原子转移自由基聚合(ATRP)在星形聚合物合成中的应用

综述了近10 年来采用原子转移自由基聚合(ATRP) 法合成星形聚合物的研究进展。从聚合单体、引发剂、聚合方法和反应条件以及聚合物性质等方面讨论了原子转移自由基聚合在星形聚合物合成中的应用,并根据聚合方法和引发剂对各种反应进行了分类。对原子转移自由基聚合技术在合成功能性复杂星形聚合物中的应用进行了展望。     

一种新型香豆素酮可见光敏化染料的合成及其光引发性质的研究

高效的可见光光敏引发体系是目前光聚合研究中的重要领域.3,3′-二(7-二乙胺基)香豆素酮(R)已被公认为一种高效的可见光聚合敏化染料,并可以与Ar⁺激光488 nm波长匹配.本文新合成了一种染料3-(4-二乙胺基-苯丙烯酰基)-7-二乙胺基香豆素(S).实验发现在普通碘钨灯照射下,S/邻氯六芳基双咪唑(HABI)体系具有比已有高效染料R/HABI体系更快的光漂白速度和更高的引发聚合效率,是一种新型高效的可见光光敏聚合引发体系.而且S在不同溶剂中的最大吸收波长在452～489 nm之间,比R红移16～30 nm,因此该体系可以更好地与Ar⁺ (488 nm)激光器匹配.本文对该染料的光敏化机理进行了探讨.     

The effect of initiators and oxidants on the morphology of poly [(±)‐2‐(sec‐butyl) aniline] a chiral bulky substituted polyaniline derivative

The nano and micro sphere synthesis of chiral bulky substituted polyaniline from monomer (±)‐2‐sec‐butylaniline in bulk and template‐free method (rapid mixing) was done successfully using ammonium peroxydisulfate (APS) and FeCl₃·6H₂O as oxidants. The effect of initiators such as p‐phenylendiamine and 1,4‐benzenediamine, temperature and concentration of monomer on morphology is demonstrated by scanning electron microscopy (SEM) images. The nano and micro sphere morphology was obtained using initiators. Smallest particles were achieved when 1,4‐benzenediamine was used as initiator in the presence of FeCl₃·6H₂O as oxidant. By increasing the concentration of monomer more uniform spheres were obtained. Characterization was made via FT‐IR, UV–Vis, ¹H and ¹³C‐NMR spectroscopy. Elemental analysis and electrical conductivity of products are also presented. All analysis data are in good agreement with nigraniline oxidation state of polyaniline. Copyright © 2015 John Wiley & Sons, Ltd.     

N-溴代丁二酰亚胺在有机反应中的应用进展

N-溴代丁二酰亚胺(NBS)是有机反应中常用的试剂, 近几年来在多种有机反应中的应用都有了新的研究进展. 综述了其作为反应过程中的催化剂、氧化剂、选择性溴代试剂以及聚合反应引发剂等方面最新的研究成果.     

Peroxide-initiated condensation of carboranes-12 with 1,2-dichloroethylene

The interaction of carboranes-12 with 1,2-dichloroethylene was investigated at 150–200°C in the presence oftert-butyl peroxide as an initiator.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, Moscow 117813. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 1017–1019, April, 1992.     

离子型遥爪聚合物分子参数的控制(Ⅰ)

本工作建立了由反应速率常数和反应初始条件以及单体转化率计算离子型遥爪聚合物的分子参数的方法,从而为各种不同类型的双官能团活性聚合反应的调节和控制提供了一定的理论基础。本工作以萘-钠(或萘-锂)为引发剂的阴离子型聚合物反应为例,将一系列单体转化率的数值代入标准程序进行具体计算,通过图和表,表明了各种分子参数随单体转化率变化的规律。     

用新型水溶性偶氮引发剂引发二甲基二烯丙基氯化铵的聚合反应

偶氮双脒式丙烷二盐酸盐在水介质中引发的二甲基二烯丙基氯化铵聚合，其引发速率较用过硫酸铵引发的快，转化率，分子量也较高。对反应助剂Ｎａ４ＥＤＴＡ和水介质的ＰＨ值对两引发体系的影响进行了研究。计算出在绝热聚合条件下三种引发体系的活化能。     

3-氯-2-氯甲基-1-丙烯引发苯乙烯原子转移自由基聚合的研究

原子转移自由基聚合(ATRP)是一种活性自由基聚合方法,通过它可以合成结构可控的官能性聚合物[1].双官能性聚合物是制备嵌段聚合物[2]和模型网络的前驱体[3,4],具有较大的理论和应用价值,寻求新的双官能引发剂以获得末端官能性聚合物已经成为当前ATRP研究领域的重要研究方向之一     

Comparison of Structure,Morphology, and Properties of Miktoarms Star Styrene-Butadiene Rubber and Star-Shaped Styrene-Butadiene Rubbe/Polybutadiene Rubber Blends

Four miktoarms star-shaped polybutadiene-Sn-poly(styrene-butadiene) rubber (MSS-PB-PSBR) with 1,1-diphenylhexyl at the ends of the arms were prepared by two different coupling techniques. One technique was a one-step technology, from which two miktoarms star styrene-butadiene rubbers, called AMSS-PB-PSBR, were obtained in which the four arm stars had varying ratios of PB:PSBR arms; another was a two-step technology, from which another two miktoarms star styrene-butadiene rubbers, called BMSS-PB-PSBR, were obtained in which all consisted of PB-Sn-(PSBR)₃ stars. The molecular structure parameters and morphology-properties of the four MSS-PB-PSBR were determined and studied, and compared with that of a star-shaped styrene-butadiene rubber (S-SSBR)/poly butadiene rubber (PBR) blend. The results showed that the total coupling efficiency (the ratio of the total number of polymer chains (arms) coupled by SnCl₄ to that of the total number of polymer chains) of the MSS-PB-PSBR was higher than 60%. However, the coupling efficiency of the polybutadiene arms of BMSS-PB-PSBR was obviously higher than that of the AMSS-PB-PSBR. Compared with the S-SSBR/PBR blend, MSS-PB-PSBR had a more uniform distribution of the PB phase and a smaller phase size of PB. It was found that MSS-PB-PSBR composites filled with carbon black (CB) had a lower Payne effect than the S-SSBR/PBR/CB composite, with the BMSS-PB-PSBR/CB composites being especially lower. The BMSS-PB-PSBR/CB composites had higher mechanical properties and lower rolling resistance than the AMSS-PB-PSBR/CB composites due to the high coupling efficiency of the polybutadiene arms; the results indicated that the two-step technology was better than the one-step technology for preparing the tread material of “green” tires.