Study on the spin probe‐added polymeric dense membranes by 13C solid‐state nuclear magnetic resonance spectroscopy

This article is a duplicate of an article previously published in the Journal of Applied Polymer Science, Vol. 99, No. 6, March 15, 2006, pp. 3062‐3069 http://doi.wiley.com/10.1002/app.22908 . We regret any inconvenience this may have caused.     

A replicated investigation of nitroxide‐mediated radical polymerization of styrene over a range of reaction conditions

A comprehensive experimental investigation of nitroxide‐mediated radical polymerization (NMRP) of styrene using 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) as controller is presented. Polymerizations with a bimolecular initiator (benzoyl peroxide; BPO) were carried out at 120 and 130°C, with TEMPO/BPO molar ratios ranging from 0.9 to 1.5. Results indicate that increasing temperature increases the rate of polymerization while the decrease in molecular weights is only slight. It was also observed that increasing the ratio of TEMPO/BPO decreased both the rate of polymerization and molecular weights. Probably for the first time in the history of such investigations, the paper contains a comprehensive database, appropriate for parameter estimation in aid of future modelling studies, since it comes from a systematic data collection containing independent replication.     

TEMPO and Carboxylic Acid Functionalized Imidazolium Salts/Sodium Nitrite: An Efficient,Reusable, Transition Metal‐Free Catalytic System for Aerobic Oxidation of Alcohols

An effective catalytic system comprising a 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) functionalized imidazolium salt ([Imim‐TEMPO]⁺ X⁻), a carboxylic acid substituted imidazolium salt ([Imim‐COOH]⁺ X⁻), and sodium nitrite (NaNO₂) was developed for the aerobic oxidation of aliphatic, allylic, heterocyclic and benzylic alcohols to the respective carbonyl compounds with excellent selectivity up to >99%, even at ambient conditions. Notably, the catalyst system could preferentially oxidize a primary alcohol to the aldehyde rather than a secondary alcohol to the ketone. Moreover, the reaction rate is greatly enhanced when a proper amount of water is present. And a high turnover number (TON 5000) is achieved in the present transition metal‐free aerobic catalytic system. Additionally, the functionalized imidazolium salts are successfully reused at least four times. This process thus represents a greener pathway for the aerobic oxidation of alcohols into carbonyl compounds by using the present task‐specific ionic liquids in place of the toxic and volatile additive, such as hydrogen bromide, bromine, or hydrogen chloride (HBr, Br₂ or HCl), which is commonly required for the transition metal‐free aerobic oxidation of alcohols.     

Synthesis and reactivity of functionalized alkoxyamine initiators for nitroxide‐mediated radical polymerization of styrene

The synthesis and examination of different functionalized (2,2,6,6‐tetramethyl‐1‐piperidinyloxy free radical) TEMPO‐containing alkoxyamine initiators for nitroxide‐mediated radical polymerization of styrene are reported. Initiators with ester and carbonate functional groups were synthesized by a low‐temperature radical‐abstraction reaction of the functionalized ethylbenzene in the presence of TEMPO to introduce the functional groups onto the initiating chain‐end of polystyrene. An initiator with two alkoxyamine groups symmetrically located at each end of a carbonate bond was also synthesized and used for nitroxide‐mediated styrene polymerization. Styrene polymerization using these initiators followed first‐order kinetics up to approximately 60 min at 140 °C or 30% monomer conversion. Alkoxyamines bearing an acetoxy or tert‐butylcarbonate group at the p‐position of 1‐(2,2,6,6‐tetramethyl‐1‐piperidinyloxy)ethylbenzene behave in a similar way to the unfunctionalized initiator. With an initiator containing two alkoxyamine groups, the resulting polymer molecular weight was twice that of the polymer obtained from initiators with only one alkoxyamine group, as expected from propagation from both chain‐ends. Upon hydrolysis of the carbonate bond, it was revealed that equivalent polymer chain growth occurred from each alkoxyamine site in the difunctional initiator. Copyright © 2003 Society of Chemical Industry     

TEMPO催化醇氧化反应的最新研究进展

有机小分子催化剂2,2,6,6-四甲基哌啶-1-氧自由基（TEMPO）催化醇的氧化,反应条件温和,具有高活性和高选择性,成为醇选择氧化的一个重要方法。综述了近几年TEMPO催化醇氧化反应的发展过程及其固定化方法的研究进展。     

Grafting of polystyrene branches to polyethylene and polypropylene

Polyethylene (PE) and polypropylene (PP) were reacted with benzoyl peroxide (BPO) and 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) to prepare PE‐TEMPO and PP‐TEMPO macroinitiators, respectively. Molecular weight of PP decreased, whereas that of PE increased during the reaction with the BPO/TEMPO system. Polystyrene (PS) branches were grafted to PE and PP backbone chains as a result of bulk polymerization of styrene with the PE‐TEMPO and PP‐TEMPO macroinitiators. A significant amount of PS homopolymer was produced as a byproduct. Weight of the resulting PE‐g‐PS and PP‐g‐PS increased with the polymerization time up to 20 h and then leveled off. Melting point of PE and PP domains in PE‐g‐PS and PP‐g‐PS, respectively, lowered as the content of PS in the copolymers increased. However, glass transition of the copolymers was almost identical with that of PS homopolymer, indicating that the constituents in the copolymers were all phase‐separated from each other. In scanning electron microscopy of the incompatible PE/PS, PP/PS, and PE/PP/PS compounded with PE‐g‐PS and PP‐g‐PS, any clear indication of enhanced adhesion between the phases was not observed. However, phase domains in the blends were, nevertheless, reduced significantly to raise mechanical properties such as maximum stress and elongation at break by 20–75%. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1103–1111, 2002     

Activation of Dioxygen by Cobaloxime and Nitric Oxide for Efficient TEMPO‐Catalyzed Oxidation of Alcohols

The aerobic oxidation of alcohols to their corresponding carbonyl compounds could be efficiently accomplished by using the combination of cobalt nitrate, dimethylglyoxime and 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO) as a novel catalytic system, and various alcohols including primary and secondary benzylic, allylic and aliphatic alcohols could be quantitatively converted to the corresponding aldehydes or ketones at 70 °C under 0.4 MPa dioxygen pressure in dichloromethane. During the oxidation, the in situ generated cobaloxime and nitric oxide (NO) were responsible for the activation of dioxygen, respectively, thereby, two concerted catalytic routes exist: cobaloxime‐activating‐dioxygen TEMPO‐catalyzed and NO‐activating‐dioxygen TEMPO‐catalyzed aerobic oxidation of alcohols.     

聚苯乙烯负载TEMPO催化醇的选择性氧化

将4-羟基-TEMPO通过醚键负载于聚苯乙烯氯球上制得负载TEMPO氯球(TEMPO-PS),考察了TEMPO-PS/CuCl体系催化苄醇选择性氧气氧化的性能。结果表明,在离子液体[bmi m][PF6]中,TEMPO-PS/CuCl体系对各种苄醇均有较好的催化活性。催化体系经3次循环使用活性无明显降低。     

低温等离子体辐射聚氨酯表面自由基浓度的研究

利用TEMPO（2，2，6，6-四甲基哌啶-1-氧自由基）法测定了经氮气低温等离子体处理后的聚氨酯膜表面自由基的浓度，而后引发聚氨酯与丙烯酸的接枝聚合以验证TEMPO法的可行性，探讨了等离子处理条件对自由基浓度和接枝率的影响、实验结果表明，自由基浓度的测定值与实验接枝率的变化规律基本吻合。     

TOCNF与磁性羧甲基壳聚糖纳米粒子复合物的制备及吸附Pb2+的特性

水体中铅污染对环境及人的健康安全造成了极大的危害。本文将四甲基呱啶（TEMPO）氧化的纤维素纳米纤维（TEMPO-oxidized cellulose nanofibers,TOCNF）与磁性羧甲基壳聚糖纳米粒子（magnetic carboxymethyl chitosan nanoparticles,MCCN）交联复合制备一种经济高效且对环境无毒害的Pb²⁺吸附剂,对复合前后的材料进行结构表征。通过单因素实验研究pH、Pb²⁺初始浓度、吸附时间及温度对Pb²⁺吸附效率的影响,确定最优吸附条件后比较TOCNF/MCCN及TOCNF对Pb²⁺的吸附效果,研究复合材料对Pb²⁺的吸附特性。研究结果表明,Fe₃O₄成功被羧甲基壳聚糖纳米粒子包裹并与TOCNF交联复合,在最优吸附条件（pH=5,Pb²⁺初始浓度为100mg/L,吸附时间为240min,常温下进行实验）下,TOCNF/MCCN吸附Pb²⁺的饱和容量为193.5mg/g,比TOCNF高了近一倍。复合吸附剂吸附Pb²⁺的过程更符合准二级动力学方程,说明决定吸附速率的主要是化学吸附。等温吸附方程的相关系数R²表明,Langmuir方程能更好地拟合吸附过程,说明复合吸附剂对Pb²⁺的吸附主要是表面基团的单分子层吸附。通过线性方程的斜率计算得到的理论饱和吸附量为201.1mg/g,与实际值差3.8%,经过5次解吸再吸附的过程,吸附剂的吸附效率仅下降了13%,表明该吸附剂有良好的可再生性,具有很好的应用前景。