含手性联萘冠醚侧基的聚苯型共轭聚合物的合成与表征

用钯催化的Suzuki缩聚法合成了一类新型主链为共轭聚苯结构,侧基数手性联萘冠醚取代基团的光学活性共轭聚合物。用1^H-NMR、紫外吸收光谱、园二色性、荧光光谱、热失重及差热分析等方法进行了表征。结果表明该光学活性聚苯具有良好的热稳定性和高的比旋度,在溶液中能络合碱金属离子,其荧光发射强度随着离子浓度的增大而逐渐降低。该光学活性聚苯的荧光光谱在410nm处出现最大发射峰,是一类潜在的发蓝光材料。     

在丙烯酰胺聚合反应中聚苯乙烯磺酸的大分子效应

本文研究了聚苯乙烯磺酸对丙烯酰胺聚合反应的影响。采用红外光谱、元素分析和电子能谱等手段研究了聚苯乙烯磺酸同丙烯酰胺分子间的相互作用。发现二者间存在着由磺酸基与酰胺基相互作用而形成的铵盐的结合形式,从而提出了在聚苯乙烯磺酸存在下丙烯酰胺聚合历程的模式,并以此机理解释了聚苯乙烯磺酸在丙烯酰胺聚合反应中的作用。     

Synthesis and characterization of dendronized poly(methylsiloxane) with appendent Fréchet-type dendrons

A new kind of dendronized poly(methylsiloxane) (3a and 3b) with appendent Fre-chet-type poly(aryl ether) dendrons has been synthesized and characterized by GPC, DSC, TGA, fluorescence and UV-Vis spectra.     

基于L-(+)-酒石酸二乙酯的光学活性聚酯的合成与表征

对基于Ｌ （＋） 酒石酸二乙酯和邻、间、对位苯二甲酰氯的光学活性聚酯进行了合成．这类聚酯的比旋光度与所采用的二酰氯有关,依次为对苯＞间苯＞邻苯．通过模型化合物、最小能量优化及圆二色谱等分析表征阐明了这类聚酯不同的结构形态特征．     

“Living”/controlled radical copolymerization of N-phenylmaleimide and styrene using Fréchet-type dendritic initiators

Polyarylether dendrons as macroinitiators for the "living"/controlled free radical copoly-merization of N-phenylmaleimide (PhMI) and styrene (St) have been demonstrated. The copoly-merization was carried out in bulk or anisole with CuBr/bipy catalyst at 100-130℃. It is found that the resulting copolymers possess predetermined molecular weights and narrower polydispersities (1.18 < Mw/Mn<1.32). The effects of reaction temperature and monomer feed on the copolymeri-zation kinetics were investigated in detail. By using the Fineman-Ross method, the apparent monomer reactivity ratios for the atom transfer radical copolymerization of PhMI and St were determined to be rphM1 = 0.0207, and rst = 0.0484, respectively.     

模板聚合——一类新的聚合方法

聚合方法的研究,在高分子合成化学中具有重要的地位。正是由于新聚合方法的不断出现,高分子化学的面貌才得以日新月异,新品种、新材料的出现才层出不穷。模板聚合(Template polymcrization)就是其中一类新聚合方法,它是在某些小分子晶体所提供的特定空     

HELIX SENSE-SELECTIVE COPOLYMERIZATION OF TRIPHENYLMETHYL METHACRYLATE WITH CHIRAL ANIONIC INITIATORS

Optically active copolymers of pairs of three monomers, triphenyl (methyl methacrylate)and one or two pyridyl substituted methyl methacrylate homologues, were obtained by helix-sense-selective copolymerization using complexes of organolithium with chiral ligand as anionicinitiators in toluene at low temperature. The copolymers obtained with (-)-sparteine (Sp) and(S,S)-(+)-and (R, R)-(-)-2, 3-dimethoxy-1, 4-bis (dimethylamino) butanes((+)-and (-)-DDB) complexes of organolithium showed low optical activity, but PMP complex with N, N-diphenylethyleneamine monolithium amide (PMP-DPEDA-Li) was effective in synthesizingcopolymers of high optical rotation ([α]_D~(25) about+320～1370°)which were comparable to thoseof relative homopolymers with one-handed helical structure.     

聚酰胺——聚对苯二甲酰对苯二胺的研究

详细地研究了对苯二甲酰-对苯二胺低温溶液缩聚时,各种反应条件对聚合体分子量的影响,获得了适合于液晶纺丝的高分子量聚合体,其η_(inh)可达5—7。结果表明,聚合体系的水份、单体克分子浓度、各种混合溶剂体系比对聚合体分子量有明显的影响。为获得高分子量聚合体,混合溶剂体系的最佳组成分别为:HMPA:DMAC=4:1(体积比)、HMPA:NMP=7:3 和 HMPA:THF=9:1。当水份含量大于100ppm时,将严重妨碍高分子量聚合体的得到。在缩聚反应初期,聚合体η_(inh)随时间迅速增长,两三分钟内出现凝聚现象,聚合转化率达100％。体系凝聚后缩聚反应仍然进行,聚合体仍有增长。     

STEREOREGULARITY OF POLY (METHYL METHACRYLATE) OBTAINED WITH CHIRAL ANIONIC COMPLEX INITIATOR

The stereoregular polymerization of methyl methacrylate (MMA) have been investigatedwith chiral anionic complex initiator[FILi-(-)SP]in toluene, THF and toluene/THF [1/1(v/v)]. The tacticities of PMMAs obtained in the three solvents have been found to be mainly asyndiotactic triads(s-PMMA)with content of 72.3, 67.7 and 71.4%,respectively.     

树状化-线形两亲嵌段聚合物的合成及自组装研究

合成了缩酮保护的一代甲基丙烯酸羟乙酯单体DHEMA(G1),通过顺序ATRP聚合方法,制备得到大分子引发剂PDHEMA(G1)-Br,再引发苯乙烯单体得到一代嵌段聚合物PDHEMA(G1)-b-PS.以PDHEMA(G1)-b-PS为反应前体,通过重复的缩酮保护和脱保护反应,进一步得到了二代和三代的树状化-线形两亲嵌段...