1,5-己二烯交联烯烃聚合物的合成及其抗剪切稳定性

以金属配合物为催化剂、1,5-己二烯为交联剂,采用本体聚合法合成了交联超高相对分子质量烯烃类聚合物(简称交联聚合物)。用傅里叶变换红外光谱、核磁共振、凝胶渗透色潜表征交联聚合物的结构和相对分子质量。用旋转黏度计和超声波仪研究了1,5-己二烯用量对交联聚合物溶液表观黏度的影响及交联聚合物的相对分子质量对交联聚合物溶液抗剪切稳定性的影响。实验结果表明,在最佳聚合条件(单体80mL、助催化剂0．4mL、CS-1催化剂0．090g、1,5-己二烯0．40mL、0℃、24 b)下所合成的交联聚合物的重均相对分子质量为7．7×106,数均相对分子质量3．6×106。加入少量1,5-己二烯能提高交联聚合物的抗剪切能力,同时也能提高交联聚合物的相对分子质量。交联聚合物的相对分子质量越大,抗剪切稳定性越好。1,5-己二烯用量约为0．1 mL时(单体40 mL),交联聚合物溶液的表观黏度达到最大值(16．8 mPa·s)。     

喹喔啉类衍生物与甲基噻吩共聚物的合成及性质

在二价镍配合物催化下,2,5-二溴-3-甲基噻吩格氏试剂与5,8-二溴-萘基喹喔啉和5,8-二溴-菲基喹喔啉共聚,得到相应的喹喔啉类共轭共聚物,收率分别为65%和68%。通过FT IR、1H-NM R对聚合物及中间体的结构进行了表征。聚合物的循环伏安图中,分别在0.66 V(Epa)/0.37 V(Epc)(Copo ly-m er I),0.78 V(Epa)/-0.06V(Epc)和1.26(Epa)/0.46(Epc)(Copo lym erⅡ)处观察到氧化还原峰,表明该类聚合物有电化学活性。在紫外-可见光谱中,分别在263 nm,323 nm处(Copo lym erⅠ)和299 nm,402 nm处(Copo lym erⅡ)出现吸收峰。所得聚合物分别在504 nm和513 nm处出现荧光最大发射峰。     

超强吸水性树脂的制备及吸水性能研究

合成了以丙三醇为交联剂的聚丙烯酸类高分子吸水剂,讨论了丙三醇作交联剂时,引发剂用量、 交联剂用量、中和度、反应温度及时间对树脂吸水能力的影响。所制树脂吸水率达800g/g。对0.9％食盐水吸水 率最大为70g/g。     

Preparation of π-conjugated polymers consisting of 2-decylbenzimidazole and thiophene units and chemical properties of the polymers

Polycondensation by Stille coupling of 2-decyl-4,7-dibromobenzimidazoles and N-methyl-2-decyl-4,7-dibromobenzimidazole with 2,5-bis(trimethylstannyl)thiophene and 5,5′-bis(trimethylstannyl)-2,2′-bithiophene gave the corresponding π-conjugated polymers, poly(2-decylbenzimidazole-4,7-diyl-thiophene-2,5-diyl) 1b, poly(2-decylbenzimidazole-4,7-diyl-bithiophene-2,5-diyl) 1c and poly(N-methyl-2-decylbenzimidazole-4,7-diyl-thiophene-2,5-diyl) 2b, in 98-99% yields. The polymers 1b and 2b were fully soluble in CF₃COOH, and partially soluble in DMF (about 60 and 40% for 1b and 2b, respectively) and NMP (about 70 and 40%, respectively). The NMP soluble part of 1b and DMF soluble part of 2b gave values of 0.36 and 0.24 dl g⁻¹ in NMP and DMF, respectively. The DMF soluble part of 1b, 1c and 2b showed absorption peaks at about 458, 465 and 388 nm, respectively, in DMF. In an alkaline medium the absorption peaks of 1b and 1c are shifted to a longer wavelength by 92-101 nm; the observed shifts in the acidic medium and alkaline medium were much larger than those observed with usual benzimidazoles with low molecular weights. Packing structures of 1b, 1c and 2b are discussed based on their XRD patterns.     

丙烯酸β-环糊精酯共聚物对染料的吸附性能

以丙烯酸β-环糊精酯共聚物为吸附剂,采用分光光度法测定该吸附剂对亚甲基蓝和碱性品红溶液的静态吸附效果,考察了吸附时间、体系pH值等对吸附量的影响。结果表明:常温下,亚甲基蓝的较佳吸附条件为静态吸附时间约7h、体系pH=8.0时,最大吸附量达到166.3mg/g;碱性品红的较佳吸附条件为静态吸附时间约7h、体系pH=10时,最大吸附量达到137.9mg/g。该共聚物对亚甲基蓝染料吸附性能更好。     

Novel poly(arylene ethynylene) derivatives containing main chain triphenylamine and pendent quinoxaline moieties: synthesis and elementary characterization

BACKGROUND: Various poly(arylene ethynylene)s (PAEs) have been prepared and applied as molecular wires, in sensors, in nonlinear optics and as electroluminescent materials. But, to our knowledge, there has been no attention paid to the investigation of conjugated PAEs containing both triarylamine and quinoxaline groups. The influence imparted by the introduction of triarylamine and quinoxaline on the photophysical and electrochemical properties of PAEs is of interest. RESULTS: Two kinds of novel PAE derivatives, with electron‐donating triphenylamine groups in the backbone and electron‐accepting pendent quinoxaline moieties and bearing side chains of different lengths, were successfully synthesized with the Sonogashira coupling reaction. These polymers are soluble in common organic solvents and exhibit good film‐forming ability and thermal stability. UV‐visible investigations indicate that the ground states of these materials are unaffected by the polarity of their medium. An efficient intramolecular charge transfer effect is observed from an investigation of their photoluminescence properties in different solvents. Cyclic voltammetry study reveals that these polymers possess relatively high highest occupied molecular orbital levels due to the incorporation of triphenylamine segments into the polymer backbones. CONCLUSION: Primary characterization of these novel PAE derivatives shows that they might serve as potential active materials in optoelectronic devices. Copyright © 2009 Society of Chemical Industry     

Studies on structural,dielectric and charge transport properties of PVA:LiBr solid polymer electrolyte films

In the present study, solid polymer electrolytes (SPEs) based on poly (vinyl alcohol) (PVA) doped with lithium bromide (LiBr) were prepared by solution casting method. Fourier transform infrared spectroscopy results affirm the complexation of LiBr with PVA. X-ray diffraction results exhibit the increase of amorphous nature of the polymer electrolytes, which is also observed in scanning electron microscopy images and atomic force microscopy topographs. Thermogravimetric analysis thermographs endorse the increase of thermal stability of the polymer due to doping. Dielectric studies exhibit non-Debye nature of the polymer electrolytes. Conductivity spectra reveal the maximum ionic conductivity (1.15 × 10⁻⁴ S/cm) for 20 wt% LiBr/PVA electrolyte at ambient temperature. Impedance analysis reveals the decrease of ionic relaxation in the polymer electrolytes and the studied transport properties of the electrolyte show that the major contribution to the conduction in this polymer electrolyte is ions.     

甘露醇交联的聚丙烯酸钠吸水树脂综合应用性能的测试

采用溶液聚合法合成了甘露醇交联的聚丙烯酸钠吸水树脂。用红外光谱和热重分析方法对聚丙烯酸钠超强吸水树脂产品进行了表征,测定了该树脂的溶胀动力学、耐热、耐寒、耐光性能及不同pH溶液对树脂吸水率的影响,分析了该树脂的羧酸根和凝胶含量,测试了不同温度下的吸水率、保水率。结果表明,该树脂在蒸馏水中的吸水率为1 750mL/g,在0.9%NaC l水溶液中的吸盐水率为130mL/g。利用热重分析法对该树脂的热分解动力学过程进行研究,并计算了热分解的活化能及指前因子。实验结果表明,该树脂的溶胀动力学扩散摸模型为non-Fickon扩散;热分解过程为一级反应。该树脂具有较好的综合应用性能。     

长侧链减阻聚烯烃的合成及其抗剪切稳定性的研究

用溶液聚合法,以轻质油为溶剂,一氯二乙基铝/四氯化钛为催化体系,C10-14α-烯烃为单体,合成了一种长侧链聚烯烃类油溶性减阻剂.该聚合物未经脱溶剂处理,减阻率高达45%(添加质量浓度为0.01kg/m3),超过了本体聚合法得到的聚合物(减阻率为40.1%).热重分析表明,聚合物在380℃开始分解,唯一的热失重阶段大约为380℃～450℃.聚合物溶胀前后XRD测试结果显示溶胀前聚合物结构规整性较差,溶胀后使主链和侧链部分展开,规整性提高.最后研究了聚合物溶液的抗剪切稳定性.     

基于芴和噻吩的共轭聚合物的固相合成及其表征

通过Stille偶合反应合成了2,7位二噻吩基取代的新型芴类衍生物并首次应用固相聚合法合成出聚-2,7-二噻吩基芴.在25℃测得聚合物的特性粘度为0.68dl/g.通过核磁共振(1H-NMR)、红外光谱(FTIR)对单体和聚合物的结构进行了表征确认,同时研究了聚合物的光学、结晶态形貌及热学性能.研究发现,2,7-二噻吩基芴在研磨过程中发生了聚合反应且其偶合发生在e,e′位置.