新引发体系引发MMA活性自由基聚合

近年来 ,关于活性自由基聚合的研究极为活跃 ,已经发现了多种基于增长链自由基被可逆钝化形成休眠种的活性自由基聚合方法[1,2 ] .它们主要包括引发转移终止剂 ( Iniferter) ,稳定自由基聚合( SFRP) ,原子转移自由基聚合 ( ATRP) ,可逆加成 -断链链转移聚合 ( RAFT)等 .其中 ATRP因其具有可聚合单体多 ,反应条件相对缓和等优点而成为该领域的研究热点 [3～ 5] .ATRP活性自由基聚合的实现主要是在过渡金属催化剂的作用下 ,通过循环往复的碳 -卤键的活化、加成、碳 -卤键的再形成而得到最终活性的聚合物 ,引发体系由引发剂、过渡金属…     

原子转移自由基聚合的最新研究进展*

原子转移自由基聚合(ATRP)是目前为止最具工业化应用前景的“活性”/可控自由基聚合之一。近年来对其广泛的研究使这一技术逐渐向着“提高可操作性”与“尽可能地减少金属催化剂用量”方面发展;与此同时,诞生了不同催化体系的ATRP衍生技术,如反向原子转移自由基聚合(RATRP)、正向反向同时引发的原子转移自由基聚合(SR&NI ATRP)、引发剂连续再生催化剂原子转移自由基聚合(ICAR ATRP)、电子转移生成催化剂的原子转移自由基聚合(AGET ATRP)和电子转移再生催化剂原子转移自由基聚合(ARGET ATRP)等多种基于ATRP的新方法。本文概述了这几种ATRP体系的发展历程与基本原理,并对其国内外的最新研究进展进行了综述。     

原子转移自由基聚合方法在纤维素及其衍生物改性方面的应用Ⅰ

原子转移自由基聚合反应(atom transfer radical polymerization,ATRP)是一种活性/可控的自由基聚合反应,是大分子设计的有效工具,利用ATRP可以合成各种组成和结构的聚合物,如均聚物、嵌段共聚物、梯度共聚物、接枝共聚物、星状聚合物、超支化聚合物等.近年来,ATBP还被用于纤维素及其衍生物的修饰改性.该方法解决了传统自由基接枝改性方法中存在的问题,不仅可以保持纤维素骨架的完整性,还可以得到不包含均聚物的纯接枝共聚物,而且接枝链的长度及分子量分布均可控.本文介绍了原子转移自由基聚合方法在纤维素及其衍生物改性方面的应用.     

用原子转移自由基聚合方法制备新型含有高分子金属配合物的无机-有机杂化材料

近年来,表面引发聚合制备聚合物刷,由于其能控制无机物表面性能,在材料科学方面有广泛的应用前景．在制备聚合物刷的一系列聚合方法中,“活性”／可控自由基聚合,尤其是原子转移自由基聚合(Atom Transfer Radical Polymerization,ATRP)得到广泛使用．它可获得分子量分布较窄的结构规整的聚合物,可将一些功能性的单体引入聚合物体系获得功能聚合物,     

原子转移自由基聚合及其催化引发体系研究进展

原子转移自由基聚合(ATRP)作为一种有效的"活性"/可控聚合可对聚合物进行分子设计,制备结构和相对分子质量可控的各类聚合物,具有潜在而广泛的研究价值。本文综述了ATRP的研究进展,特别是对传统ATRP催化引发体系、RATRP催化引发体系、AGET ATRP催化引发体系、SR&NI ATRP催化引发体系、ICAR ATRP催化引发体系、ARGET ATRP催化引发体系、杂化或双金属催化体系等的催化引发机理进行了详细的介绍。并综述了ATRP聚合中各种实施方法如本体聚合法、溶液聚合法、悬浮聚合法、乳液聚合法等的研究现状。     

原子转移自由基聚合(ATRP)在二氧化硅表面接枝中的应用

ATRP方法是在二氧化硅(SiO2)表面接枝聚合物的一种有效方法.通过硅烷偶联剂把ATRP引发剂键接到SiO2表面,然后进行表面ATRP聚合,可以在SiO2表面接枝各种均聚物、嵌段共聚物、超支化聚合物.聚合可以在有机溶剂或水中进行.把ATRP方法同其它聚合方法如氮氧稳定自由基聚合或开环聚合相结合,可以在SiO2表面接枝复杂结构的聚合物如V型嵌段共聚物、梳型共聚物等.SiO2表面ATRP聚合可以通过外加引发剂或外加二价铜来实现聚合可控.     

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     

甲基丙烯酸(N,N-二甲氨基)乙酯的自引发催化氧化聚合

作为一种自身还原性单体,甲基丙烯酸(N,N-二甲氨基)乙酯(DMAEMA)可与部分氧化剂构成氧化还原引发剂体系,并引发自身的聚合.为验证该假设,进行了以CuCl2络合物催化DMAEMA的本体氧化聚合.动力学研究表明,所得聚合物的分子量随着聚合时间的延长而逐渐增加.核磁波谱分析表明,低转化率下所得低聚物同时含有甲基丙烯酸酯末端和C-Cl端基,显示DMAEMA的二甲氨基(N-CH3)被CuCl2氧化成单体自由基(N-CH2·),并通过原子转移自由基聚合(ATRP)机理形成聚合物.由于叔胺广泛地用作ATRP的络合物,由此可见,在传统ATRP体系中,来自CuCl2/叔胺的氧化还原引发不可忽略.     

含有仲氨基团的甲基丙烯酸酯单体的原子转移自由基聚合研究

聚(4-甲基丙烯酰氧基-2,2,6,6-四甲基哌啶氮氧自由基)(PTMA)是一种具有应用前景的锂离子电池正极材料,一般通过2,2,6,6-四甲基哌啶醇-4-甲基丙烯酸酯(TMPM)的自由基聚合及进一步氧化来制备.但是TMPM的可控自由基聚合受制于其分子中的仲氨基团.通过对不同的引发剂和催化体系TMPM的原子转移自由基聚合(ATRP)进行了研究,得到了TMPM最优的ATRP聚合条件,为合成具有不同分子量或拓扑结构的自由基聚合物奠定了基础.     

含有热引发转移终止剂的引发体系在反向原子转移自由基聚合中的应用

原子转移自由基聚合 (ATRP)是实现活性聚合的一种颇为有效的途径 ,可以实现多种单体的活性自由基聚合 .反向原子转移自由基聚合 (ReverseATRP)的概念始提出于 1995年 ,是对传统ATRP的改进和拓展 .近年来关于此体系的引发剂的拓展、过渡金属及单体的适用性都得到了很大发展 .本文简要综述了我们研究组在反向原子转移自由基聚合方面的研究进展     

Alumina-supported iron catalyst - long-term study of the light product distribution in Fischer-Tropsch synthesis

Several models have been proposed to describe the carbon number product distribution and mechanism in Fischer-Tropsch synthesis (FTS). However, these models have not fully explained the product distribution and mechanism owing to the wide range and complexity of hydrocarbons in FTS. This study was conducted based on the Yao and Anderson-Schulz-Flory (ASF) carbon number product distribution models for light (C₁–C₆) hydrocarbon products of a Fe/Al₂O₃ catalyst. The product distribution based on the molar ratio of olefin to paraffin (O/P) and the neighboring olefins was also studied in order to better understand the mechanism in FTS and C₂ olefin deviation during FTS.Two sets of experiments (A and B) with different reaction conditions were conducted in microtubular fixed-bed reactors on the Fe/Al₂O₃ catalyst for 2249 h and 360 h, respectively. We found that the α values from the Yao and ASF carbon number product distribution models are relatively similar. The α values from the Yao carbon number product distribution plots are relatively constant, irrespective of the reaction conditions.Interestingly, it was also found that the secondary reactions of the C₂ olefin by re-adsorption to produce paraffins and long-chain olefins are dependent on the CO conversion and the reaction temperature during the FTS. Also, the product distribution of the neighboring olefins during the reduction condition gave a similar trend to what was observed for other reaction conditions. This result confirmed what was observed in the Yao and ASF carbon number product distribution of the olefins.     

Macroscopic solvation of molecules in excited states: An MCSCF model including solvent polarization effects-I

An MCSCF model including the effects of solvent polarization is developed. The model is applied within the limitations of INDO approximations to look into the dominant effects of solvent polarization on the electronic structure in the excited states of a model system (e.g.nπ ^* states of H₂CO). Important features of macroscopic solvation-induced reorganization of electron density and some consequence thereof are noted.     

量子化学模型方法在机械力化学中的应用

机械力化学作为一种无需溶剂的绿色化学技术得到广泛关注。然而,机械力化学反应机制需要从原子和分子尺度上深入理解力诱导的化学反应。在过去的20年中,量子化学模型方法在机械力化学机理研究中得到广泛应用,高精度量化计算可得到外力下变形分子的几何结构、能量、过渡态等诸多性质。本文介绍了目前机械力化学领域的主流量子化学模型的基本原理,同时也关注了这些模型方法在软件上的具体实现,并借助典型的案例阐述了量子化学模型在解释机械力化学机理中的作用与价值。     

A study of the influence of impurities when discriminating between the terminal and penultimate copolymerization models

We investigate the effect of the presence of reactive impurities during copolymerization on mathematical model discrimination and determine if impurities adversely affect the model discrimination process, depending on the criteria and response(s) used. Nonlinear mechanistic process models are employed in a multiresponse statistical discrimination scenario. The investigation also considers, via several case studies, the extremely interesting question of whether impurity effects could lead to incorrect choices about the copolymerization mechanism itself (terminal versus penultimate model). The answers to the above questions are that reactive impurities do affect the model discrimination process and, what is more, they may mislead researchers as to the choice of the copolymerization mechanism. The latter unexpected result is further illustrated with experimental data from the literature. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2319–2332, 2000     

非线性和时变参数时间序列模型及其在水质分析中的应用

时间序列分析是根据观测值建立数学模型，研究数据的内在规律，现有文献主要是介绍线性时间序列模型。研究表明化学分析数据很多涉及非线性时间序列，且具有时变参数特性。本文在研究线性、非线性时间序列模型基础上，提出一种具有时变参数特性的非线性时间序列模型。该模型用于加酸调ｐＨ的循环冷却水系统进行预报，可使ｐＨ值极差降低３～６倍，对保证水质稳定具有重要意义。     

蛋白质离子交换平衡模型

本文综述了蛋白质的离子交换平衡模型的研究进展，包括Langmuir模型、质量作用模型以及建立在双电层理论基础上平行板模型和表面过剩模型，分析比较了各模型的特点和存在的问题，对今后的研究方向进行讨论。     

Measurement and correlation of the solubility of genistin in eleven organic solvents from T = (283.2 to 323.2) K

The solubilities of genistin in pure solvents including tetrahydrofuran, acetone, ethyl acetate, acetonitrile, isopropanol, n-butyl alcohol, methanol, cyclohexane, n-hexane, chloroform and ethanol were determined by the high performance liquid chromatography (HPLC) analysis method at T = (283.2, 293.2, 303.2, 313.2 and 323.2) K. The fusion enthalpy of genistin was estimated by the group contribution method. The solubility data of genistin were correlated by the simplified thermodynamic model, the modified Apelblat model, λh model and NRTL (Non-Random Two-Liquid) model. The calculated values by all models were in good agreement with the experimental values and however, the NRTL model could give better correlation results than other three models.     

Nonlinear Dependence of Fish Bioconcentration on n-Octanol/Water Partition Coefficient

Abstract

The log-log relationship between the bioconcentration tendency of organic chemicals in fish and the n?octanol/water partition coefficients breaks down for very hydrophobic compounds. The use of parabolic and bilinear models allows this problem to be overcome. The QSAR equation log BCF = 0.910 log P - 1.975 log (6.8 10^?7 P + 1) - 0.786 (n = 154; r = 0.950; s = 0.347; F = 463.51) was found to be a good predictor of bioconcentration in fish.     

Simplistic modeling approach to heterogeneous dilute-acid hydrolysis of cellulose microcrystallites

The classic kinetic model for cellulose hydrolysis is often referred to as pseudo-homogeneous, a term revealing the insight that the process is actually heterogeneous. During the past 10–15 yr, the shortcomings of this model have been demonstrated in various studies and the interest in the heterogeneous aspects has increased. The present work presents a simplistic model in which the intrinsic, heterogeneous hydrolysis and transport rates are coupled by the assumption of a constant glucosidic surface concentration. The mechanisms affecting these two rates are largely unknown, but the model serves as a guideline for further exploration of the process.