N,N—二乙基二硫代氨基甲酸聚氯乙烯酯引发甲基丙烯酸甲…

用铜试剂（Ｎ，Ｎ－二乙基二硫代氨基甲酸钠）取代聚氯乙烯中的部分氯原子制备了Ｎ，Ｎ－二乙基二硫代氨基甲酸聚氯乙烯酯（ＰＶＣ－ＳＲ），研究了紫外光照下ＰＶＣ－ＳＲ引发甲基丙烯酸甲酯（ＭＭＡ）的聚合反应，考察了光照时间、单体浓度、ＰＶＣ－ＳＲ用量及官能度的影响。结果表明，ＰＶＣ－ＳＲ能有效地引发ＭＭＡ聚合，其产物是交联型接枝聚合物，且具有高接枝率和接枝效率。     

二乙基二硫代氨基甲酸铜电化学传感器的研究

研制了二乙基二硫代氨基酸铜电位型传感器，并考察了电极性能，该修饰电极对Ｃｕ＾２＋具有类能斯特响应。电极已应用于试样分析。     

反应介质对N，N－二乙基二硫代氨基甲酸苄酯引发丙烯酰胺聚合反应的影响

反应介质对Ｎ，Ｎ－二乙基二硫代氨基甲酸苄酯引发丙烯酰胺聚合反应的影响杨文君，沈家骢（青岛化工学院橡塑工程研究所，青岛，２６６０４２）（吉林大学化学系）关键词聚丙烯酰胺，溶剂效应，自由基聚合，引发－转移－终止剂近年来，具有结构的有机硫化物以其优良的Ｉｎ...     

反应介质对N,N-二乙基二硫代氨基甲酸苄酯引发丙烯酰胺聚合反应的影响

The effects of reaction medium (alcohol, dioxane, dioxane/alcohol)on the heterogenous polymerization of acrylamide initiated by BDC (benzyl diethyldiothiocarbate)were studied. The results showed that herterogenous polymerization differed from homogeneous solution polymerization initiated by BDCand did not have the character of living radical polymerization. The polarity of reaction medium affected the enolization of acrylamide obviously, and made the yield of polymer and molecular weight different from each other, behaving obvious solvent effects.The UVspectra of products and polymerization of acrylamide initiated by products, show that iniferter functional groups remained in products.     

二乙基二硫代氨基甲酸银光度法测定磷矿石中砷

近年来,随着我国磷矿石出口量的逐年增加,国外用户对磷矿石的质量要求也逐年提高,合同中加入了对铅、砷、汞等一些微量有害元素的限制。本法参照国家标准方法采用银盐法测定磷矿石中微量砷,并使用500g·L^-1柠檬酸溶液取代了原标准中使用的酒石酸溶液作掩蔽剂,有效地消除了磷矿石中Fe^3＋、Hg^2＋等共存离子的干扰。该法用于磷矿石中砷含量的测定,取得较满意的结果。     

甲壳胺接枝聚合反应的研究

本文是以过硫酸钾为引发剂，研究甲基丙烯酸甲酯（ＭＭＡ）与甲壳胺的接枝聚合反应．通过对不同脱乙酰度（ｄａ）甲壳胺（ＣＴＳ）的接枝聚合反应条件实验，研究了反应时间，温度，引发剂浓度和单体浓度对接枝聚合反应的影响，从中得到优选的反应条件．在相同条件下，比较不同脱乙酰度甲壳胺及Ｎ－取代甲壳胺的接枝聚合反应结果，表明：甲壳胺中氨基参与了接枝聚合反应的引发过程．     

二(N,N-二乙基二硫代氨基甲酸)烷基黄原酸合钴(Ⅲ)与二丙胺和二丁胺反应的动力学

本文采用分光光度法研究了在甲醇介质中(N,N-二乙基二硫代氨基甲酸)烷基黄原酸合钴(Ⅲ)与二丙胺,二正丁胺在298.2K～313.2K(R=Me,Et,n-Pr)的反应动力学及机理.结果表明对配合物是准一级反应,对二正丁胺是分数级.反应速率随着基团R的增加而减小,随着温度的增加而增加,随着溶剂中水含量的增大而增加.提出了一种含有前期平衡的反应机理.据此导出了一个能够解释实验事实的速率方程,求得了速控步骤的速率常数,并给出了相应的活化参数.     

N，N－二甲基对甲苯胺引发N－对甲苯基马来酰亚胺光聚合的引发机理

Ｎ，Ｎ－二甲基对甲苯胺引发Ｎ－对甲苯基马来酰亚胺光聚合的引发机理叶克强，董建华，丘坤元，冯新德（北京大学化学系，北京，１００８７１）关键词光引发聚合机理，电荷转移复合物，激基复合物，荧光淬灭，Ｎ，Ｎ－二甲基对甲苯胺，Ｎ－对甲苯基马来酰亚胺Ｎ，Ｎ－二甲...     

2-(N,N-二乙基二硫代氨基甲酰氧基)乙酸苄酯存在下苯乙烯光聚合

研究了２ Ｎ, Ｎ 二乙基二硫代氨基甲酰氧基乙酸苄酯（ Ｂｚ Ｄ Ｃ Ａ） 引发的苯乙烯光聚合反应,发现单体转化率和数均分子量（ Ｍｎ） 都随反应时间而增加,在反应时间相同时随着 Ｂｚ Ｄ Ｃ Ａ 浓度的增加单体转化率升高而 Ｍｎ 降低．聚苯乙烯（ Ｐ Ｓ） 的 Ｍｎ 同单体转化率成线性关系并同理论计算值符合得较好．以２ 甲基 ２ 亚硝基丙烷（ Ｍ Ｎ Ｐ） 为捕捉剂用（ Ｅ Ｐ Ｒ） 技术对聚合反应机理进行了研究．认为 Ｂｚ Ｄ Ｃ Ａ 引发的 Ｓｔ 光聚合是一个“活性”聚合过程     

偶氮基团引发PMMA在纳米TiO2表面接枝聚合研究

采用表面接枝反应的方法,在纳米TiO2上接枝偶联剂KH-560,进而通过酯化反应引入偶氮基团引发甲基丙烯酸甲酯发生自由基聚合反应,并通过IR、SEM、TEM、DSC和TG等测试方法研究了反应条件对复合粒子结构和性能的影响.结果表明,反应约60 min时,TiO2表面的接枝率达42.9%;当搅拌速率为1.0×104 r/min时,TiO2均匀分散在PMMA基体中;TiO2粒子的加入使得PMMA的热稳定性有了明显提高.     

过氧化二碳酸酯和N N-二羟烷基对甲苯胺体系引发甲基丙烯酸甲酯聚合

本文以过氧化二碳酸酯BPPD和芳叔胺DHET、DHPT、DMT、DMA组成的引发体系进行MMA聚合的研究。测定了聚合速率R_p,发现添加DHET、DHPT能促进MMA的聚合,缩短诱导期,提高R_p,其效果要比DMT、DMA为好。测定了E₃和聚合速率方程。由ESR谱和端基分析证实DHET、DHPT芳胺组分产生的自由基能引发单体聚合。     

Living Polymerization of N,N‐Diphenylacrylamide with Triisobutylaluminum

Summary: N,N‐Diphenylacrylamide was polymerized in a living fashion with triisobutylaluminum in THF at 0 °C. The polymerization results showed an increase of molecular weight proportional to the amount of monomer consumed and a first‐order kinetics at −78 °C. The intermediates obtained with excess initiator at −78 °C revealed that the polymerization was initiated through 1,4‐addition of hydride from a triisobutyl group in the triisobutylaluminum and then proceeded through aluminum‐oxygen bond interchange.

N,N‐Diphenylacrylamide was polymerized in a living fashion with triisobutylaluminum in THF at 0 °C.     

烯丙基氯化镁引发己二酸酐开环聚合

以烯丙基氯化镁引发己二酸酐开环聚合制备功能化的聚己二酸酐。考察了引发剂、温度、溶剂对聚合反应的影响.核磁端基分析表明开环聚合反应可能是通过酰氧键断裂,按“配位－插入”机理进行的。     

超声引发自由基聚合制备聚苯乙烯磺酸钠接枝炭黑

通过在超声环境下,单体苯乙烯磺酸钠发生自由基聚合,生成的聚合物长链自由基被炭黑表面捕获,制备聚合物接枝炭黑.借助红外光谱、热重、粒度、透射电镜和zeta电位分析对该接枝炭黑进行表征.同时研究超声条件对接枝率的影响.结果表明,单体聚合并接枝到炭黑表面,同时炭黑的附聚体和一些大的聚集体结构被超声破碎,平均粒径大为减小;在300W超声波输出功率下,反应1h后,接枝率达到12.8%并趋于稳定.由于接枝分子链上磺酸基的存在,接枝炭黑在水中的分散稳定性显著改善.     

Photopolymerization of Cyclohexene Oxide Initiated with Iron-arene Complex

Two iron-arene complex photoinitiators with different substituents in arene ligands were synthesized, their activities in initiating photopolymerization of cyclohexene oxide (CHO) were compared with that of IRGACURE 261, a commercialized photoinitiator from Ciba-Geigy. A higher activity was found when the arene ligand was substituted with a stronger electron donating group. For the system initiated by IRGACURE 261 the concentration of active centers in CHO polymerization was determined and it was found that the concentration is maximum at around 35℃. The post (dark) polymerization was significant, the polymerization yield decreased with the increase of irradiation temperature and increased with the increase of post polymerization temperature. The results are interpreted based on the mechanism proposed by Lohse, et al..     

Atom Transfer Radical Polymerization of Methyl Methacrylate High Efficiently Initiated by Azo-containing Iniferter

Two novel azo-containing iniferters, (4,4′-(diazene-1,2-diyl) bis(4,1-phenylene) bis(2-(diethylca-rbamothioylthio)-2-methylpropanoate (BDCMP) and 4-((4-bromophenyl)diazenyl)phenyl-2-(diethylcarbamothioylthio)-2-methylpropanoate (PDCMP) were synthesized and used successfully as the initiators for atom transfer radical polymerization of methyl methacrylate (MMA). The kinetic plots were first order and the molecular weights of the polymers with narrow molecular weight distributions increased with the monomer conversions. Furthermore, the results showed that the apparent initiation efficiencies (f was close to 0.90 defined as M _n(th)/M _n(GPC)) of BDCMP and PDCMP were both higher than that (f was lower than 0.5) of 2-N,N-(diethylamino)dithiocarboyl-isobutyrate (EDCIB), which was reported previously by us (14 Zhang, W., Zhu, X. L., Cheng, Z. P. and Zhu, J. 2007. J. Appl. Polym. Sci., 106: 230–7. [Crossref] , [Google Scholar]). The obtained mono- and bi-functional PMMAs containing azo and N,N-diethyldithiocarbamate (DC) groups were confirmed by ¹H-NMR and ultraviolet absorption spectra, respectively. The block copolymer, poly (methyl methacrylate)-b-polystyrene (PMMA-b-PS), was also successfully prepared via the ATRP chain-extension experiment using the obtained PMMA as a macroinitiator.     

二价芳氧钐配合物催化苯乙烯聚合

二价芳氧钐配合物催化苯乙烯聚合齐贵中扈晶余＊沈琪（中国科学院长春应用化学研究所稀土化学与物理开放实验室长春１３００２２）（苏州大学化学系苏州）关键词钐配合物，苯乙烯，聚合１９９６－０５－１８收稿，１９９６－１０－３０修回国家科委攀登计划及国家自然科学...     

二苯基碘鎓盐引发氨酯型乙烯基醚热聚合

合成了2种固态氨酯型乙烯基醚PUE1和PUE2,并对其结构和性能进行了表征.研究发现,二芳基碘六氟磷酸盐(PI810)能引发PUE1和PUE2发生阳离子热聚合,热聚合温度远低于PI810的纯态热分解温度,且聚合转化率很高.初步认为热聚合机理是富电子的乙烯基醚双键和缺电子的二苯基碘盐阳离子之间形成中间态电荷转移复合物,降低了二苯基碘盐的热分解温度,进而生成引发活性种乙烯基醚阳离子自由基或质子酸,引发乙烯基醚的阳离子聚合反应.