CN115490835A - 一种n型共轭聚合物及其制备方法与应用 - Google Patents
一种n型共轭聚合物及其制备方法与应用 Download PDFInfo
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- CN115490835A CN115490835A CN202110679959.2A CN202110679959A CN115490835A CN 115490835 A CN115490835 A CN 115490835A CN 202110679959 A CN202110679959 A CN 202110679959A CN 115490835 A CN115490835 A CN 115490835A
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- formula
- conjugated polymer
- type conjugated
- alkyl
- solvent
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 125000003118 aryl group Chemical group 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 229920001519 homopolymer Polymers 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 230000009471 action Effects 0.000 claims abstract description 9
- 239000012429 reaction media Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 125000002947 alkylene group Chemical group 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- -1 amino, carboxyl Chemical group 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 125000000304 alkynyl group Chemical group 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011903 deuterated solvents Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
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- 125000001118 alkylidene group Chemical group 0.000 claims 1
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- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical class OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims 1
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- 230000005540 biological transmission Effects 0.000 abstract 1
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- 229920000642 polymer Polymers 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
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- 238000000862 absorption spectrum Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- UOQACRNTVQWTFF-UHFFFAOYSA-N decane-1,10-dithiol Chemical compound SCCCCCCCCCCS UOQACRNTVQWTFF-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- WAMKWBHYPYBEJY-UHFFFAOYSA-N duroquinone Chemical compound CC1=C(C)C(=O)C(C)=C(C)C1=O WAMKWBHYPYBEJY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-LIDOUZCJSA-N ethanol-d6 Chemical compound [2H]OC([2H])([2H])C([2H])([2H])[2H] LFQSCWFLJHTTHZ-LIDOUZCJSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
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Abstract
本发明属于n型半导体材料的技术领域,公开了一种n型共轭聚合物及其制备方法与应用。方法:以溶剂为反应介质,反应单体在具有氧化性的物质的作用下发生反应,获得n型共轭聚合物。n型共轭聚合物为均聚物或共聚物,n型共轭聚合物包括一种或多种聚合单元,聚合单元为式I结构和/或式II结构。本发明的原料为具有活泼亚甲基的芳香式二酮类物质,经具有氧化性的物质作用直接聚合反应。所述反应无需贵金属催化,且对反应气氛不敏感工艺简单,成本低廉,适用于商业化应用。本发明n型共轭聚合物具有优异的电子传输能力,较高的电导率以及较好的电磁波屏蔽效果。本发明的n型共轭聚合物应用于有机光电器件中,可以实现优异的光电效果。
Description
技术领域
本发明属于n型有机半导体材料的技术领域,具体涉及一种n型共轭聚合物及其制备方法和应用。
背景技术
共轭聚合物的结构中包含了由离域的π电子组成的共轭体系,因而体现出特殊的光、电特性,引起了科学家的广泛关注。光电材料与器件所运用半导体材料,不仅具备金属或半导体的电子特性,更具备低成本、质量轻、可低温加工、易于实现大面积制备等特点,满足工业化大生产和大面积推广的要求,具有广大的商业前景。目前,共轭聚合物在有机太阳电池(OPV)、有机发光二极管(OLED)、有机场效应晶体管(OFET)以及有机热电(OTE)等领域已取得一系列令人瞩目的成果。
高性能的有机电子器件在工作时通常同时需要p型和n型两种半导体材料。PEDOT:PSS作为目前已经得到商业化应用的p型材料之一,由于具有高导电率以及可印刷加工的特点,在半导体器件中取得巨大的成功。
然而相比于发展成熟的p型材料,n型有机材料,尤其是具备高导电的有机n型共轭聚合物,则缺少相对应的合成策略。受限于n型有机半导体材料电子迁移率低、空气稳定性差,以及需要较长绝缘性烷基链以实现溶液加工等因素,发展具备高电导率以及合成简单、成本低廉、可溶液加工的n型有机半导体材料是目前研究的热点。
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮分子中含有两个强吸电子官能团,可以有效降低聚合物的最低未占据轨道(LUMO),这有利于提高聚合物的电子迁移率以及确保聚合物n型掺杂的稳定性。基于3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮的聚合物已有诸多报道,如文献(Toward High Performance n-Type ThermoelectricMaterials by Rational Modification of BDPPV Backbones.J.Am.Chem.Soc.2015,137,6979)报道了基于苯并二呋喃二酮的聚合物BDPPV,经过掺杂剂的优化,可以实现最高14S/cm的电导率;文献(High Conductivity and Electron-Transfer Validation in an n-Type Fluoride-Anion-Doped Polymer for Thermoelectrics in Air.Adv.Mater.2017,29,1606928)报道了利用四丁基氟化铵掺杂基于苯并二呋喃二酮的聚合物,并获得空气稳定性较好的n型热电材料;另外,文献(Rigid Coplanar Polymers for Stable n-TypePolymer Thermoelectrics.Angew.Chem.Int.Ed.2019,58,11390)报道了利用酸催化羟醛缩合反应聚合,在避免使用贵金属催化剂的同时,获得了空气稳定同时具备高电导率的基于苯并二呋喃二酮的聚合物LPPV。
然而由于3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮优异的平面性,目前多数基于该单元的聚合物通常需要在共聚单元上引入较长的烷基链以保证其在有机溶剂中的溶解性;同时需要使用外加掺杂剂(如N-DMBI等)进行掺杂以获得高导电率,难以在空气中保持长期稳定。
而对于二酮类稠环化合物,文献(Synthese,Charakterisierung undHalbleitereigenschaften eines polymeren Indopheninhomologen.Macro.Chem.Phys.1975,176,333)公开了一种在硫酸催化的条件下可以进行脱水聚合,形成具备导电性的P型醌式聚合物;专利WO 2014/071524公布了含稠环结构的聚合物,并介绍其作为有机半导体在OFET中的应用;专利US 2019/0048015 A1公开了一类可不使用贵金属催化的近红外有机半导体聚合物。
另外,专利申请CN108699073公开了一种半导体聚合物及其合成方法,该半导体聚合物的结构为然而,该聚合物在制备的过程中所采用的原料之一为四酮A为一类经氧化反应后的中间体。合成该中间体需要耗费额外的工艺成本,导致合成路线不经济,难以商业化。同时部分四酮A结构,如在现有技术下实际上并未公开制备方法,难以通过已公开的文献获得适合于商业化的聚合物制备方法。
同时上述公开的聚合物中,并不涉及任何n型导电的性质,或者相关数据并不理想。且所公开的聚合物结构均含有烷基侧链,不含烷基链情况下仍可实现溶液加工的聚合物结构以及制备方法并未报道。
综上,如何开发一类结构简单、合成简易、成本低廉且可溶液加工的n型高导电共轭聚合物,并经过适用商业化的制备方法直接合成;同时应用于有机光电领域,并且实现理想的光电效果,是亟需解决的问题。
发明内容
为了克服现有技术的缺点和不足,本发明的目的在于提供一种n型共轭聚合物及其制备方法。本发明的方法中所采用的原料为具有活泼亚甲基的芳香式二酮类物质,在氧化剂存在的条件下,聚合反应直接得到n型共轭聚合物。所述反应无需贵金属催化,且对反应气氛不敏感,工艺简单,成本低廉,适用于商业化应用。通过本发明的方法所获得的n型共轭聚合物在一般的有机溶剂中具有良好的溶解性,可以实现溶液加工。同时,该n型共轭聚合物应用于有机光电器件中,可以实现优异的光电效果。
本发明的另一目的在于提供由上述方法制备得到的n型共轭聚合物的应用。所述n型共轭聚合物应用于有机光电器件中。具体的,本发明的n型共轭聚合物应用于有机太阳电池中,作为电子传输层;或者用作热电材料,或电磁屏蔽材料。
本发明的目的通过以下技术方案实现:
一种n型共轭聚合物为均聚物或共聚物,n型共轭聚合物包括一种或多种聚合单元,聚合单元为式I结构和/或式II结构:
进一步地,n型共轭聚合物,其结构具体为式I、式II、式I与式II组成的结构,式I与式I组成的结构、或者式II与式II组成的结构;其中式I与式I组成的结构中式I与式I不同,式II与式II组成的结构中式II与式II不同;式I与式II组成的结构中含有1个或多个式I,含有1个或多个式II,式I相同或不同,式II相同或不同。
式I中,X独立地选自O、S、Se、Te或N-R1;
所述R1选自氢原子、烷基、亚烷基(R′-Cn′H2n′,R′为取代基,Cn′H2n′为亚烷基)、烷基衍生物、亚烷基衍生物的一种或多种;
所述烷基衍生物是指烷基上的一个或多个碳,被氧原子、氨基、砜基、羰基、芳基、烯基、炔基、酯基、氰基、硝基的一个或多个取代;
和/或
所述烷基衍生物上的一个或多个氢,被卤素、羟基、氨基、羧基、氰基、硝基、芳基、烯烃基、炔烃基的一个或多个取代;
n为正整数;
所述M为n型共轭聚合物结构中的共轭部分,所述M的结构选自芳环、芳杂环、稠合芳环、稠合芳杂环的一种;
所述芳环是指拥有共轭平面环体系,原子间成键是被离域π电子云覆盖的环状结构。如苯环及其衍生物。
所述芳杂环是指拥有共轭平面环体系,原子间成键是被离域π电子云覆盖的;且构成环的原子除碳原子外,还至少含有一个杂原子(如N、O、S等)的环状结构。如噻吩、呋喃、吡咯等。
所述稠合芳环是指拥有共轭平面环体系,原子间成键是被离域π电子云覆盖的两个或多个芳香环稠合(即共用环边)而成的结构。如萘、蒽及其衍生物。
所述稠合芳杂环是指拥有共轭平面环体系,原子间成键是被离域π电子云覆盖的两个或多个芳香环稠合而成的结构,并且至少一个环中的构成原子除碳原子外,还至少含有一个杂原子(如N、O、S等)。如喹啉、吲哚及其衍生物。
本发明中,所述n型高导电共轭聚合物具有多种共振形式。以M为苯环结构时为例,包括但不限于以下共振形式:
为方便起见,本发明的内容中均以第一种共振形式进行表达。
进一步地,所述M的结构选自以下结构:
其中,所述X2-X4独立地选自O、S、Se、Te或N-R1;
所述R2-R5独立地选自氢原子、羟基、硝基、卤素、氰基、硝基、烷基、烷基衍生物的一种或多种;
所述烷基衍生物上的一个或多个碳,被氧原子、氨基、砜基、羰基、芳基、烯基、炔基、酯基、氰基、硝基的一个或多个取代;
和/或
所述烷基衍生物上的一个或多个氢,被卤素、羟基、氨基、羧基、氰基、硝基、芳基、烯烃基、炔烃基的一个或多个取代。
进一步地,所述n型共轭聚合物为均聚物或共聚物,
当所述n型共轭聚合物为均聚物时,所述n型共轭聚合物的结构选自如下结构的一种:
当所述n型共轭聚合物为共聚物时,所述n型共轭聚合物包括至少两种聚合单元;
所述每个聚合单元的结构独立地选自如下结构:
其中
所述R1选自氢原子、烷基、烷基衍生物的一种或多种;
所述烷基衍生物上的一个或多个碳,被氧原子、氨基、砜基、羰基、芳基、烯基、炔基、酯基、氰基、硝基的一个或多个取代;
和/或
所述烷基衍生物上的一个或多个氢,被卤素、羟基、氨基、羧基、氰基、硝基、芳基、烯烃基、炔烃基的一个或多个取代;
所述n1-n6独立地为正整数;
所述M为n型共轭聚合物结构中的共轭部分,所述M的结构选自芳环、芳杂环、稠合芳环、稠合芳杂环的一种。
上述结构中R1、M如前面式I、式II所定义。
所述n型共轭聚合物的制备方法,包括如下步骤:
以溶剂为反应介质,反应单体在具有氧化性的物质的作用下发生反应,获得n型共轭聚合物。
所述反应单体为
结构中M,X如上述n型共轭聚合物所定义。
当n型共轭聚合物为均聚物时,反应单体为同一种结构的化合物;
当n型共轭聚合物为共聚物时,反应单体为不同结构的化合物;即反应单体为式I′化合物中两种以上或II′化合物中两种以上;或者反应单体为式I′化合物与II′化合物;
当n型共轭聚合物为共聚物时,n型共轭聚合物的制备方法,还可以为:
1)将不同的反应单体分别在溶剂中以及具有氧化性的物质的作用下发生反应,分别获得不同聚合单元;
2)以溶剂为反应介质,步骤1)中不同聚合单元在具有氧化性的物质的作用下进一步发生共聚反应,获得n型共轭聚合物。
不同聚合单元优选为以下结构中两种以上:
当n型共轭聚合物为共聚物时,共聚物可以为二元共聚物或多元共聚物,不同的聚合单元之间可以相互聚合,从而形成新的长链共聚物。共聚物的结构,可以但不限于如下结构中的一种:
所述具有氧化性的物质选自有机类具有氧化性的物质、无机类具有氧化性的物质的一种或多种的混合物。
进一步地,所述具有氧化性的物质为氧气、过氧化物、金属卤化物、过硫酸盐、过硼酸盐、次卤酸盐、亚卤酸盐、醌类化合物、过苯甲酸类化合物中的一种以上。
具体地,上述具有氧化性的物质可以但不限于:如氧气、过氧化氢、过氧化钠、过氧化钾、过氧化钙、过氧化锌、过氧化铜、硝酸铁、硝酸锌、硝酸镍、硝酸铝、硝酸镁、硝酸铵、氟化铁、氯化铁、溴化铁、碘化铁、高氯酸钠、高氯酸钾、高溴酸钠、高溴酸钾、高碘酸钠、高碘酸钾、过氯酸钾、过氯酸钠、过溴酸钾、过溴酸钠、过氯酸镁、过硫酸钠、过硫酸钾、过硫酸镁、过硫酸锌、过硫酸铁、过硫酸铜、过硫酸钙、过硼酸钾、过硼酸锌、过硼酸镁、过硼酸钙、次氟酸钠、次氟酸钾、次氯酸钠、次氯酸钾、次氯酸铁、次氯酸铜、次溴酸钠、次溴酸钾、次碘酸钠、次碘酸钾、亚氯酸钠、亚氯酸钾、亚氯酸铁、亚溴酸钠、亚溴酸钾、亚碘酸钠、亚碘酸钾、苯醌及其衍生物、萘醌及其衍生物、蒽醌及其衍生物、菲醌及其衍生物、过苯甲酸及其衍生物中的一种以上。
所述溶剂选自溶剂1,或溶剂2,或溶剂1和溶剂2的混合物;
所述溶剂1选自水、腈类溶剂、芳香族类溶剂、脂环烃类溶剂、脂环烃类溶剂、卤化烃类溶剂、醇类溶剂、醚类溶剂、酯类溶剂、砜类溶剂、酮类溶剂、酰胺类溶剂的一种或多种的混合物;
所述溶剂2为所述溶剂1的氘代溶剂。
具体地,上述溶剂1优选为极性溶剂,可以但不限于为:如四氢呋喃、甲基四氢呋喃、二氯甲烷、氯仿、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲苯、二甲苯、三甲苯、氯苯、二氯苯、三氯苯、甲醇、乙醇、丙醇、乙二醇、异丁醇、丙二醇、乙腈、甲酸、乙酸、丙酸、三氟乙酸、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、二甲基乙酰胺、丙酮、丁酮、环己酮、甲基丁酮、甲醚、乙醚、丙醚、吡啶、苯酚、N-甲基吡咯烷酮、乙二醇单甲醚、三甘醇单甲醚、三乙胺、四甲基乙二胺、三辛胺、苯胺、六甲基磷酸三胺的一种以上。
具体地,上述溶剂2为上述溶剂1所相对应的氘代溶剂,例如,溶剂2可以但不限于:氘代氯仿、氘代氯苯、氘代乙醇等。
优选地,所述溶剂选自溶剂1。
上述n型共轭聚合物在有机光电器件中的应用。所述n型共轭聚合物在电子传输层中应用。所述电子传输层包括上述n型共轭聚合物。
所述n型共轭聚合物在热电材料中的应用。所述热电材料包括上述n型共轭聚合物。
所述n型共轭聚合物在电磁屏蔽材料中的应用。所述电磁屏蔽材料包括上述n型共轭聚合物。
与现有技术相比,本发明具有如下优点及有益效果:
1.本发明所得的n型共轭聚合物原料为具有活泼亚甲基的芳香式二酮类物质,在具有氧化性的物质存在的条件下,聚合反应直接得到。所述反应无需贵金属催化,且对反应气氛不敏感,工艺简单,成本低廉,适合大规模商业化应用;所得产物溶解性优异,适用于溶液加工型的有机光电器件中。
2.本发明所得的n型共轭聚合物应用于有机太阳电池中,可作为电子传输层,相比于传统的电子传输层ZnO,具有更加优异的电子传输能力,从而获得更为优异的光电转换效率。
3.本发明所得的n型共轭聚合物,可作为热电材料,在不使用额外掺杂剂的情况下,电导率最高可达到1060S/cm,应用于热电材料中可获得超过130μWm-1K-2的功率因子。
4.本发明所得的n型共轭聚合物,可作为电磁屏蔽材料,可以在2mm厚度下屏蔽超过96%的电磁波,且具有宽频相应功能。
附图说明
图1中(a)、(b)和(c)分别为实施例1、实施例6和实施例7中的n型共轭聚合物,在溶液和薄膜状态下的吸收光谱图;
图2为测试例2中分别基于ZnO和实施例1的作为电子传输层的有机太阳电池器件的J-V曲线图;
图3中(a)为实施例2中的n型共轭聚合物的热电压差变化趋势图,图3中(b)为实施例2中的n型聚合物的热电压差随温度的变化趋势拟合图;
图4为实施例1和实施例2的n型共轭聚合物的电导率-Seebeck系数-功率因子性能图;
图5中(a)为实施例2的n型共轭聚合物在不同频率的电磁屏蔽比例图;图5中(b)为实施例2的聚合物在不同频率的电磁屏蔽效能图。
具体实施方式
为了更清楚地说明本发明的技术方案,列举如下实施例。实施例中所出现的原料、反应和后处理手段,除非特别声明,均为市面上常见原料,以及本领域技术人员所熟知的技术手段。
本发明实施例中的原料之一,3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮,按照文献(A BDOPV-Based Donor–Acceptor Polymer for High-Performance n-Type andOxygen-Doped Ambipolar Field-Effect Transistors.Adv.Mater.2013,25(45),6589)进行制备;实施例中的具有氧化性的物质采用杜醌或者辅酶Q10,采购自上海毕得医药科技股份有限公司。
本发明采用原料芳香式二酮类物质和具有氧化性的物质的用量可以为任意比例,如:摩尔比为1:1、0.01:1、1:0.01等,芳香式二酮类物质和具有氧化性的物质的用量不为0。
原料芳香式二酮类物质在具有氧化性的物质的作用下进行反应时,反应温度没有特别的要求,只要反应能进行即可,如:反应的温度为常温~150℃。
反应完后,进行后续处理;所述后续处理为采用常规后续处理方式,如:过滤,透析;或者过滤,洗涤,干燥;又或者在沉淀剂中沉淀。
实施例1:n型共轭聚合物NCPO的制备
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol),和杜醌(1mmol),溶于2ml的DMF中,经真空脱气后,充入氮气进行保护。在氮气氛围、100℃下搅拌反应4h。然后将所得粗产物用DMF稀释至约10mg/ml后,利用0.45μm孔径的聚四氟乙烯滤头过滤,所得滤液采用旋转蒸发仪浓缩,利用透析袋(截断分子量=10kDa)在DMF溶液中透析3天,得到产物NCPO。所得产物NCPO经以DMF为流动相的凝胶渗透色谱测试,分子量Mn=14kDa,PDI=4.02。
实施例2:n型共轭聚合物NCPO的制备
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol),和杜醌(1mmol),溶于2ml的DMSO中,经真空脱气后,充入氮气进行保护。在氮气氛围、100℃下搅拌反应1h。然后将所得粗产物用DMSO稀释至约10mg/ml后,利用0.45μm孔径的聚四氟乙烯滤头过滤,所得滤液采用旋转蒸发仪浓缩,利用透析袋(截断分子量=15kDa)在DMSO溶液中透析3天,得到产物NCPO。所得产物NCPO经以DMSO为流动相的凝胶渗透色谱测试,分子量Mn=220kDa,PDI=2.02。
实施例3:n型共轭聚合物NCPO的制备
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol),和辅酶Q10(1mmol),溶于2ml的DMF中,经真空脱气后,充入氮气进行保护。在氮气氛围、100℃下搅拌反应4h。然后将所得粗产物用DMF稀释至约10mg/ml后,利用0.45μm孔径的聚四氟乙烯滤头过滤,所得滤液采用旋转蒸发仪浓缩,利用透析袋(截断分子量=10kDa)在DMF溶液中透析3天,得到产物NCPO。所得产物NCPO经以DMF为流动相的凝胶渗透色谱测试,分子量Mn=21kDa,PDI=1.98。
实施例4:n型共轭聚合物NCPO的制备
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol),和辅酶Q10(10mmol),溶于4ml的DMF中,经真空脱气后,充入氮气进行保护。在氮气氛围、100℃下搅拌反应2h。然后将所得粗产物用DMF稀释至约15ml后,利用0.45μm孔径的聚四氟乙烯滤头过滤,所得滤液采用旋转蒸发仪浓缩,利用透析袋(截断分子量=10kDa)在DMF溶液中透析7天,得到产物NCPO。所得产物NCPO经以DMF为流动相的凝胶渗透色谱测试,分子量Mn=76kDa,PDI=1.72。
实施例5:n型共轭聚合物NCPO的制备
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol),和氧化剂杜醌(0.1mmol),溶于2ml的DMSO中。在100℃下搅拌反应24h。然后将所得粗产物用DMSO稀释至约10ml后,利用0.45μm孔径的聚四氟乙烯滤头过滤,所得滤液采用旋转蒸发仪浓缩,利用透析袋(截断分子量=15kDa)在DMSO溶液中透析3天,得到产物NCPO。所得产物NCPO经以DMSO为流动相的凝胶渗透色谱测试,分子量Mn=23kDa,PDI=1.20。
实施例6:n型共轭聚合物NCPS的制备
(1)将苯并二噻吩(23mmol)溶解于无水四氢呋喃中(300ml)后,降温至-78℃,在90min内缓慢加入正丁基锂(2.5M的正己烷溶液,25.8ml,64.4mmol),于-78℃下搅拌3h后升温至0℃,加入硼酸三正丁酯(60mmol),搅拌1h后逐渐升到室温25℃,继续搅拌8h。利用旋转蒸发仪浓缩溶液至200ml,加入0.5M盐酸200ml,过滤得到粗产物。将粗产物利用四氢呋喃/正己烷沉淀出产物,并用冰甲苯洗涤,干燥固体(产率=61%),用于下一步反应。
(2)将上一步所的固体(7.5mmol)溶解于在四氢呋喃(100ml)中,于0℃下加入2.5ml过氧化氢水溶液(30wt%),于室温下搅拌6h。利用旋转蒸发仪除去溶剂后,利用硅胶填充层析色谱柱(200-300目),以乙酸乙酯:石油醚=4:1为洗脱剂提纯产物,得到固体用正己烷和甲醇洗涤,得到3,7-二氢苯并[1,2-b:4,5-b']二噻吩-2,6-二酮(产率=53%)。1HNMR(CDCl3,500MHz)δppm:7.31(s,2H),3.98(s,4H)。
(3)3,7-二氢苯并[1,2-b:4,5-b']二噻吩-2,6-二酮(1mmol),和杜醌(1mmol),溶于2ml的DMF中,经真空脱气后,充入氮气进行保护。在氮气氛围、120℃下搅拌48h,将溶液稀释至约10mg/ml后,利用0.45μm孔径的聚四氟乙烯滤头过滤。将溶液利用旋转蒸发仪浓缩,利用透析袋(截断分子量=5kDa)在DMF溶液中透析三天,所得溶液利用DMF定容至15mg/ml后直接用于后续使用。经以DMF为流动相的凝胶渗透色谱测试分子量,Mn=8.9kDa,PDI=1.18。
实施例7:n型共轭聚合物NCP的制备
(1)在500ml圆底反应烧瓶中加入150ml甲醇,在冰盐水浴的条件下缓慢同时加入醋酸乙烯酯(0.64mol)以及液溴(0.636mol),滴加过程中体系温度控制在5℃以下。滴加完成后,逐渐升至室温反应12h。将混合溶液倒入冰水(200ml)中,分批次加入NaHCO3(0.67mol),并搅拌30min。待不再产生气泡后,加入二氯甲烷(3×200ml)萃取,合并有机相,用NaCl水溶液洗涤(3×100ml)。经无水硫酸镁干燥后,利用旋转蒸发仪除去低沸点溶剂,所得无色液体直接用于下一步反应。
(2)将所得无色液体加入250ml圆底反应瓶中,在冰浴条件下,分批次加入无水叔丁醇钾(0.64mol),升至室温搅拌10h后,蒸馏收集,得到叔丁醇以及1,1-二甲氧基乙烯的混合溶液,直接用于下一步反应。
(3)在500ml圆底烧瓶中,加入氨基钠(0.73mol),加入对二溴苯(0.12mol)以及150ml无水四氢呋喃。加入上一步所得全部溶液后,在80℃下搅拌8h。利用旋转蒸发仪除去易挥发性溶剂,所得粘稠棕色固体以乙酸乙酯:石油醚=1:5为洗脱剂,利用硅胶填充层析色谱柱提纯。所得粗产物使用正己烷洗涤后,用乙醇/水重结晶得到白色固体三环[6.2.0.03,6]癸-1,3(6),7-三烯-4,9-二酮(产率=12%)。1H NMR(CDCl3,500MHz)δppm:7.84(s,2H),4.04(s,4H)。
(4)三环[6.2.0.03,6]癸-1,3(6),7-三烯-4,9-二酮(1mmol),和杜醌(1mmol),溶于2ml的DMSO中,经真空脱气后,充入氮气进行保护。在氮气氛围下,120℃下搅拌48h,将溶液稀释至约10mg/ml后,利用0.45μm孔径的聚四氟乙烯滤头过滤。将溶液利用旋转蒸发仪除去溶剂,并依次用水(10ml)、四氢呋喃(20ml)和乙腈(20ml)洗涤所得固体,并经过真空干燥得到产物NCP。
实施例8:n型共轭聚合物NCPN的制备
(1)将1,4-环己二酮(50.0mmol)溶解于500mL乙醇中,向其中加入正己胺(100mmol)。将所得混合物在空气下常温搅拌4h。通过减压蒸馏除去溶剂得到粗产物,并通过柱层析色谱纯化(石油醚:二氯甲烷:乙酸乙酯=10:10:1),得到灰黄色固体状的化合物(产率=54.7%)。1H NMR(CDCl3,500MHz)δppm:6.54(s,4H),3.15(br,2H),3.03(tr,4H),1.55-1.60(m,4H),1.24-1.40(m,12H),0.83-0.89(m,6H)。
(2)在0℃下向氯乙酰氯(3.56mmol)的THF(5mL)溶液中逐滴滴加上述灰黄色固体状的化合物(1.19mmol)和4-(二甲氨基)吡啶(DMAP)(1.11mmol)的THF(10ml)溶液。搅拌1小时后,加入50mL水淬灭反应,过滤收集不溶物。将收集的固体用水和甲醇洗涤后,真空干燥,得到白色固体状的产物(产率=62.7%)。1H NMR(CDCl3,500MHz)δppm:7.32(s,4H),3.82(s,4H),3.27(t,4H),1.53-1.55(m,4H),1.26-1.32(m,12H),0.87-0.88(m,6H)。
(3)在氩气保护下,将上述白色固体状的产物(11.6mmol)和无水氯化铝(81.5mmol)的混合物于190℃加热20分钟。冷却后,加入冰水淬灭反应,过滤收集沉淀。用水和甲醇洗涤后,干燥固体得到粗产物,通过柱层析色谱纯化(二氯甲烷∶乙酸乙酯=10∶1),得到白色固体状的1,5-二己基-5,7-二氢-1H,3H-吡咯并[2,3-f]吲哚-2,6-二酮(产率=66.1%)。1H NMR(CDCl3,600MHz)δppm:6.78(m,2H),3.68(m,4H),3.55(m,4H),1.61-1.69(m,4H),0.98-1.48(m,12H),0.88-0.89(m,6H)。
(4)将上述1,5-二己基-5,7-二氢-1H,3H-吡咯并[2,3-f]吲哚-2,6-二酮(1mmol),和杜醌(1mmol),溶于2ml的DMSO中。在氮气氛围下,120℃下搅拌48h,将溶液稀释至约10mg/ml后,利用0.45μm孔径的聚四氟乙烯滤头过滤。将所得溶液利用旋转蒸发仪除去溶剂,并依次用水(10ml)、四氢呋喃(20ml)和乙腈(20ml)洗涤所得固体,并经过真空干燥得到产物NCPN(产率=48%)。
实施例9 n型共轭聚合物NCPO的制备
3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(1mmol),溶于2ml的DMF中,然后持续通入空气。在100℃下搅拌反应72h。然后将所得粗产物用DMF稀释至约10mg/ml后,利用0.45μm孔径的聚四氟乙烯滤头过滤,所得滤液采用旋转蒸发仪浓缩,利用透析袋(截断分子量=5kDa)在DMF溶液中透析3天,得到产物NCPO。所得产物NCPO经以DMF为流动相的凝胶渗透色谱测试,分子量Mn=8kDa,PDI=1.98。
实施例10 一种n型共轭聚合物NCPO0.5-NCPS0.5的制备
将3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(0.5mmol)以及3,7-二氢苯并[1,2-b:4,5-b']二噻吩-2,6-二酮(0.5mmol),溶于2ml的六甲基磷酸三胺(HMPA)中,加入杜醌(1mmol)。在100℃下搅拌反应22h。然后将所得溶液逐渐缓慢滴加于200mL二氯甲烷中,过滤收集其中沉淀,得到产物NCPO0.5-NCPS0.5。所得产物经以DMSO为流动相的凝胶渗透色谱测试,分子量Mn=12kDa,PDI=2.01。
实施例11 一种n型共轭聚合物NCPO0.7-NCPN0.3的制备
将3,7-二氢苯并[1,2-b:4,5-b']二呋喃-2,6-二酮(0.7mmol)以及1,5-二己基-5,7-二氢-1H,3H-吡咯并[2,3-f]吲哚-2,6-二酮(0.3mmol),溶于2ml的六甲基磷酸三胺(HMPA)中,加入双氧水(1mmol,30wt%的水溶液)。在100℃下搅拌反应20h。然后将所得溶液逐渐缓慢滴加于200mL二氯甲烷中,过滤收集其中沉淀,得到产物NCPO0.7-NCPN0.3。所得产物经以DMSO为流动相的凝胶渗透色谱测试,分子量Mn=2.8kDa,PDI=1.08。
实施例12 一种n型共轭聚合物NCPS0.5-NCPN0.5的制备
将3,7-二氢苯并[1,2-b:4,5-b']二噻吩-2,6-二酮(0.5mmol)以及1,5-二己基-5,7-二氢-1H,3H-吡咯并[2,3-f]吲哚-2,6-二酮(0.5mmol),溶于2ml的六甲基磷酸三胺(HMPA)中,加入三氯化铁(1mmol)。在100℃下搅拌反应72h。然后将所得溶液逐渐缓慢滴加于200mL二氯甲烷中,过滤收集其中沉淀,得到产物NCPS0.5-NCPN0.5。所得产物经以DMSO为流动相的凝胶渗透色谱测试,分子量Mn=3.0kDa,PDI=1.11。
图1中(a)、(b)和(c)分别为实施例1、实施例6和实施例7中的n型共轭聚合物,在溶液和薄膜状态下的吸收光谱图。从图中可以看出,制备的n型共轭聚合物在近红外区具有宽而强的吸收,这与其n型极化子相对应,体现出了显著的n型共轭聚合物的行为。这说明了本发明的制备方法在不使用常用n型掺杂剂的情况下(如N-DMBI),可以实现n型聚合物的原位掺杂,获得导电n型聚合物。
测试例1
分别将实施例1和2所得的n型共轭聚合物,用DMF(针对实施例1的NCPO)和DMSO(针对实施例2的NCPO)定容至溶质浓度为15mg/ml,然后将上述溶液分别旋涂成膜,待膜干燥后,利用四足探针法测量薄膜电导率。具体步骤为:
将石英玻璃片依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇作清洗溶剂在超声清洗仪洗涤,洗涤完后用氮气吹干表面,并用红外灯烘干,之后置于恒温烘箱中备用。使用前,将玻璃片在等离子体刻蚀仪中以等离子体轰击10min。
完成玻璃片的准备后,将其放在加热台上,110℃加热后转移至旋转匀胶仪(KW-4A)上,用以上制备的n型共轭聚合物高速旋涂(共轭聚合物溶液的质量浓度为15mg/ml),并同时用台阶仪实测监控膜的厚度。成膜完成后,利用四足探针电导率测试仪(RTS-8型四探针测试仪)测试其方阻,并计算电导率。所得结果如表1所示。
表1实施例1-2的n型共轭聚合物的电导率测试
共轭聚合物 | 方阻(Ω/□) | 厚度(nm) | 导电率(S/cm) |
实施例1 | 360 | 54 | 514 |
实施例2 | 180 | 68 | 817 |
从表1可知,本发明制备的共轭聚合物具有高的导电率。
测试例2
将实施例1中所制备的n型共轭聚合物,作为电子传输层,应用于有机太阳电池中,并测试相关的器件数据。作为对比,同时将ZnO作为电子传输层,在器件结构相同的实验条件下进行测试。有机太阳电池器件的制备采用常规工艺,其制备过程,均在氧气和水含量低于1ppm的手套箱中进行。
有机太阳电池结构为:ITO(100nm)/实施例1所制备的NCPO(或ZnO)(50nm)/活性层(PM6:Y6=1:1.5,m/m共混,并加入1wt%的二碘辛烷)(120nm)/氧化钼(60nm)/银电极(60nm)。
其中,单个器件有效面积为0.0516cm2。
ZnO采购自Sigma-Aldrich公司,型号为544906;
PM6和Y6采购自VAC公司,PM6和Y6的结构式如下:
模拟太阳光的能量在测试前利用经过美国国家可再生能源实验室(NREL)校准的硅光电二极管和一个KG5滤波器校正为100mW/cm2。器件的能量转换效率在标准太阳光谱AM1.5太阳模拟器(型号91192,Oriel,USA)下测得,分别用Keithley 2410和Keithley 236数字源表记录太阳电池器件的电流-电压(J-V)特性。
图2为分别基于ZnO和实施例1的作为电子传输层的有机太阳电池的J-V曲线图,可以看出,后者的短路电流明显优于前者。所得器件的光电转换效率如表2所示。
表2基于不同界面层的有机太阳电池性能
从表2可以看出,基于实施例1所制备的NCPO作为电子传输层的有机太阳电池,其短路电流和填充因子两个参数,比基于ZnO作为电子传输层的有机太阳电池数据更为理想,这也导致了最终的光电转换效率更高。
测试例3
对实施例1-2中所得的NCPO进行热电测试。
材料的热电性能常用热电优值(ZT)来描述,具体公式如下:
ZT=S2σT/κ;
其中S代表Seebeck系数,σ代表电导率,κ代表热导率,T代表器件工作时的温度。对于有机材料而言,其热导率远低于无机材料,因此常用功率因子(PF)来描述有机材料的热电性能,其中PF=S2σ。
在该测试例中我们以实施例1-2所制备的n型共轭聚合物为例,利用滴涂法在玻璃基底上制备薄膜,测试其电导率和Seebeck系数,表征其热电性能。电导率测试采用四探针测试法。
将玻璃基底依次用去离子水、异丙醇清洗后,用氮气吹干表面。将玻璃在等离子体刻蚀仪中以等离子体轰击5min。然后将不同n型共轭聚合物溶液滴涂于基底上,并于80℃退火15min后测量电导率。电导率测试结果如表3所示。
表3利用滴涂法制备薄膜的电导率
共轭聚合物 | 实施例1 | 实施例2 |
电导率(S/cm) | 720 | 1060 |
Seebeck系数测试器件加工方法与电导率测试的加工方法相似,使用玻璃作为基底,利用光刻方法得到金电极作为测试电极。将玻璃基底依次用去离子水、异丙醇清洗后,用氮气吹干表面。将玻璃在等离子体刻蚀仪中以等离子体轰击5min。然后将不同n型共轭聚合物溶液滴涂于基底上,并于80℃退火15min。
将器件两端放置于温度梯度场中,图3中(a)为实施例2中的n型共轭聚合物的热电压差变化趋势图,图3中(b)为实施例2中的n型聚合物的热电压差随温度的变化趋势拟合图。通过器件两端温差的变化测试对应的温差电动势,进而测得Seebeck系数。从图3中a-b上可以看出,本发明实施例的聚合物在微弱的温差下,展示出n型聚合物的Seebeck效应,并产生超过30μV/K的温差电动势。
图4为实施例1和实施例2的电导率-Seebeck系数-功率因子性能图,其中功率因子由PF=S2σ所得。由上述测试可以得到室温下功率因子最大为139.5μWm-1K-2,在现有n型共轭聚合物中处于较高水平。相关数据如表4所示。
表4利用滴涂法制备薄膜的Seebeck系数
共轭聚合物 | 实施例1 | 实施例2 |
Seebeck系数(μV/K) | -31.48±0.16 | -36.28±1.88 |
功率因子(μWm<sup>-1</sup>K<sup>-2</sup>) | 77.5 | 139.5 |
测试例4
为了本发明中的聚合物在电磁屏蔽上的应用,采用同轴法和波导法在1-18GHz波段,对实施例2中的NCPO进行介电常数以及电磁屏蔽性能测试。将实施例2中的NCPO的实验样品粉末与石蜡按照50%的重量比共混研磨后所得粉末材料,利用模具压制成外径7mm、内径3.04mm、厚2mm的同轴环。将样品放置于波导管中。主机采用DR-S01矢量网络分析仪,通过网络分析仪测试出样品的S参数,然后使用S参数根据文献(Review of ScientificInstruments.2003,74,1098-1102)计算得到薄膜样品的反射率、吸收率参数,进而得到薄膜样品的电磁屏蔽性能。
实施例2中的NCPO的粉末材料的电磁屏蔽效率与吸收占比如图5(a)所示,其在1-18GHz的宽屏范围内均可实现超过96%的电磁波屏蔽,其中约40%的电磁波被粉末材料所吸收。图5中(b)为实施例2的聚合物在不同频率的电磁屏蔽效能图。图5中(b)显示了该粉末材料对电磁波的屏蔽效能超过20dB,展现出对宽频电磁波优异的屏蔽性能。其中材料对电磁波的吸收作用对应的吸收屏蔽效能超过15dB,样品表面的反射作用对应的反射屏蔽效能平均值为4.2dB。因此,NCPO可以实现宽频段优异的电磁屏蔽,在电磁屏蔽上的应用上具有良好的应用潜力。
以上测试例说明本发明中的n型共轭聚合物在各种有机光电器件中均有广泛的应用。
Claims (10)
2.根据权利要求1所述n型共轭聚合物的制备方法,其特征在于:
R1中,所述烷基衍生物是指烷基上的一个或多个碳,被氧原子、氨基、砜基、羰基、芳基、烯基、炔基、酯基、氰基、硝基的一个或多个取代;
和/或
所述烷基衍生物上的一个或多个氢,被卤素、羟基、氨基、羧基、氰基、硝基、芳基、烯烃基、炔烃基的一个或多个取代;
所述M独自选自以下结构:
其中,所述X2-X4独立地选自O、S、Se、Te或N-R1;N-R1中R1选自氢原子、烷基、亚烷基、烷基衍生物、亚烷基衍生物的一种或多种;
所述R2-R5独立地选自氢原子、羟基、硝基、卤素、氰基、硝基、烷基、烷基衍生物的一种或多种;
上述M的结构中,芳环中的虚线---表示此处与相邻的五元环或四元环的相互稠合即共用环边;
所述具有氧化性的物质选自有机类具有氧化性的物质、无机类具有氧化性的物质的一种或多种;
所述溶剂选自溶剂1,或溶剂2,或溶剂1和溶剂2的混合物;
所述溶剂1选自水、腈类溶剂、芳香族类溶剂、脂环烃类溶剂、脂环烃类溶剂、卤化烃类溶剂、醇类溶剂、醚类溶剂、酯类溶剂、砜类溶剂、酮类溶剂、酰胺类溶剂的一种或多种;
所述溶剂2为溶剂1的氘代溶剂。
3.根据权利要求2所述n型共轭聚合物的制备方法,其特征在于:
所述具有氧化性的物质为氧气、过氧化物、金属卤化物、过硫酸盐、过硼酸盐、次卤酸盐、亚卤酸盐、醌类化合物、过苯甲酸类化合物中的一种以上;
所述溶剂1为四氢呋喃、甲基四氢呋喃、二氯甲烷、氯仿、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲苯、二甲苯、三甲苯、氯苯、二氯苯、三氯苯、甲醇、乙醇、丙醇、乙二醇、异丁醇、丙二醇、乙腈、甲酸、乙酸、丙酸、三氟乙酸、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、二甲基乙酰胺、丙酮、丁酮、环己酮、甲基丁酮、甲醚、乙醚、丙醚、吡啶、苯酚、N-甲基吡咯烷酮、乙二醇单甲醚、三甘醇单甲醚、三乙胺、四甲基乙二胺、三辛胺、苯胺、六甲基磷酸三胺中的一种以上;
所述溶剂2为溶剂1所相对应的氘代溶剂。
4.根据权利要求1所述n型共轭聚合物的制备方法,其特征在于:
n型共轭聚合物的结构为式I、式II、式I与式II组成的结构、式I与式I组成的结构或者式II与式II组成的结构;其中式I与式I组成的结构中式I与式I不同,式II与式II组成的结构中式II与式II不同;式I与式II组成的结构中含有1个或多个式I,含有1个或多个式II,式I相同或不同,式II相同或不同;
当n型共轭聚合物为均聚物时,反应单体为同一种结构的化合物;
当n型共轭聚合物为共聚物时,反应单体为不同结构的化合物;即反应单体为式I′化合物中两种以上或II′化合物中两种以上;或者反应单体为式I′化合物与II′化合物;
式I′与II′中X、M如式I、式II所定义。
5.根据权利要求4所述n型共轭聚合物的制备方法,其特征在于:
当n型共轭聚合物为均聚物时,所述n型共轭聚合物的结构选自如下结构的一种:
当n型共轭聚合物为共聚物时,所述n型共轭聚合物包括至少两种聚合单元;
所述每个聚合单元的结构独立地选自以下结构:
其中
n型共轭聚合物中,所述R1选自氢原子、烷基、亚烷基、烷基衍生物、亚烷基衍生物的一种或多种;
所述烷基衍生物或亚烷基衍生物上的一个或多个碳,被氧原子、氨基、砜基、羰基、芳基、烯基、炔基、酯基、氰基、硝基的一个或多个取代;
和/或
所述烷基衍生物或亚烷基衍生物上的一个或多个氢,被卤素、羟基、氨基、羧基、氰基、硝基、芳基、烯烃基、炔烃基的一个或多个取代;
所述n1-n6独立地为正整数;
所述M的结构选自芳环、芳杂环、稠合芳环、稠合芳杂环的一种。
7.根据权利要求6所述n型共轭聚合物在有机光电器件中的应用,其特征在于:所述n型共轭聚合物用于电子传输层、热电材料和/或电磁屏蔽材料。
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CN116554735A (zh) * | 2023-05-31 | 2023-08-08 | 深圳市光羿科技有限公司 | 一种导电油墨及其制备方法和应用 |
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