CN110372848A - 一种含氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物及其制备与应用 - Google Patents
一种含氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物及其制备与应用 Download PDFInfo
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- CN110372848A CN110372848A CN201910527754.5A CN201910527754A CN110372848A CN 110372848 A CN110372848 A CN 110372848A CN 201910527754 A CN201910527754 A CN 201910527754A CN 110372848 A CN110372848 A CN 110372848A
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- polymer
- selenole
- octyl
- decyl
- alkyl
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- 229920000642 polymer Polymers 0.000 title claims abstract description 91
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 125000001153 fluoro group Chemical group F* 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010409 thin film Substances 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims abstract 2
- -1 2- ethylhexyl Chemical group 0.000 claims description 31
- 239000010408 film Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920006254 polymer film Polymers 0.000 claims description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000010129 solution processing Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 229910052711 selenium Inorganic materials 0.000 description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 12
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
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Classifications
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—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
- C08G61/123—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
-
- 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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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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Abstract
本发明涉及一种含氟代2,1,3‑苯并硒二唑与二噻吩并环戊二烯的聚合物及其制备与应用，如通式I所示。采用二噻吩并环戊二烯的单体与含氟取代2,1,3‑苯并硒二唑的单体，通过金属催化的偶联缩聚反应制备得到。本发明的聚合物具有优异的载流子迁移率，具备良好的热稳定性以及溶液加工性能，而且合成简洁有效、成本低廉，在实现高迁移率的聚合物方面具有较大的潜在价值。另外本发明还公开了上述聚合物在有机薄膜晶体管中的应用。
Description
技术领域
本发明属于有机半导体材料及其制备和应用领域，特别涉及一种含氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物及其制备与应用。
背景技术
上世纪七十年代，日本科学家百川英树发现高浓度掺杂的聚乙炔具有导电性，这一历史性发现打破了塑料是绝缘体、不能导电这一传统观念。从那时起，科学家一直致力于开发零带隙的导电聚合物，期望使其能够替代昂贵的金属作为导体使用。然而，经过科学家20-30 年不懈的努力发现实现这一目标几乎不太可能。具有共轭特性的聚合物中存在两种化学键，一种是定域的σ键，其构成聚合物的分子骨架。另一种是离域的π键，其在聚合物主链上形成π电子云，π电子能够在聚合物主链上移动。具有离域的π电子聚合物往往具有荧光特性，同时可以传输载流子，这些特性使得共轭聚合物可以作为有机半导体材料使用。上世纪90年代后期以来，聚合物有机半导体材料在有机太阳能电池(OPV)，有机薄膜晶体管晶体管(OTFT)，有机电致发光材料(OLED)，有机光电探测器(OPD)等领域的应用逐渐占据了有机导体材料研究的主流。Wynberg等人在1992年提出的D-A材料设计理念是有机半导体材料最常用的设计策略。D-A共聚物(Donor-Acceptor Polymers)，即给体－受体共聚物，是指将一种或几种分子内具有缺电子基团的、作为受体的单元，与一种或几种分子内具有给电子基团的、作为给体的单元通过共价键链接所形成的交替聚合物。化学家可以通过改变给体和受体的推拉电子的能力，精细化调控共轭聚合物的HOMO-LUMO能级，从而实现对材料的光电性能产生积极影响。
聚合物主链上通常含助溶性基团，这将有利于使用有机溶剂溶解有机共轭聚合物，通过旋涂、刮涂、滴涂、喷墨打印等溶液加工成膜方式制备高质量的聚合物薄膜。在聚合物薄膜的基础上，可以进一步地制备一系列有机半导体电子器件。相比于小分子材料，聚合物的分离提纯不需要复杂的柱色谱，通过简单的沉淀、索氏提取即可以得到目标产品。
硒与硫同属氧族元素，二者具有相似的电负性(硒：2.4，硫：2.5)和化学性质。但是，硒的原子半径更大(硒：0.116nm，硫：0.102nm)，极化性更强。有机硒化合物的相比于同类的硫化合物偶极矩更大，硒与硒、硒与氮之间的弱相互作用有利于分子在固态时形成面对面堆积和更加有序的结构(Hollinger,J.；Jahnke,A.A.；Coombs,N.；Seferos,D.S.J.Am.Chem. Soc.2010,132,8546-8547；Pati,P.B.；Zade,S.S.Cryst.GrowthDes.2014,14,1695-1700)。因此，采用硒原子取代硫原子可以提高激子的拆分效率和载流子的传输性能。PCDTFBT(Wang, M.；Ford,M.；Phan,H.；Coughlin,J.；Nguyen,T.-Q.；Bazan,G.C.Chem.Commun.2016,52, 3207-3210.)(指出该文献中的PCDTFBT存在的缺陷，从而引出下列本发明克服现有技术…的缺陷或填补…的空白)本发明在PCDTFBT(Wang,M.；Ford,M.；Phan,H.；Coughlin,J.； Nguyen,T.-Q.；Bazan,G.C.Chem.Commun.2016,52,3207-3210.)的基础上，进一步采用原子半径更大的硒原子取代氟代苯并噻二唑中的硫原子，拓宽聚合物在近红外的吸收光谱，同时使分子在薄膜时的堆积更加紧密，取得更高的载流子迁移率。
需要注意的是，相关专利中报道了包含氟代2,1,3-苯并硒二唑与(WO 2015/121775 A1)的有机半导体材料。但是，其集中于小分子和寡聚物在有机太阳能电池中的应用，而且相关的有机半导体材料还包含大量的噻吩单元，与本发明含有氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物有本质区别。
发明内容
本发明所要解决的技术问题是提供一种含氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物及其制备与应用，克服现有技术硫原子半径较小、分子堆积的紧密程度还有进一步提升空间的缺陷，本发明基于二噻吩并环戊二烯与氟代2,1,3-苯并硒二唑的给-受体型聚合物，其中烷基为助溶性基团，作为传输载流子的有机共轭聚合物。
本发明的一种如通式I所示的含有氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物，
其中R1和R2各自独立的1～30个碳原子的烷基链、1～30个碳原子的烷氧基链、5～30 个碳原子的环烷基、2～30个杂烷基链中的一种；n为区域规整性聚合物重复单元的数目，n ≧6且为整数；取代基X与Y至少有一个为氟原子；
所述R1、R2分别选1～30个碳原子的烷基链为甲基，乙基，丙基，丁基，戊基，已基，庚基，辛基，壬基，癸基，十一烷基，十二烷基，十六烷基，三十烷基，异丙基，异丁基，2-乙基已基,2-丁基己基，2-丁基辛基，2-己基辛基，2-己基癸基，2-已基十二烷基，2-辛基癸基，2-辛基十二烷基，2辛基十四烷基，2-辛基十六烷基，2-癸基十二烷基，2-癸基十四烷基，2-葵基十六烷基，2-十烷基十四烷基，2-十烷基十六烷基，2-十一烷基十八烷基中的一种或几种；或者为1～30个碳原子的烷氧基链、5～30个碳原子的环烷基或者2～30个杂烷基链中的一种。
所述聚合物为：
其中6≤n≤600，且n为整数。
本发明的一种权利要求1所述含有氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物的制备方法，包括：
采用二噻吩并环戊二烯的单体与(含)单氟取代2,1,3-苯并硒二唑的单体，通过金属催化的偶联缩聚反应制备得到。
进一步，本发明制备如下：
本发明的一种含有氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物薄膜，将所述含有氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物成膜，成膜方式为旋涂、刮涂、滴涂、喷墨打印等。
本发明的一种所述含有氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物在有机薄膜晶体管中的应用。
本发明一种含含有氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物聚合物可应用于制作有机场效应晶体管中的活性层。
有益效果
(1)本发明的此类聚合物表现出优异的载流子迁移率，具备良好的热稳定性以及溶液加工性能，而且合成简洁有效、成本低廉，在实现高迁移率聚合物方面具有较大的潜在价值；
(2)本发明中含含有氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物形成D-A型聚合物，使得聚合物具有理想的HOMO和LUMO能级水平、能量带隙以及吸收光谱；
(3)本发明的聚合物具有多个烷基支链，使得聚合物在常见有机溶剂中具有良好的溶解性，聚合物溶解于溶剂后所形成的溶液，可通过滴涂或者旋涂等方式形成聚合物薄膜，且得到的薄膜具有较好的形貌；
(4)基于本发明的聚合物所制备的机薄膜晶体管具有较高的载流子迁移率；
(5)本发明和现有PCDTFBT相比，采用硒原子取代氟代苯并噻二唑中的硫原子，拓宽聚合物在近红外的吸收光谱，同时使分子在薄膜时的堆积更加紧密，在相同器件制备的条件下，可以取得更高的载流子迁移率。
附图说明
图1为化合物CDT-C16的核磁共振氢谱(600MHz,CDCl3,25℃)；
图2为化合物CDT-Sn的核磁共振氢谱(600MHz,CD2Cl2,25℃)；
图3为化合物2FBSeCDT的核磁共振氢谱(600MHz,CDCl3,25℃)；
图4为化合物2FBSeCDT的核磁共振氟谱(564MHz,CDCl3,25℃)；
图5为聚合物PCDTFBSe-C16的高温GPC曲线(150℃,1,2,4-三氯苯)；
图6为聚合物PCDTFBSe-C16的TGA曲线；
图7为聚合物PCDTFBSe-C16的DSC曲线；
图8为聚合物PCDTFBSe-C16的循环伏安(CV)曲线；
图9为聚合物PCDTFBSe-C16的溶液(A)和薄膜(B)吸收光谱；
图10为底栅底接触有机薄膜晶体管器件的结构示意图；
图11为基于聚合物PCDTFBSe-C16的有机薄膜晶体管的转移曲线。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
无水四氢呋喃采用钠/二酮甲酮回流得到；
二噻吩并环戊二烯酮购买于苏州纳凯有限公司；
溶剂购买于国药化学有限公司。
叔丁醇钠、硼氢化钠、十六烷基溴、正丁基锂、三甲基氯化锡购买于百灵威科技有限公司；四三苯基膦钯购买于Strem公司；2-溴噻吩购买于阿拉丁试剂(上海)有限公司。
FBSe的制备参考文献(Li,Y.-X.；Pan,Z.Miao,L.；Xing,Y.；Li,C.；Chen,Y.Polym.Chem. 2014,5,330-334)合成，2FBSe的制备参考文献(WO 2018/035695A1)合成；
含有氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物具体制备过程反应式如下所示：
或者
实施例1
FBSe的制备：在50mL干燥的反应瓶中加入4,7-二溴-5氟代苯并噻二唑(1g,3.2mmol)和25mL无水乙醇，将此反应液冷却至0摄氏度，分批次加入硼氢化钠(2.2g,18.5倍当量)，加完后回到室温反应过夜。蒸干溶剂后将粗产品过一快速柱得白色固体，直接投入下一步反应。
在50mL干燥的反应瓶中加入上一步反应所得的产物，加入10mL无水乙醇，将反应液加热至50摄氏度后慢慢滴加二氧化锡的水溶液，滴加完毕后回流3个小时。冷却至室温后，过滤得粗产品，将粗产品使用乙酸乙酯重结晶得白色晶体，两步产率约为35％。
物质的核磁表征与参考文献(Li,Y.-X.；Pan,Z.Miao,L.；Xing,Y.；Li,C.；Chen,Y.Polym.
Chem.2014,5,330-334)一致。
2FBSe的制备：在50mL干燥的反应瓶中加入4,7-二溴-5,6-二氟代苯并噻二唑(1g,3.0 mmol)和25mL无水乙醇，将此反应液冷却至0摄氏度，分批次加入硼氢化钠(2g,18.5倍当量)，加完后回到室温反应过夜。蒸干溶剂后将粗产品过一快速柱得白色固体，直接投入下一步反应。
在50mL干燥的反应瓶中加入上一步反应所得的产物，加入10mL无水乙醇，将反应液加热至50摄氏度后慢慢滴加二氧化锡的水溶液，滴加完毕后回流3个小时。冷却至室温后，过滤得粗产品，将粗产品使用乙酸乙酯重结晶得白色晶体，两步产率约为32％。
物质的核磁表征与参考文献(WO 2018/035695A1)一致。
CDT-C16的制备：向250mL的干燥反应瓶中加入二噻吩并环戊二烯(3g，16.83mmol)，氩气保护下加入二甲基亚砜(50mL)和叔丁醇钠(6.46g，4倍当量)。将反应液加热至50 摄氏度，缓缓滴加十六烷基溴(13mL，2.5倍当量)反应过夜。冷却至室温后，使用水和二氯甲烷(50×3mL)萃取，合并有机相后使用无水硫酸镁干燥后，旋干后将粗产品使用层析硅胶柱提纯(洗脱剂为石油醚)，最后得到白色固体9.05g，产率约为86％。
1H NMR测试(600MHz,CDCl3,δ,ppm):7.16(d,1H),6.95(d,1H),1.82(t,2H), 1.31-1.13(m,28H),0.88(t,3H)。
CDT-Sn的制备：在100mL的干燥圆底烧瓶中，加入CDT-C16(510mg，0.813mmol)和50mL新蒸的四氢呋喃，冷却至-78摄氏度。缓缓滴加正丁基锂(0.81mL，2.03mmol)至反应物中，滴完后保温1小时后加入三甲基氯化锡(2.4mL，2.4mmol)，回到室温反应过夜。淬灭反应后，使用水和二氯甲烷(25×3mL)萃取，合并有机相后使用无水硫酸镁干燥后，旋干后即得白色产物620mg，产率约为80％。
1H NMR测试(600MHz,CD2Cl2,δ,ppm):6.99(s,1H),1.78(t,2H),1.31-1.15(m,28H),0.86(t,3H),0.38(t,9H)。
2FBSeCDT的制备：在20mL干燥的微波反应管中，加入CDT-Sn(1.61g，1.69mmol)、4,7-二溴-5氟-2,1,3-苯并硒二唑(1g，3.38mmol)、催化剂四(三苯基膦)钯(98mg，0.085mmol)和15mL新蒸甲苯，封盖后将反应液热到100摄氏度反应三天。冷却至室温后淬灭反应，使用水和二氯甲烷(25×3mL)萃取，合并有机相后使用无水硫酸镁干燥后，旋干后得到的粗产品使用过用层析柱提纯(石油醚:二氯甲烷＝5:1，v/v)，最后得到黑色目标产物530mg，产率约为30％。
1H NMR测试(600MHz,CDCl3,δ,ppm):7.97(s,1H),7.32(d,1H),2.00(t, 2H),1.29-1.18(m,28H),0.89(t,3H)。
19F NMR测试(564MHz,CDCl3,δ,ppm):-103.09,-103.11。
PCDTFBSe-C16的制备：在干燥的10毫升微波反应管中，加入CDT-Sn(213.9mg，0.243 mmol)，和2FBSeCDT(307mg，1.07倍量)和催化剂四(三苯基膦)钯(14.1mg，0.012mmol)。抽换气三次后加入1.6mL邻二甲苯，封盖后加热至150摄氏反应过夜。聚合反应完毕后继续向反应管中加入四(三苯基膦)钯(5mg)和2-溴噻吩(0.1mL)，在150摄氏度下反应6小时对聚合物进行封端。冷却至室温后，将反应液滴至剧烈搅拌的250mL甲醇中，过滤并收集固体后利用索氏提取器进行提纯，所采用的溶剂依次用丙酮，正己烷，二氯甲烷，氯仿。将氯仿部分过一快速硅胶柱后，在旋转蒸发仪上浓缩后再次在甲醇中析出并过滤，将聚合物进行真空干燥，最后得331mg黑绿色固体，产率约为79％。
PRF(结构式如下所示)的制备：在干燥的10毫升微波反应管中，加入CDT-Sn(300mg， 0.315mmol)，和4,7-二溴-5-氟-2,1,3-苯并硒二唑(106mg，0.294mmol)和催化剂四(三苯基膦)钯(0.05倍当量)。抽换气三次后加入1.6mL邻二甲苯，封盖后加热至150摄氏反应过夜。聚合反应完毕后继续向反应管中加入四(三苯基膦)钯(5mg)和2-溴噻吩(0.1mL)，在150摄氏度下反应6小时对聚合物进行封端。冷却至室温后，将反应液滴至剧烈搅拌的250 mL甲醇中，过滤并收集固体后利用索氏提取器进行提纯，所采用的溶剂依次用丙酮，正己烷，二氯甲烷，氯仿。将氯仿部分过一快速硅胶柱后，在旋转蒸发仪上浓缩后再次在甲醇中析出并过滤，将聚合物进行真空干燥，最后得250mg黑绿色固体。
PPCDT2FBe(结构式如下所示)的制备：在干燥的10毫升微波反应管中，加入CDT-Sn(300mg，0.315mmol)，和4,7-二溴-5,6-二氟-2,1,3-苯并硒二唑(111mg，0.294mmol)和催化剂四(三苯基膦)钯(0.05倍当量)。抽换气三次后加入1.6mL邻二甲苯，封盖后加热至150摄氏反应过夜。聚合反应完毕后继续向反应管中加入四(三苯基膦)钯(5mg)和2- 溴噻吩(0.1mL)，在150摄氏度下反应6小时对聚合物进行封端。冷却至室温后，将反应液滴至剧烈搅拌的250mL甲醇中，过滤并收集固体后利用索氏提取器进行提纯，所采用的溶剂依次用丙酮，正己烷，二氯甲烷，氯仿。将氯仿部分过一快速硅胶柱后，在旋转蒸发仪上浓缩后再次在甲醇中析出并过滤，将聚合物进行真空干燥，最后得210mg黑绿色固体，产率约为 79％。
实施例2
将实施例1所得的聚合物PCDTFBSe-C16、PRF、PCDT2FBSe进行溶解度测试：
聚合物PCDTFBSe-C16、PRF、PCDT2FBSe能够溶于常见的有机溶剂，包括三氯甲烷,四氢呋喃，氯苯，邻二氯苯等溶剂。更为重要的是，聚合物PCDTFBSe-C16、PRF、PCDT2FBSe 在这些溶剂中的溶解度均超过10mg/mL。聚合物PCDTFBSe-C16、PRF、PCDT2FBSe的溶解度测试表明，该聚合物可以采用旋涂的方式得到高质量的聚合物薄膜，可以使用溶液加工的方法制备有机薄膜晶体管。
实施例3
聚合物的分子量采用美国安捷伦科技PL-GPC 220测试，流动相为1，2，4-三氯苯，测试温度为150摄氏度，聚苯乙烯作为标样。聚合物PCDTFBSe-C16的数均分子量(Mn)为32KDa，重均分子量为62.6kDa，分子量分布系数(PDI)为2.23。
聚合物PRF的数均分子量(Mn)为21.3KDa，重均分子量为45.6kDa，分子量分布系数(PDI)为2.14。
聚合物PCDT2FBSe的数均分子量(Mn)为19.7KDa，重均分子量为38.3kDa，分子量分布系数(PDI)为1.94。
实施例4
将实施例1所得的聚合物PCDTFBSe-C16进行热重分析(TGA)。
聚合物的热失重曲线采用美国TA公司的TGA55，在氮气气氛下以5摄氏度的升温速率得到。测试的温度范围为50至650摄氏度。定义聚合物5％质量损失时对应的温度为热分解温度，聚合物PCDTFBSe-C16的TGA曲线表明，该聚合物的热分解温度为361摄氏度。如此高的热分解温度说明该聚合物具有较好的热稳定性，在器件制备过程中可以使用较高的温度进行热退火处理聚合物薄膜。
实施例5
将实施例1所得的聚合物PCDTFBSe-C16进行差示量热扫描分析(DSC)。聚合物的差示量热扫描曲线采用美国TA公司的DSC250，在氮气气氛下以5摄氏度的升温/降温速率得到。测试的温度范围为50至350摄氏度并取第二次加热/降温部分曲线。聚合物PCDTFBSe-C16 的DSC曲线表明，聚合物在50-350摄氏度没有明显的吸热或者放热峰。
实施例6
电化学循环伏安曲线由上海辰华CHI730E电化学工作站和三电极体系测量，将聚合物的氯仿溶液(5mg/mL)滴至玻碳电极成膜后作为工作电极，铂丝作为对电极，饱和Ag/AgCl 作为参比电极，六氟磷酸四丁基铵的乙氰溶液(0.1M)作为电解质溶液。扫描速度为50mV/s，氮气气氛条件测得，并使用二茂铁进行标定。聚合物薄膜的循环伏安曲线表明，其氧化起始电位为0.554伏特，还原起始电位为-0.756伏特。作为标定的二茂铁的半波电位为0.485伏特，经计算得聚合物PCDTFBSe-C16的HOMO能级为-4.87eV,LUMO能级为-3.56eV。从电化学循环伏安曲线得聚合物PCDTFBSe-C16的带隙约为1.31eV。
实施例7
聚合物PCDTFBSe-C16的溶液和薄膜吸收在美国PerkinElmer Lambda950紫外可见分光光度计上测得，测试范围为1200至300nm。聚合物在氯苯中的浓度为10-3mg/mL时，归一化的溶液吸收如图。从图中可以看出，聚合物PCDTFBSe-C16的溶液最大吸收波长为445nm和815nm,吸收边位于1030nm处。PCDTFBSe-C16的溶液吸收为典型的“dual-band”，第一个吸收带主要是由于聚合物组成单元中π→π*的跃迁引起的，第二个吸收带为D-A吸收带，即分子内电荷转移引起的吸收。聚合物PCDTFBSe-C16的薄膜(采用5mg/mL的氯苯溶液在1500rpm的转速下旋涂15秒制得)最大吸收波长相对于溶液吸收略有红移，分别为452nm 和836nm。聚合物PCDTFBSe-C16薄膜的吸收边为1084nm，对应材料的光学带隙为1.14 eV。聚合物的溶液和薄膜吸收表明，引入硒原子后材料的堆砌更加紧密。
实施例8
采用底栅底接触(BGBC)的有机薄膜晶体管器件结构表征聚合物PCDTFBSe-C16的载流子迁移率，器件结构如图10所示。其中，沟道的宽度W＝1000μm,长度L＝80μm。有机薄膜晶体管的衬底为N型重掺杂的单晶硅硅片，其上生长约200nm厚的二氧化硅作为绝缘层。清洗后，在高真空下利用金属掩膜板蒸镀一层厚约nm的作为源漏电板。进一步使用丙酮、异丙醇、去离子水洗涤，利用氮气干燥，在120摄氏度下等离子处理(最好是中文表示)15分钟。使用十八烷基三氯硅烷修饰二氧化硅绝缘层，最后在氮气条件下进行干燥。将配好的聚合物氯苯溶液(10mg/mL)经旋涂25秒成膜，转速1000rpm，成膜后在200摄氏度下退火20分钟。用Keithley4200半导体参数分析仪表征，薄膜晶体管的载流子迁移率使用饱和区通过IDS＝(W/2L)Ciμh(VG-VT)2。
通过计算聚合物PCDTFBSe-C16的空穴迁移率为0.22cm2/Vs，开关比为103，高于经典的聚合物PCDTFBT(同等条件下制备的有机薄膜晶体管器件的空穴迁移率为0.16cm2/Vs)。有机薄膜晶体管器件表明，使用硒原子取代硫原子可以提高材料的载流子迁移率。考虑到聚合物PCDTFBT在学术界和工业界的巨大成功，有理由相信聚合物PCDTFBSe高性能的有机薄膜晶体管器件中具有巨大潜力。
Claims (6)
1.一种如通式I所示的含氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物，
其中R1和R2各自独立的1～30个碳原子的烷基链、1～30个碳原子的烷氧基链、5～30个碳原子的环烷基、2～30个杂烷基链中的一种；n为区域规整性聚合物重复单元的数目，n≧6且n为整数；取代基X与Y至少有一个为氟原子。
2.根据权利要求1所述聚合物，其特征在于，所述R1、R2分别选1～30个碳原子的烷基链为甲基，乙基，丙基，丁基，戊基，己基，庚基，辛基，壬基，癸基，十一烷基，十二烷基，十六烷基，三十烷基，异丙基，异丁基，2-乙基已基，2-丁基己基，2-丁基辛基，2-己基辛基，2-己基癸基，2-已基十二烷基，2-辛基癸基，2-辛基十二烷基，2辛基十四烷基，2-辛基十六烷基，2-癸基十二烷基，2-癸基十四烷基，2-癸基十六烷基，2-十烷基十四烷基，2-十烷基十六烷基，2-十一烷基十八烷基中的一种或几种；或者为1～30个碳原子的烷氧基链、5～30个碳原子的环烷基或者2～30个杂烷基链中的一种。
3.根据权利要求1所述聚合物，其特征在于，所述聚合物为：
其中X为H，Y为F；或X为F，Y为H；其中6≤n≤600，且n为整数。
4.一种权利要求1所述的含氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物的制备方法，包括：
采用二噻吩并环戊二烯的单体与氟取代2,1,3-苯并硒二唑的单体，通过金属催化的偶联缩聚反应制备得到。
5.一种氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物薄膜，其特征在于，将权利要求1所述的聚合物通过溶液加工方法成膜得到。
6.一种权利要求1所述含氟代2,1,3-苯并硒二唑与二噻吩并环戊二烯的聚合物在有机薄膜晶体管中的应用。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060982A (zh) * | 2010-12-03 | 2011-05-18 | 华南理工大学 | 含萘[1,2-c:5,6-c]二[1,2,5]噻二唑的有机半导体材料及其应用 |
| CN102083883A (zh) * | 2008-07-02 | 2011-06-01 | 巴斯夫欧洲公司 | 基于供体/受体交替共聚物的高性能可溶液加工半导体聚合物 |
| CN103833981A (zh) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | 并[3,4-b]二噻吩-苯并二(苯并硒二唑)共聚物及其制备方法和应用 |
| CN103865044A (zh) * | 2012-12-12 | 2014-06-18 | 海洋王照明科技股份有限公司 | 含环戊二烯二噻吩和苯并二(苯并硒二唑)单元的共聚物及其制备方法和应用 |
| CN105399930A (zh) * | 2015-12-24 | 2016-03-16 | 杨荣 | 一种用于有机半导体的共轭聚合物及其制备方法 |
-
2019
- 2019-06-18 CN CN201910527754.5A patent/CN110372848A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102083883A (zh) * | 2008-07-02 | 2011-06-01 | 巴斯夫欧洲公司 | 基于供体/受体交替共聚物的高性能可溶液加工半导体聚合物 |
| CN102060982A (zh) * | 2010-12-03 | 2011-05-18 | 华南理工大学 | 含萘[1,2-c:5,6-c]二[1,2,5]噻二唑的有机半导体材料及其应用 |
| CN103833981A (zh) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | 并[3,4-b]二噻吩-苯并二(苯并硒二唑)共聚物及其制备方法和应用 |
| CN103865044A (zh) * | 2012-12-12 | 2014-06-18 | 海洋王照明科技股份有限公司 | 含环戊二烯二噻吩和苯并二(苯并硒二唑)单元的共聚物及其制备方法和应用 |
| CN105399930A (zh) * | 2015-12-24 | 2016-03-16 | 杨荣 | 一种用于有机半导体的共轭聚合物及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| MING WANG: "Fluorine substitution influence on benzo[2,1,3]thiadiazole based polymers for field-effect transistor applications", 《CHEM.COMMUN.》 * |
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