Properties of poly(n‐butyl methacrylate) prepared by reverse atom transfer radical polymerization in an aqueous dispersed system

Reverse atom transfer radical polymerization (ATRP) of n‐butyl methacrylate (BMA) in waterborne media using Cu(II) complexes with azo initiators (i.e., reverse ATRP) was conducted. The influence of several factors, such as surfactant, catalyst, and reaction time, on the stability of the emulsion, the particle size, the morphology of the emulsion particles, and the control of the polymerization was investigated. The results showed great differences between ATRP and conventional emulsion polymerization, especially the nucleation mechanism and the kinetics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1542–1547, 2003     

Simulation of continuous solid‐phase polymerization of nylon 6,6. III. Simplified model

Solid‐phase polymerization (SPP) reactors are used to increase the degree of polymerization (DP) during nylon 6,6 production. In previous articles, a reactor model with partial differential equations (PDEs) in time and two spatial dimensions was developed to describe dynamic changes in polymer property profiles (DP, temperature, and moisture content) over the height of the reactor and within the polymer particles. In the current article, a simplified model is developed by deriving appropriate expressions for heat‐ and mass‐transfer coefficients and performing a lumped heat‐ and mass‐transfer analysis. Using this approach, the radial dimension is removed from the PDEs, so that the effort required to solve the model equations is substantially reduced. Predictions of the complex and simplified models are compared through simulation of two different start‐up processes. Good agreement between simplified and complex models is obtained, indicating that the simplified model can be used in place of the complex model if the polymer properties profiles within individual particles are not of particular concern to the model user. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3701–3712, 2003     

Preparation and characterization of new photoactive polyamides containing 4‐(4‐dimethylaminophenyl)urazole units

4‐(4‐dimethylaminophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( DAPTD ) was prepared from 4‐dimethylaminobenzoic acid in five steps. The compound DAPTD was reacted with excess acetyl chloride in N,N‐dimethylacetamide (DMAc) solution and gave 1,2‐bisacetyl‐4‐[4‐(dimethylaminophenyl)]‐1,2,4‐triazolidine‐3,5‐dione as a model compound. Solution polycondensation reactions of monomer with succinyl chloride (SucC), suberoyl chloride (SubC), and sebacoyl chloride (SebC) were performed under conventional solution polymerization techniques in the presence of triethylamine and pyridine as a catalyst in N‐methylpyrrolidone (NMP) and led to the formation of novel aliphatic polyamides. These novel polyamides have inherent viscosities in the range of 0.09–0.21 dL/g in N,N‐dimethylformamide (DMF) at 25°C. Fluorimetric studies of the model compound as well as polymers were performed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 947–954, 2007     

不同官能度环氧树脂的阳离子光固化研究

对4种不同官能度的环氧树脂在紫外光辐照下用一种二苯基碘钅翁盐或两种二烷基苯甲酰锍盐光引发剂进行阳离子光固化的体系作了系统的研究。研究结果表明,二氨基二苯甲烷环氧树脂AG-80不能阳离子光固化,而E-51,711和TDE-85均可在二苯基碘钅翁六氟磷酸盐或1-甲基-1-十二烷基苯甲酰甲基六氟锑酸锍盐作用下进行紫外光引发阳离子聚合,其中二苯基碘钅翁六氟磷酸盐引发E-51环氧树脂阳离子光固化的效果最好,该树脂体系可用做紫外光固化复合材料的树脂基体。研究还发现,在停止紫外光辐照后,由于阳离子聚合链终止困难而使碘钅翁盐引发的环氧树脂光固化体系存在后固化现象,后固化速度与后固化时的温度有关。     

两性聚丙烯酰胺的合成方法及应用进展

结合国内外研究情况，从技术路线和实施方法两个角度着重阐述了制备两性聚丙烯酰胺的方法，同时简单介绍了其应用情况，并对今后的研究工作提出了一些建议。     

拟活性阳离子聚合——异丁烯与苯乙烯嵌段共聚物的合成与表征

以丙烯酸正丁酯-四氯化钛-二甲基亚砜为引发体系,于二氯甲烷中、-45℃下进行异丁烯与苯乙烯的拟活性阳离子嵌段共聚反应。结果表明,选择适当的反应条件,可得到两单体的共聚效率为50％,共聚物中平均苯乙烯结合量为31.7％(质量),分子量为3万,分子量分散指数约为1.8的嵌段共聚物。     

A Semi‐Batch Process for Nitroxide Mediated Radical Polymerization

Summary: A semi‐batch process using nitroxide mediated polymerization, was explored for the design of low molecular weight solvent‐borne coatings, typical of those used in the automotive industry. While living radical polymerization (LRP) offers many advantages in the control of polymer chain microstructure that may confer important physical and chemical property benefits to coatings, adapting LRP to a semi‐batch process poses significant challenges in the design and operation of the process. Using styrene monomer, various two‐component initiating systems (free radical initiator, 4‐hydroxy‐TEMPO) were studied to understand the effects of different initiators on the course of polymerization. In addition, an alkoxyamine was synthesized and used as the initiating source. The initiators Luperox 7M75 and Luperox 231 give higher polymerization rates and reasonable control over polymerization, while benzoyl peroxide (BPO), Vazo 67, and the alkoxyamine are less effective. The number of polymer chains in the final product is always less than the theoretical value, reflecting poor initiation efficiency, probably resulting from undesirable termination reactions that become important due to the nature of the semi‐batch process. Adding camphorsulfonic acid (CSA) or charging initiator concurrently with monomer during semi‐batch feed, can increase the polymerization rate while maintaining the living character of the polymerization. The copolymerization of styrene and butyl acrylate is also shown to exhibit living character.

Schematic representation of the exchange reaction to produce N‐TEMPO capped polymer chains.     

聚乳酸的熔融聚合法的改进研究

采用熔融聚合法合成聚乳酸,对实验条件进行了优化选择。筛选出SnC l2为最适宜催化剂进行熔融聚合。最佳工艺条件为:催化剂用量为0.5%质量分数,反应温度为180℃,反应时间7.5 h,同时利用搅拌与鼓泡真空法使缩聚后期体系粘稠大搅拌脱水困难问题进一步得到解决,使熔融聚合产物的粘均分子量Mη达83483。     

Bulk free radical polymerizations of methyl methacrylateunder non-isothermal conditions and with intermediate additionof initiator: Experiments and modeling

Experimental data on the monomer conversion, x_m, and the weight average molecular weight, M_w, have been generated under several isothermal and non-isothermal conditions for the polymerization of methyl methacrylate in a rheometer-reactor assembly. The non-isothermal results, in particular, can be used to provide more stringent tests of kinetic models than isothermal data alone. A simple empirical model has been used to describe this system that accounts for the gel (Trommsdorff) and glass effects. The model involves only x_m and the temperature, and is quite general. The model parameters are tuned using only three sets of isothermal data. Good agreement is found between the experimental results and model predictions for a whole variety of experimental conditions, including non-isothermal operation and with intermediate addition of initiator. Because of its generality, this model is quite suitable for use for on-line optimizing control as well as for describing industrial reactors.     

环保型反应性乳化剂在水性木器乳液聚合中的应用

介绍了环保型反应性乳化剂ADEKA?REASOAP?SR-10、ER-30的结构和特性,重点分析了反应性乳化剂在水性木器乳液聚合中的应用及其对聚合物性能的影响。实验证明,应用反应性乳化剂所得的聚合物性能要远远优于非反应性乳化剂所得聚合物性能,而且应用了非离子反应性乳化剂所得的聚合物性能要优于单独使用阴离子反应性乳化剂所得聚合物性能。最后预测了环保型反应性乳化剂的良好应用前景。