烯-co-4,7-二(4-己基噻吩-2-基)-2,1,3-苯并噻二唑)(P2)的制备
将2,7-二(4,4,5,5-四甲基-1,3-二氧-2-硼烷基)-9,9-二正辛基芴(321mg,0.5mmol),2,7-二溴-9,9-二正辛基芴(236mg,0.43mmol),2,10-二溴-双(S,S-二氧-二苯并噻吩)并环戊二烯(41.2mg,0.05mmol)和4,7-二(5-溴-(4-己基噻吩)-2-基)-2,1,3-苯并噻二唑(12.5mg,0.02mmol)加入到10mL甲苯中,同时加入5mg四(三苯基膦)钯和0.5mL四乙基羟氨,温度稳定在80℃反应30小时,之后加入0.5mL溴苯封端并反应8小时,之后将反应停止冷却到室温,沉析到甲醇中,过滤之后索氏提取(先后用甲醇,丙酮和正己烷),之后将聚合物用甲苯溶解过层析柱,再次沉析到甲醇中过滤,得到纤维状聚合物(280mg,70%)。1H-NMR(600MHz,CDCl3,δ)8.21(br,ArH),8.00(br,ArH),7.86-7.80(br,ArH),7.71-7.60(br,ArH),7.48(br,ArH),7.37(br,ArH),2.13(br,CH2),1.33-1.15(br,CH2),0.83-0.80(t,CH3),0.72(br,CH2);元素分析:[(C29H40)0.93(C41H44O4S2)0.05(C26H30N2S3)0.02]理论值:C87.87%,H 9.91%,N 0.14%,S 0.97%实测值:C 88.24%,H 10.02%,N 0.12%,S1.10%.
实施例9
聚(9,9-二正辛基芴-alt-2,10-双S,S-二氧-二苯并噻吩并环戊二烯)(P3)的制备
将2,7-二(4,4,5,5-四甲基-1,3-二氧-2-硼烷基)-9,9-二正辛基芴(321mg,0.5mmol),2,10-二溴-双(S,S-二氧-二苯并噻吩)并环戊二烯(412mg,0.5mmol)加入到20mL甲苯和10mL四氢呋喃的混合溶液中,同时加入10mg四(三苯基膦)钯和1mL四乙基羟氨,温度稳定在50℃反应30小时,之后加入1mL溴苯封端并反应8小时,之后将反应停止冷却到室温,沉析到甲醇中,过滤之后索氏提取(先后用甲醇,丙酮和正己烷),之后将聚合物用甲苯溶解过层析柱,再次沉析到甲醇中过滤,得到粉末状固体(375mg,71%)。1H-NMR(600MHz,CDCl3,δ)8.21(br,ArH),8.10-8.00(br,ArH),7.87-7.80(br,ArH),7.67-7.50(br,ArH),7.38(br,ArH),2.13-2.08(br,CH2),1.25-1.12(br,CH2),0.80(t,CH3),0.71(br,CH2);元素分析:[(C29H40)0.5(C41H44O4S2)0.5]理论值:C 79.77%,H 7.98%,S 6.08%实测值:C 80.17%,H7.53%,S 5.75%.
实施例10
聚(9,9-二正辛基芴-co-5,7-双S,S-二氧-二苯并噻吩并吡咯)(P4)的制备
将2,7-二(4,4,5,5-四甲基-1,3-二氧-2-硼烷基)-9,9-二正辛基芴(321mg,0.5mmol),2,7-二溴-9,9-二正辛基芴(257.8mg,0.47mmol)和5,7-二溴-双(S,S-二氧-二苯并噻吩)并吡咯(28.1mg,0.03mmol)加入到10mL甲苯中,同时加入10mg四(三苯基膦)钯和1mL四乙基羟氨,温度稳定在80℃反应30小时,之后加入1mL溴苯封端并反应8小时,之后将反应停止冷却到室温,沉析到甲醇中,过滤之后索氏提取(先后用甲醇,丙酮和正己烷),之后将聚合物用甲苯溶解过层析柱,再次沉析到甲醇中过滤,得到粉末状固体(320mg,80%)。1H-NMR(600MHz,CDCl3,δ)8.70(br,ArH),8.25(br,ArH),7.95-7.63(br,ArH),4.77(s,N-CH),2.47(br,CH2),2.06(br,CH2),1.33-1.18(br,CH2),0.82-0.77(br,CH3);元素分析:[(C29H41N)0.97(C48H59NO4S2)0.03]理论值:C 85.69%,H 10.03%,N 3.38%,S 0.46%实测值:C85.53%,H 9.79%,N 3.23%,S 0.42%.
实施例11
聚(9,9-二正辛基芴-co-5,7-双S,S-二氧-二苯并噻吩并吡咯-co-4,7-2,1,3-苯并噻二唑)(P5)的制备
将2,7-二(4,4,5,5-四甲基-1,3-二氧-2-硼烷基)-9,9-二正辛基芴(321mg,0.5mmol),2,7-二溴-9,9-二正辛基芴(246.8mg,0.45mmol),5,7-二溴-双(S,S-二氧-二苯并噻吩)并吡咯(28.1mg,0.03mmol)和4,7-二溴-2,1,3-苯并噻二唑(6mg,0.02mmol)加入到10mL甲苯中,同时加入10mg四(三苯基膦)钯和1mL四乙基羟氨,温度稳定在80℃反应30小时,之后加入1mL溴苯封端并反应8小时,之后将反应停止冷却到室温,沉析到甲醇中,过滤之后索氏提取(先后用甲醇,丙酮和正己烷),之后将聚合物用甲苯溶解过层析柱,再次沉析到甲醇中过滤,得到纤维状固体(235mg,60%)。1H-NMR(600MHz,CDCl3,δ)8.72(br,ArH),7.86-7.82(br,ArH),7.68(br,ArH),2.13(br,CH2),1.26-1.09(br,CH2),0.82-0.79(t,CH3);元素分析:[(C29H40)0.95(C48H59NO4S2)0.03(C6H2N2S)0.02]理论值:C 88.52%,H 10.09%,N0.25%,S 0.65%实测值:C 88.76%,H 9.84%,N 0.21%,S 0.61%.
实施例12
聚(9,9-二正辛基芴-alt-5,7-双S,S-二氧-二苯并噻吩并吡咯)(P6)的制备
将2,7-二(4,4,5,5-四甲基-1,3-二氧-2-硼烷基)-9,9-二正辛基芴(321mg,0.5mmol),和5,7-二溴-双(S,S-二氧-二苯并噻吩)并吡咯(469mg,0.5mmol)加入到10mL甲苯中,同时加入10mg四(三苯基膦)钯和1mL四乙基羟氨,温度稳定在80℃反应30小时,之后加入1mL溴苯封端并反应8小时,反应停止冷却到室温,沉析到甲醇中,过滤之后索氏提取(先后用甲醇,丙酮和正己烷),之后将聚合物用甲苯溶解过层析柱,再次沉析到甲醇中过滤,得到粉末状固体(265mg,46%)。1H-NMR(600MHz,CDCl3,δ)9.12-9.09(br,ArH),8.67-8.60(br,ArH),8.50-8.41(br,ArH),7.96-7.32(br,ArH),5.20(d,N-CH2),4.78(s,N-CH),2.03(br,CH2),1.33-1.13(br,CH2),0.87-0.79(br,CH3);元素分析:[(C29H40)0.5(C48H59NO4S2)0.5]理论值:C79.25%,H 8.49%,N 1.20%,S 5.49%实测值:C 78.66%,H8.88%,N 1.02%,S 5.89%.
实施例13
聚(2,10-双S,S-二氧-二苯并噻吩并环戊二烯)(P7)的制备
在氮气手套箱中将2,10-二溴-双(S,S-二氧-二苯并噻吩)并环戊二烯(825mg,1.0mmol)加入到30mL四氢呋喃中,同时加入2.0g双(1,5-环辛二烯)镍,1,5-环辛二烯1.0g和联吡啶1.5mg,温度稳定在80℃反应4天,之后加入0.5mL溴苯封端并反应20小时,之后将反应停止冷却到室温,沉析到甲醇中,过滤之后索氏提取(先后用甲醇,丙酮和正己烷),之后将聚合物用氯仿溶解过层析柱,再次沉析到甲醇中过滤,得到粉末固体(300mg,45%)。1H-NMR(600MHz,CDCl3,δ)8.18-8.15(br,ArH),8.06-7.99(br,ArH),7.91-7.89(br,ArH),7.81-7.69(br,ArH),2.13-2.11(m,CH2),1.25-1.08(m,CH2),0.79(t,CH3),0.59(m,CH2);元素分析:[(C41H44O4S2)n]理论值:C 74.06%,H 6.67%,S 9.64%实测值:C 74.42%,H7.02%,S9.17%.
实施例14
聚(5,7-双S,S-二氧-二苯并噻吩并吡咯)(P8)的制备
在氮气手套箱中称取5,7-二溴-双(S,S-二氧-二苯并噻吩)并吡咯(938mg,1.0mmol)加入到15mL甲苯中,同时加入加入2.0g双(1,5-环辛二烯)镍,1,5-环辛二烯1.0g和联吡啶1.5g,温度稳定在80℃反应5天,之后加入0.5mL溴苯封端并反应1天。反应停止冷却到室温,沉析到甲醇中,过滤之后索氏提取(先后用甲醇,丙酮和正己烷),之后将聚合物用氯仿溶解过层析柱,再次沉析到甲醇中过滤,得到粉末状固体(250mg,32%)。1H-NMR(600MHz,CDCl3,δ)8.49-8.27(br,ArH),7.86-7.51(br,ArH),7.35-7.33(br,ArH),4.32(d,N-CH2),2.58(s,CH),1.45-1.08(br,CH2),0.94-0.80(br,CH3);元素分析:[(C48H59NO4S2)n]理论值:C 73.85%,H 7.56%,N 1.79%,S 8.21%实测值:C 74.23%,H 7.11%,N1.57%,S 8.44%.
实施例15
共聚物电致发光器件的制备
在预先做好的氧化铟锡(ITO)玻璃上,其方块电阻为10-20Ω,先依次用丙酮,洗涤剂,去离子水和异丙醇超声清洗,等离子处理10分钟。在ITO上旋涂参杂有聚苯乙烯磺酸的聚乙氧基噻吩(PEDOT:PSS)膜,厚度约为150nm。PEDOT:PSS膜在真空烘箱里80℃下干燥8小时。随后将聚合物的二甲苯溶液(1wt.%)旋涂在PEDOT:PSS膜的表面,厚度约为80nm;最后在发光层上依次蒸镀一层1.5nm厚的CsF和120nm厚的金属Al层。
表1共聚单体组成、聚合物分子量及分子量分布
*为4,7-二(5-溴-(4-己基噻吩)-2-基)-2,1,3-苯并噻二唑(DHTBT)
表2聚合物器件发光性能
器件结构:ITO/PEDOT:PSS/聚合物/CsF/Al
图1为聚合物P1、P2、P3热重分析曲线,图中可以看出聚合物的热分解温度均接近或超过400℃,说明聚合物具有较刚性的分子主链,赋予聚合物较好的热稳定性。
图2为聚合物P1、P4、P7和P8薄膜中的紫外-可见吸收光谱,图中可以看出聚合物P1、P4和P7的吸收峰值在均390nm附近,此处吸收为分子主链π-π*的跃迁吸收,P7分子间相互作用增强,吸收光谱发生宽化,P8为双(S,S-二氧-二苯并噻吩)并吡咯单元的本征吸收。
图3为聚合物P1、P4、P7和P8的薄膜光致发光光谱,图中可以看出相比于聚合物P1,聚合物P4的发射有明显的蓝移和窄化,这主要是由于聚合物主链中双(S,S-二氧-二苯并噻吩)并吡咯单元的空间扭转构型抑制了光谱的红移,P4实现深蓝发射,聚合物P7由于分子间较强的电荷转移作用导致光谱红移和宽化,P8为双(S,S-二氧-二苯并噻吩)并吡咯单元的本征发射。
图4为聚合物P4、P6和P8的循环伏安特性曲线,从图中可以看出聚合物P4、P6和P8的HOMO和LUMO能级逐渐降低,氧化电位和还原电位逐渐右移,说明随着双(S,S-二氧-二苯并噻吩)并吡咯单元含量的增加,化合物的电负性逐渐增大,有利于得到具有较好电子传输性能的材料。
图5为聚合物P1、P3和P7的循环伏安特性曲线,从图中可以看出随着双(S,S-二氧-二苯并噻吩)并环戊二烯单元含量的增加,材料的HOMO能级逐渐降低,说明双砜基的存在可以显著降低材料的HOMO能级,使材料具备较好的电子传输性能。
图6为聚合物P1、P2、P4和P5的电压-电流密度-亮度曲线,从图中可以看出聚合物具有较低的启亮电压和较高的亮度,说明材料成膜性较好,能级相对匹配,具有很好的荧光特性。
图7为聚合物P1、P2、P4和P5器件EL光谱曲线,从图中可以看出,对比聚合物P1和P4,由于P4分子链结构扭曲,光谱长波长方向的发射部分受到抑制,P4聚合物实现了较好的深蓝发射。
Claims (4)
1.双S,S-二氧-二苯并噻吩并五元环单体的聚合物,其特征在于,结构式如下,
式中:x,y为单元组分的摩尔分数,满足:0<x≤1,x+y=1,n=1~300;R1为碳原子数为1~30的烷基;
其中,具有如下结构之一:
2,10-取代双(S,S-二氧-二苯并噻吩)并环戊二烯
3,9-取代双(S,S-二氧-二苯并噻吩)并环戊二烯。
2.双S,S-二氧-二苯并噻吩并五元环单体的聚合物,其特征在于,结构式如下,
式中:x,y为单元组分的摩尔分数,满足:0<x≤1,x+y=1,n=1~300;R1为碳原子数为1~30的烷基;
其中,具有如下结构之一:
3,9-取代双(S,S-二氧-二苯并噻吩)并吡咯
2,10-取代双(S,S-二氧-二苯并噻吩)并吡咯
5,7-取代双(S,S-二氧-二苯并噻吩)并吡咯。
3.根据权利要求1或2所述双S,S-二氧-二苯并噻吩并五元环单体的聚合物,其特征在于,Ar为如下结构之一:
2,7-取代芴;
3,6-取代芴;
2,7-取代螺芴;
2,7-取代硅芴;
2,7-取代锗芴;
2,7-取代咔唑;
3,6-取代咔唑;
3,9-取代吲哚咔唑;
2,8-取代吲哚咔唑;
3,9-取代茚芴;
2,8-取代茚芴;
1,4-取代苯;
4,7-取代2,1,3-苯并噻二唑;
4,7-取代-2,1,3-苯并硒二唑;
4,7-二(4-取代苯基)-2,1,3-苯并噻二唑;
4,7-二(4-取代苯基)-2,1,3-苯并硒二唑;
4,7-二(5-取代-4-烷基噻吩-2-基)-2,1,3-苯并噻二唑;
4,7-二(5-取代-4-烷基噻吩-2-基)-2,1,3-苯并硒二唑;
4,7-二(N-(4-取代苯基)-N-(4-烷基苯基)胺基)-2,1,3-苯并噻二唑;
4,7-二(N-(4-取代苯基)-N-(4-烷基苯基)胺基)-2,1,3-苯并硒二唑;
4,7-二(4-(N-(4-取代苯基)-N-(4-烷基苯基)胺基)苯基)-2,1,3-苯并噻二唑;
4,7-二(4-(N-(4-取代苯基)-N-(4-烷基苯基)胺基)苯基)-2,1,3-苯并硒二唑;
3,7-二(N-(4-取代苯基)-N-(4-烷基苯基)胺基)-二苯并噻吩-S,S-二氧;
2,8-二烷基-3,7-二(N-(4-取代苯基)-N-(1-苯基)胺基)-二苯并噻吩-S,S-二氧;
3,7-二(4-(N-(4-取代苯基)-N-(4-烷基苯基)胺基)苯基)-二苯并噻吩-S,S-二氧;
2,8-二烷基-3,7-二(4-(N-(4-取代苯基)-N-(1-苯基)胺基)苯基)-二苯并噻吩-S,S-二氧;
其中,Z1、Z2包括如下组合:Z1=H,Z2=H、或者Z1=H,Z2=F、或者Z1=F,Z2=F;
R2为碳原子数为1~30的烷基、1~30的烷氧基或H原子。
4.权利要求1或2所述的聚合物在有机电致发光器件、有机太阳能电池和有机场效应晶体管中的应用。
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