聚[2—甲氧基—5—（4—溴—丁氧基）对苯乙炔]新型前聚物的合成及…

采用不同方法由三铳盐合成新型的聚电解质前聚物及可溶于有机溶剂的侧链溴代聚对苯乙炔前聚物，发现侧链烷氧取代基上的铳盐并不参与聚合，所得前聚物加热都可转化为聚对苯乙炔。     

聚[2-甲氧基-5-(4-溴-丁氧基)对苯乙炔]新型前聚物的合成及表征]

采用不同方法由三锍盐合成新型的聚电解质前聚物及可溶于有机溶剂的侧链溴代聚对苯乙炔前聚物,发现侧链烷氧取代基上的锍盐并不参与聚合,所得前聚物加热后都可转化为聚对苯乙炔.光物理初步研究表明,溴代侧链聚对苯乙炔与C₆₀掺杂后具有良好的光电特性.以IR、UV-Vis、¹H NMR、DSC对单体及前聚物进行了表征.     

5，8-二呋喃基萘基喹喔啉与对苯撑乙炔交替共聚物的合成及其性能

利用Stille耦合反应合成了新型单体5,8-二呋喃基萘基喹喔啉,溴化后与不同长链烷氧基侧链的对苯撑乙炔共聚,合成了聚[2,5-二（辛氧基）-1,4苯撑乙炔撑-5,8-二（呋喃基）萘基喹喔啉]（PⅠ）和聚[2,5-二（十二烷氧基）-1,4-苯撑乙炔撑-5,8-二（呋喃基）萘基喹喔啉]（PⅡ）。通过FT—IR、1H—NMR等手段对单体和共聚物的结构进行了表征,采用紫外-可见吸收光谱、荧光发射光谱和循环伏安法对聚合物的光、电性能进行了探讨。结果表明：单体和共聚物PⅠ、PⅡ在长波处的紫外-可见吸收峰分别为435、418、423nm,相应的荧光发射峰分别为551、589、579nm。2种共聚物均在1．54V处出现氧化峰,无相应的还原峰。     

5，8-二呋喃基萘基喹喔啉与对苯撑乙炔交替共聚物的合成及其性能北大核心CSCD

利用Stille耦合反应合成了新型单体5,8-二呋喃基萘基喹喔啉,溴化后与不同长链烷氧基侧链的对苯撑乙炔共聚,合成了聚[2,5-二(辛氧基)-1,4-苯撑乙炔撑-5,8-二(呋喃基)萘基喹喔啉](PⅠ)和聚[2,5-二(十二烷氧基)-1,4-苯撑乙炔撑-5,8-二(呋喃基)萘基喹喔啉](PⅡ)。通过FT-IR、1 H-NMR等手段对单体和共聚物的结构进行了表征,采用紫外-可见吸收光谱、荧光发射光谱和循环伏安法对聚合物的光、电性能进行了探讨。结果表明:单体和共聚物PⅠ、PⅡ在长波处的紫外-可见吸收峰分别为435、418、423nm,相应的荧光发射峰分别为551、589、579nm。2种共聚物均在1.54V处出现氧化峰,无相应的还原峰。     

沉淀剂对含有氨侧基的聚苯撑乙炔发光性能的影响

通过单体4-[(2,5-二溴苯)乙炔基]苯胺和1,4-二乙炔基-2,5-二戊氧基苯之间的Sonogashira偶合反应合成了带有p-氨基苯乙炔基共轭侧基的聚对苯撑乙炔（(PAnPE）). 该共轭聚合物的THF溶液（(2××10-－5 mol•·L-－1）)在473和519 nm处呈现两个比较强的荧光发射峰. 通过调节在聚合物PAnPE-THF溶液中所加入三种沉淀剂（(甲醇、乙酸、稀盐酸溶液）)的体积比例, 来改变PAnPE分子链的聚集态结构, 进而研究对其发光性能的影响规律. 实验结果表明: 由于沉淀剂与聚合物PAnPE分子链之间相互作用能力与方式的不同, PAnPE两个荧光峰的发射强度因聚合物分子链聚集结构不同而呈现不同的变化规律, 这有助于实现在化学传感器中的应用.     

5,8-二(3,4-乙撑二氧噻基)-萘基喹喔啉与对苯乙炔交替共轭聚合物的合成及其性能

合成了一种新单体5,8-二(5′-溴-3,4-乙撑二氧噻基)-萘基喹喔啉,并通过Sonogashira偶合反应将此单体与带有不同长链烷氧基的对苯乙炔进行交替共聚,得到了聚[(2,5-二庚氧基-1,4-苯撑)乙炔撑-5,8-二(3,4-乙撑二氧噻基)-萘基喹喔啉](PI)和聚[(2,5-二十二烷氧基-1,4-苯撑)乙炔撑-5,8-二(3,4-乙撑二氧噻基)-萘基喹喔啉](PII)。采用核磁共振氢谱、傅里叶红外光谱、紫外-可见光谱、荧光光谱、循环伏安和热重分析对聚合物进行了表征。结果表明:共聚物PI和PII有相似的光学特性,均在490 nm处出现紫外-可见最大吸收峰,在613 nm处出现荧光最大发射峰;热稳定性和电化学活性较好;在-1.0~2.0 V出现电致变色现象,颜色由红色变为深蓝色。     

耐高温交联侧基苯乙炔封端酰亚胺预聚体

合成了含有苯乙炔基的二胺单体 3,5-二氨基-4'-苯乙炔苯甲酮(DPEB), 并与3,3',4,4'-联苯四酸二酐(s-BPDA)和1,4-双(4'-氨基苯氧基)-2-(苯基)苯(p-TPEQ)进行了缩聚反应, 以4-苯乙炔苯酐作为封端剂, 合成了交联侧基苯乙炔封端酰亚胺预聚体(n=4). DSC测试结果表明, 引入交联侧基后预聚体依然保持着较宽的加工窗口. 利用所合成的预聚体在370℃热压1 h制备了热固性薄膜. DMA测试结果表明, 引入交联侧基的预聚体树脂具有更高的玻璃化转变温度, 并且其储存模量在玻璃化转变后有很好的保持.     

非共价键自组装制备聚对苯撑乙炔/聚丙烯酸水溶性荧光纳米粒子及其光物理行为研究

通过功能化聚对苯撑乙炔(含羟基与氨基)和聚丙烯酸之间的非共价键自组装制备了一系列含共轭聚合物的水溶性荧光纳米粒子, 并进行了相关结构和光学性质表征. 研究表明, 纳米粒子的大小和聚丙烯酸/聚对苯撑乙炔质量比直接相关. 光物理性质研究表明, 形成水溶性纳米粒子后, 疏水的聚苯撑乙炔链在纳米粒子中易于形成π-链间聚集, 其光物理性质与其在薄膜态时相似.     

聚对苯撑乙烯齐聚物及其衍生物电子结构和发光机理的理论研究

运用量子化学从头算ab initio HF方法对聚对苯撑乙烯剂聚物及其衍生物的几何结构进行了优化,分析了前线分子轨道成分,确认了电子光谱的跃迁轨道。计算结果表明,聚苯撑乙烯剂聚物及衍生物的电子云分布与其结构密切相关,不同取代基修饰下的二聚苯撑乙烯的电子光谱发生红移,且随取代基推电子能力加强红移显。电子光谱跃迁主要是最高占据轨道向最低空轨道之间的π－π^*跃迁,计算结果和实验吻合得很好。     

1,4—双（取代苯乙炔基）苯及反,反—1,4—双（β—取代苯乙…

测定了１，４－双（取代苯乙炔基）苯（Ⅰ）和反，反－１，４－双（β－取代苯乙烯基）苯（Ⅱ）的紫外光谱、荧光光谱。用ＣＮＤＯ／Ｓ－ＣＩ和ＨＭＯ方法对苯乙炔、二苯乙炔和（Ⅰ）及苯乙烯、１，２－二苯乙烯和（Ⅱ）的激发能进行了计算和研究。讨论了化合物结构对光谱的影响。     

轴向为烷氧基配位的萘酞菁硅配合物的光谱及光稳定性

轴向为烷氧基配位的萘酞菁硅配合物的光谱及光稳定性;萘酞菁硅;轴向烷氧基配位;光谱性质;光稳定性     

无柔性间隔基侧链型液晶高分子复合定形相变材料的制备与性能研究

设计合成了一系列具有不同烷氧基尾链长度的单体4′-烷氧基-4-联苯酚甲基丙烯酸酯Mbi Cm(m=1,2,4,6,8,10,12,14,16,18),通过自由基聚合方法合成了相应的具有不同烷氧基尾链长度的无柔性间隔基侧链型液晶高分子PMbi Cm,将所得的侧链型液晶高分子和相变材料石蜡按一定质量比混合,通过"加热-冷却法"成功制备了定形相变材料.通过凝胶测试发现当尾链长度为m=12,14,16,18时,高分子对固体石蜡具有良好的凝胶定形效果,且随着烷氧基尾链的增长,聚合物和石蜡的相容性增加,最低凝胶浓度降低,得到定形相变材料的凝胶解缔温度也相应下降.通过示差扫描量热法(DSC)、热重分析法(TG)、流变(Rheology)等测试考察了定形相变材料的相变储能性能、热稳定性和流变性能,实验结果表明该定形相变材料具有相变焓值高、热稳定性好、凝胶强度高等优点.通过红外光谱(FTIR)、偏光显微镜(POM)和扫描电镜(SEM)等测试发现PMbi Cm通过非共价键作用力自聚集形成三维凝胶网络结构,对石蜡起固定支撑作用.     

Synthesis and characterization of stable blue light‐emitting poly(spirobifluorene) derivatives containing alkoxy group

Polymers containing alkoxy‐substituted spirobifluorene have been prepared from nickel(0)‐mediated coupling or palladium‐catalyzed Suzuki coupling. The polymers were characterized using various spectroscopies, such as ¹H‐NMR, FT‐IR, and elemental analysis. The high glass transition temperature and high decomposition temperature suggested that the resulting polymers possessed a high thermal stability. The obtained polymers possessed weight average molecular weight of 4500–33,000 with polydispersity index of 1.1–1.9 and good solubility. The low onsets of the oxidation potential suggested that the polymers containing alkoxy substituted spirobifluorene possessed a good hole injection property. The photoluminescence and electroluminescence of the polymers containing alkoxy substituted spirobifluorene showed stable blue color by suppressing the excimer formation due to intermolecular interaction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2316–2324, 2005     

New conducting polythiophenes containing substituted polyfluorinated alkoxy chain

A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structures in electronic effect and higher stabilities of their polymers than conventional alkoxy chain substituted polymers.     

PREPARATION AND CHARACTERIZATION OF SHISH-KEBAB TYPE LIQUID CRYSTALLINE POLY（p-PHENYLENEVINYLENE）

Novel shish-kebab type liquid crystalline poly（p-phenylenevinylene） derivatives were synthesized by Stille coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer l） and 1,2-bis（tributylstannyl） ethylene （monomer 2）. The polymers with alkoxy groups are soluble in common organic solvents and exhibit blue fluorescence. Both the cast film and the annealed film have large red-shifts in fluorescence spectra and show yellow fluorescence. The polymers with CN and NO2 groups show poor solubility and green fluorescence. All the polymers possess liquid crystalline smectic phases. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The polymers are easily aligned under a magnetic field of 10 Tesla. It is found that the conjugated backbone and LC side chain are aligned perpendicular and parallel to the magnetic field, respectively. The polymers show optical dichroism in fluorescence spectra, suggesting that they are available for advance materials with linear optical polarization.     

Preparation of semi‐alternating conjugated polymers using direct arylation polymerization (DArP) and improvement of photovoltaic device performance through structural variation

The results herein expand on optimized direct arylation polymerization (DArP) conditions for defect‐free poly[(2,5‐bis (2‐hexyldecyloxy)phenylene)‐alt‐(4,7‐di(thiophen‐2‐yl)benzo[c][1,2,5] thiadiazole)] (PPDTBT). Semi‐alternating and alternating donor–acceptor polymers containing alkoxy phenylene, dithienyl‐substituted thieno[3,4‐c]pyrrole‐4,6‐dione (DTTPD), and dithienyl‐substituted diketopyrrolopyrrole (DTDPP) were prepared via DArP, including a four‐component semi‐alternating copolymer PPDTDPPTPD. Variation of the alkoxy substituents on the phenylene donor including n‐hexyl, 2‐ethylhexyl, or 2‐hexyldecyl allowed for the tuning of thephysical and electronic properties. Molecular weights (M _n) ranged from 3.07 to 28.3 kDa for the PPDTTPD polymers and 2.63‐44.0 kDa for the PPDTDPP polymers, depending on the alkoxy substituents. Absorbance maxima and HOMO energies were varied from 550 to 602 nm and ?5.31 to ?5.69 eV for the PPDTTPD polymers and from 671 to 794 nm and ?5.41 to ?5.55 eV for the PPDTDPP polymers, respectively. Additive‐free, bulk heterojunction (BHJ) solar cells were fabricated, and the fill‐factors obtained (0.57–0.63) are some of the highest reported for polymers prepared using DArP. Higher molecular weight polymers for both PPDTTPD (28 kDa) and PPDTDPP (44 kDa) series performed poorly in solar cells. In contrast, the semi‐alternating polymers of lower M _n for the PPDTTPD (12.4 kDa) and PPDTDPP (9.05 kDa) series, incorporating both n‐hexyl and 2‐hexyldecyl alkoxy phenylene donors, provided power conversion efficiencies (PCE) of 3.26% and 3.49%, respectively. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3370–3380     

Structure–property studies and orientation effects of polythiophenes containing mesogenic side chains

Liquid crystalline materials display unique properties, which can be exploited in organic light emitting diodes. Polythiophene model compounds containing phenyl groups linked with azomethine, ester, and alkoxy groups [thiophene‐3‐alkyloxy benzoyloxy aniline series (N series) and thiophene‐3‐alkoxy phenoxy amino benzoate series (R Series)] were synthesized. Molecular orbital calculations were performed and the predicted band gaps compared to understand the effects of spacer length and linkage. The experimental photoabsorption characteristics are compared with the theoretically predicted band gap. Photoabsorption and emission studies on N series and R series polymers as the function of polarizer angle suggest that polymers of both series emit polarized light in all base color ranges. The electroemission characteristics of the above‐synthesized polymers were also recorded as the function of polarizer angle. The results show that the compounds also emit polarized electroemission, and the EL polarization ratio decreases with the increase of alkoxy chain length for N and R polymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1463–1477, 2008     

Photophysical properties of hydroxylated amphiphilic poly(p-phenylene)s

A homologous series of polyhydroxylated poly(p-phenylene)s with different alkoxy groups (C6PPPOH, C12PPPOH, and C18PPPOH) were synthesized with use of the Suzuki polycondensation reaction. Comparative studies of the structure correlation between their photophysical properties and film morphology is described. The absorption and emission spectra of polymers in solution and thin films showed similar features indicating that the electronic properties in solution were retained in the film state. Compared to the polymer with the short alkoxy chains (C6PPPOH), the polymers with long alkoxy groups (C12PPPOH and C18PPPOH) showed improved film forming properties with continuous and smooth film morphology. The absorption properties of the C12PPPOH showed an enhanced effective conjugation length and high quantum yield implying planarization of the backbone through alkoxy chain packing (C12H25O-) and potential hydrogen bonds. No overlap in the absorption and emission spectra was observed, which indicated minimized excimer formation or excitation energy transfer in the films. Time-resolved fluorescence measurements showed that the decay times increased from 43 ps (C6PPPOH) to 78 ps (C12PPPOH) and 99 ps (C18PPPOH). Electrochemical studies were performed for all polymers and the observed oxidation potential for C6PPPOH was higher than that of C12PPPOH and C18PPPOH. In addition, the C12PPPOH has the lowest band gap of DeltaE = 2.59 eV when compared to the 3.1 (C6PPPOH) and 2.61 eV (C18PPPOH) gaps. The optical band gaps estimated from the absorption onset of the polymers are significantly higher than those obtained from electrochemical data. C12PPPOH was chosen for investigating the charge carrier mobility by the time-of-flight (TOF) technique. The observed results also showed negative field dependent values of the drift mobility for the polymer C12PPPOH.     

Tunable Thermoresponsive Pyrrolidone‐Based Polymers from Pyroglutamic Acid,a Bio‐Derived Resource

A series of pyrrolidone‐based polymers is prepared from pyroglutamic acid, a bio‐derived resource. Polymers bearing simple alkoxy substituents (e.g., methoxy, ethoxy, and butoxy) are soluble in common organic solvents and possess glass transition temperatures that are dependent on the length of the alkoxy residue. Replacing these substituents with an ether moiety (CH₃OCH₂CH₂O—) affords a highly sensitive and reversible thermoresponsive polymer with a lower critical solution temperature (LCST) of 42 °C in water. Copolymers composed of repeat units bearing both the ether and simple alkoxy residues are found to exhibit LCSTs that are highly dependent on the nature of the hydrophobic alkoxy residue suggesting that the LCSTs of these polymers can be successfully tuned by simply tailoring the copolymer structure.     

Asymmetric anionic polymerizations of 7‐cyano‐7‐alkoxycarbonyl‐1,4‐benzoquinone methides

Asymmetric anionic polymerizations of 7‐cyano‐7‐alkoxycarbonyl‐1,4‐benzoquinone methides ( 1 ) with various alkoxy groups were performed using chiral initiators such as lithium isopropylphenoxide (ⁱPrPhOLi)/(S)‐(–)‐2,2′‐isopropylidene‐bis(4‐phenyl‐2‐oxazoline) ((–)‐PhBox) and lithium isopropylphenoxide (ⁱPrPhOLi)/(–)‐sparteine ((–)‐Sp) to investigate the effect of the alkoxy groups of alkoxycarbonyl substituent in the monomers 1 and chiral ligands of chiral initiators on the control of chiral center in the formation of polymers. Molar optical rotation values of the polymers were significantly dependent upon alkoxy groups, and the polymers with higher molar optical rotation were obtained in monomers with primary alkoxy groups. The asymmetric anionic oligomerizations of the quinone methides having methoxy( 1a ), ethoxy( 1b ), and n‐propoxy( 1c ) groups with chiral initiators were carried out. Both 1‐mers and 2‐mers were isolated and their optical resolutions were performed to determine the extent of stereocontrol. High stereoselectivity was observed at the propagation reaction, but not at the initiation reaction. The effect of the counterion on the control of chiral center in the formation of the polymer was investigated in the asymmetric anionic polymerizations of 1b with ⁱPrPhOM(M = Li, Na, K)/(–)‐Sp and ⁱPrPhOM(M = Li, Na, K)/(–)‐PhBox initiators and discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011