二苯基金刚烷改性3,6-咔唑共聚物的合成及性能

doi:10.16085/j.issn.1000-6613.2018-1406

摘要/Abstract

摘要： 咔唑类蓝色发光材料固有的低玻璃化转变温度严重限制了实际应用，为了解决这个问题，本文制备了一种高稳定性聚咔唑蓝光材料。以单体3，6-二溴-9-（2-乙基己基）咔唑和N-（2-乙基己基）-3，6-二（4，4，5，5-四甲基-1，3，2-二氧硼戊烷-2-基）咔唑、1，3-二（4-溴苯基）金刚烷为原料，以四（三苯基膦）钯为催化剂，通过调整单体比例，经Suzuki反应合成了数均分子量约3500~6000的3，6-咔唑-二苯基金刚烷共聚物。差热扫描量热测试结果表明，在加入摩尔分数分别为10%、30%和50%的二苯基金刚烷后，共聚物玻璃化转变温度从3，6-咔唑均聚物的66℃分别显著升高至78℃、93℃、106℃，热重测试的失重5%热分解温度同样随着二苯基金刚烷含量的升高而升高。低含量二苯基金刚烷改性共聚物的荧光量子产率较3，6-咔唑均聚物高，显示了优良的荧光传递特性。且共聚物薄膜态时的最大荧光发射波长均处于蓝光最适波长范围内。研究结果表明：二苯基金刚烷的加入显著改善了咔唑聚合物的热稳定性能，还改善了发光性能，制备的共聚物是一种非常有应用前景的新型蓝光材料。

关键词: 3,6-咔唑, 二苯基金刚烷, 蓝光, 聚合物, 稳定性, 发光性能

Abstract: The inherent low glass transition temperature of carbazole blue luminescent materials severely limits its practical applications. To solve this problem, a kind of highly stable polycarbazole blue light material was prepared. By using 3,6-dibromo-9-(2-ethylhexyl)carbazole and N-(2-ethylhexyl) -3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole, 1,3-bis(4-bromophenyl)adamantane as the monomers, several 3,6-carbazole-diphenyladamantane copolymers were synthesized by palladium-catalyzed Suzuki coupling reaction. The number average molecular weight of the copolymer was in the range of 3500-6000. The DSC test results showed that after adding 10%, 30% and 50% molar contents of diphenyladamantane, the glass transition temperature of the copolymer significantly rose from 66℃ of the 3,6-carbazole homopolymer to 78℃, 93℃ and 106℃, respectively. As the content of diphenyladamantane increased, the thermal decomposition temperature (at 5% weight loss) of the copolymer also rose. The low-content diphenyladamantane modified copolymer had higher fluorescence quantum yield than the 3,6-carbazole homopolymer, showing excellent fluorescence transfer ability. The maximum fluorescence emission wavelength in the copolymer film state was within the optimal blue light wavelength range. The results showed that the addition of diphenyladamantane significantly improved the thermal stability of the carbazole polymer and the luminescence properties. The prepared copolymer was a new type of blue light emitting material with promising application.

Key words: 3,6-carbazole, diphenyladamantane, blue light, polymers, stability, luminous properties

中图分类号:

TQ311

柳滢春, 郭建维, 罗涛, 王伟彬. 二苯基金刚烷改性3,6-咔唑共聚物的合成及性能[J]. 化工进展, 2018, 37(12): 4765-4772.

LIU Yingchun, GUO Jianwei, LUO Tao, WANG Weibin. Synthesis and properties of diphenyladamantane modified 3,6-carbazole copolymers[J]. Chemical Industry and Engineering Progress, 2018, 37(12): 4765-4772.

参考文献

[1] WANG B, YIN J, XUE M Z, et al. Dibenzothiophene-5,5-dioxide-containing PPV based copolymer as green-blue electroluminescent material[J]. Synthetic Metals, 2003, 132(2):191-195.
[2] GRISORIO R, PILIEGO C, COSMA P, et al. Random poly (fluorenylene-vinylene)s containing 3,7-dibenzothiophene-5,5-dioxide units:synthesis, photophysical, and electroluminescence properties[J]. Journal of Polymer Science Part A, Polymer Chemistry, 2009, 47(8):2093-2104.
[3] YANG S H, HUANG C H, CHEN C H, et al. Synthesis and electroluminescent properties of disubstituted polyacetylene derivatives containing multi-fluorophenyl and cyclohexylphenyl side groups[J]. Macromolecular Chemistry & Physics, 2010, 10(1):37-47.
[4] GAL Y S, JIN S H, SHIM S Y, et al. Photovoltaic properties of polyacetylene derivative for quasi-solid state dye-sensitized solar cell applications[J]. Molecular Crystals & Liquid Crystals, 2017, 654(1):83-89.
[5] LEE Y Z, CHEN X, CHEN S A, et al. Soluble electroluminescent poly(phenylene vinylene)s with balanced electron-and hole injections[J]. Journal of the American Chemical Society, 2001, 123(10):2296-2307.
[6] WANG H, LIAN D, YONG Q, et al. Synthesis and electroluminescence properties of a novel poly(paraphenylene vinylene)-based copolymer with tri(ethylene oxide) segments on the backbone[J]. Journal of Applied Polymer Science, 2002, 83(10):2195-2200.
[7] GORDON K C, MACARTHUR S, DAVID G, et al. Experimental and computational studies of substituted terthiophene oligomers as electroluminescent materials[J]. Synthetic Metals, 2005, 153(1):225-228.
[8] MARTÍNEZ F, NECULQUEO G, VÁSQUEZ S O, et al. Synthesis, characterization and theoretical studies of thiophene/phenylene derivatives as electroluminescent materials[J]. Journal of Molecular Structure, 2010, 973(1):56-61.
[9] PARK M J, SHIM H K. Synthesis, characterization and electroluminescence of polyfluorene copolymers with phenothiazine derivatives; their application to white-and red-emitting pleds[C]//Advanced Photonics and Renewable Energy. Karlsruhe:Optical Society of America, 2010:JAW7
[10] CHAO T. Polyfluorene and its derivatives as electroluminescent materials[J]. Progress in Chemistry, 2007, 19(10):1553-1561.
[11] WANG P, JIN H, LIU W, et al. Bipolar copolymers comprised mesogen-jacketed polymer containing oxadiazole units and PVK as host materials for electroluminescent devices[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2010, 46(23):7861-7867.
[12] LEE J W, KIM J K, YOON Y S. Performance improvement of organic light emitting diodes using poly(N-vinylcarbazole) (PVK) as a blocking Layer[J]. Chinese Journal of Chemistry, 2010, 28(1):115-118.
[13] BLOUIN N, LECLERC M. Poly(2,7-carbazole)s:structure-property relationships[J]. Accounts of Chemical Research, 2008, 41(9):1110-1119.
[14] TANG W, LIN T, KE L, et al. Synthesis, photophysics, theoretical modeling, and electroluminescence of novel 2,7-carbazole-based conjugated polymers with sterically hindered structures[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2010, 46(23):7725-7738.
[15] 朱小雪, 张青, 薛敏钊, 等. 聚亚苯基乙烯衍生物作为电致发光材料的研究进展[J]. 化工进展, 2008, 27(8):1181-1191. ZHU X X, ZHANG Q, XUE M Z, et al. Progress of poly(p-phenylenevinylene) derivatives as electroluminescent materials[J]. Chemical Industry and Engineering Progress, 2008, 27(8):1181-1191.
[16] 刘卫军, 陈阳如, 熊国宣. 含1,3,4-噁二唑环的有机电致发蓝光材料及器件研究进展[J]. 化工进展, 2006, 25(8):895-900. LIU W J, CHEN Y R, XIONG G X. Progress of blue light-emitting organic electroluminescet materials containing 1,3,4-oxadiazole ring and related devices[J]. Chemical Industry and Engineering Progress, 2006, 25(8):895-900.
[17] 刘卅, 郭建维. 相转移催化法合成新型金刚烷基聚芳酯[J]. 化工学报, 2008, 59(6):1556-1564. LIU S, GUO J W. Synthesis of novel polyarylates based adamantane via phase transfer catalysis[J]. Journal of Chemical Industry and Engineering (China), 2008, 59(6):1556-1564.
[18] 朱华, 郭建维, 刘卅, 等. 金刚烃类化合物研究进展(Ⅱ)制备与应用[J]. 化工进展, 2011, 30(4):807-812. ZHU H, GUO J W, LIU S, et al. Development of diamondoids (Ⅱ) preparation and applications[J]. Chemical Industry and Engineering Progress, 2011, 30(4):807-812.
[19] ZHENG S Y, SHI J M, MATEU R. Novel blue light emitting polymer containing an adamantane moiety[J]. Chemistry of Materials, 2000, 12(7):1181-1814.
[20] JIAN L, HIRAYAMA Y, SANO T, et al. Reduction of chain interactions in a class of blue fluorene copolymers with adamantane units[J]. Thin Solid Films, 2006, 515(4):2686-2691.
[21] ZHAO Q, WU W. Synthesis and photoluminescence properties of thermal-stable polyfluorenes modified with adamantane derivatives as inserted-backbone units or chain ends[J]. Synthetic Metals, 2009, 159(12):1153-1157.
[22] GU Y, ZHU L, LI Y, et al. Adamantane-based wide-bandgap host material:blue electrophosphorescence with high efficiency and very high brightness[J]. Chemistry, 2015, 21(22):8250-8256.
[23] LIU Q, TANG Z, WU M, et al. Design, preparation and application of conjugated microporous polymers[J]. Polymer International, 2014, 63(3):381-392.
[24] ZHANG K, WANG L, LIANG Y, et al. A thermally and electrochemically stable organic hole-transporting material with an adamantane central core and triarylamine moieties[J]. Synthetic Metals, 2012, 162(5):490-496.
[25] PALIULIS O, OSTRAUSKAITE J, GAIDELIS V, et al. Synthesis of conjugated carbazole trimers and pentamers by Suzuki coupling[J]. Macromolecular Chemistry and Physics, 2003, 204(14):1706-1712.
[26] BEGINN C, GRAZULEVICIUS J V, STROHRIEGL P, et al. Synthesis of poly(9-hexyl-3,6-carbazolyleneethynylene) and its model compounds[J]. Macromolecular Chemistry & Physics, 2010, 195(7):236-239.
[27] 刘然升, 曾文进, 杜斌, 等. 新型基于3,6-咔唑与噻吩衍生物的红光聚合物的合成与性能研究[J]. 化学学报, 2007, 65(9):847-852. LIU R S, ZENG W J, DU B, et al. Synthesis and characterization of novel red-light-emitting polymers based on 3,6-carbazole and thiophene derivatives[J]. Journal of Chemical Industry and Engineering (China), 2007, 65(9):847-852.
[28] HATTORI Y, MIYAJIMA T, SAKAI M, et al. Synthesis and thermal characterization of novel adamantane-based polysiloxane[J]. Polymer, 2008, 49(12):2825-2831.
[29] 杨洗, 潘祖亭, 马勇. 用罗丹明B作标准物测定二氯荧光素的荧光量子产率[J]. 分析科学学报, 2003, 19(6):588-589. YANG X, PAN Z T, MA Y. Rhoda mine B as standard substance to measure the fluorescence-quantum yield of dichlorofluorescein[J]. Journal of Analytical Science, 2003, 19(6):588-589.
[30] GRELL M, BRADLEY D D C, UNGAR G, et al. Interplay of physical structure and photophysics for a liquid crystalline polyfluorene[J]. Macromolecules, 1999, 32(18):5810-5817.