光引发氮氧自由基调控聚合反应研究进展

氮氧自由基调控聚合(NMP)是制备微观结构可控(如窄分子量分布)的聚合物材料最主要的技术手段之一。在过去的二十年间,NMP取得了相当大的成就,实现了MMA、n-BA、丙烯酰胺,二烯烃和丙烯腈等多种单体的可控/"活性"聚合,分子量分布达到1.1以下,同时利用NMP制备了具有既定结构的聚合物,如嵌段聚合物、接枝聚合物、星形聚合物和梳形聚合物等。而与光聚合技术的结合,使NMP聚合取得了更大的突破,实现了室温下的光可控/"活性"聚合,且大大提升了聚合反应速率。近年来光引发氮氧自由基调控聚合的研究进展主要集中在光敏化技术方面,包括分子内敏化和分子间敏化,本文对其各自的敏化机理和研究成果进行总结和评述,希望有助于国内读者了解这方面研究工作的状况,促进国内相关研究工作的发展。     

NIPAM共聚物多孔水凝胶的光引发RAFT合成及其溶胀性能

采用光引发可逆加成-断裂链转移(RAFT)方法,在室温下先合成了链端含有三硫代碳酸酯基的大分子链转移剂聚(N,N'-二甲基丙烯酰胺)(PDMAM),然后与N-异丙基丙烯酰胺(NIPAM)、N,N'-二甲基双丙烯酰胺(BIS)交联共聚合,并通过聚乙二醇的制孔作用制得PNIPAM-g-PDMAM梳型/多孔水凝胶.采用FTI...     

Synthesis of natural rubber-g-maleic anhydride and its use as a compatibilizer in natural rubber/short nylon fiber composites

Natural rubber grafted maleic anhydride (NR-g-MAH) was synthesized by mixing maleic anhydride (MAH) and natural rubber (NR) in solid state in a torque rheometer using dicumyl peroxide (DCP) as initiator. Then the self-prepared NR-g-MAH was used as a compatibilizer in the natural rubber/short nylon fiber composites. Both the functionalization of NR with MAH and the reaction between the modified rubber and the nylon fiber were confirmed by Fourier transform infrared spectroscopy (FTIR). Composites with different nylon short fiber loadings (0, 5, 10, 15 and 20 phr) were compounded on a two-roll mill, and the effects of the NR-g-MAH on the tensile and thermal properties, fiber-rubber interaction, as well as the morphology of the natural rubber/short nylon fiber composites were investigated. At equal fiber loading, the NR-g-MAH compatibilized NR/short nylon fiber composites showed improved tensile properties, especially the tensile modulus at 100% strain which was about 1.5 times that of the corresponding un-compatibilized ones. The equilibrium swelling tests proved that the incorporation of NR-g-MAH increased the interaction between the nylon fibers and the NR matrix. The crosslink density measured with NMR techniques showed that the NR-g-MAH compatiblized composites had lower total crosslink density. The glass transition temperatures of the compatibilized composites were about 1 K higher than that of the corresponding un-compabilized ones. Morphology analysis of the NR/short nylon fiber composites confirmed NR-g-MAH improved interfacial bonding between the NR matrix and the nylon fibers. All these results signified that the NR-g-MAH could act as a good compatilizer of NR/short nylon fiber composites and had a potential for wide use considering its easy to be prepared and compounded with the composites.     

DEPN调控自由基聚合研究进展

氮氧自由基调控聚合是通过在氮氧自由基与增长链自由基之间建立一种动态的热力学可逆平衡来控制聚合反应动力学和聚合产物的分子量及其分布的聚合方法。SG1的出现拓展了氮氧自由基调控聚合（NMP）的研究领域,从聚合体系的扩展到动力学研究的深入,进一步完善了聚合反应动力学调控理论的基础研究,确立了实验条件及影响因素。本文主要综述了...     

甲基丙烯酸正丁酯正相微乳液可控/“活性”光聚合动力学研究

以末端含溴原子的光引发剂2-溴异丁酰氧基-2-甲基-1-苯基甲酮(HMPP-Br)为引发剂,2,2,6,6-四甲基哌啶-1-氧自由基(TEMPO)和2,2,6,6-四甲基哌啶醇(TMP)为调控剂,采用光聚合方法研究了甲基丙烯酸正丁酯(n-BMA)/十二烷基硫酸钠(SDS)/水/正丁醇 O/W型正相微乳液体系的光聚合反应动力学.结果表明,改性后的引发剂具有一定的引发活性,且聚合微乳液体系较稳定,聚合反应获得了良好的ln[M]₀/[M]与时间、数均分子量与转化率之间的线性动力学关系,制备了分子量分布较窄的Poly(n-BMA)均聚物.