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41.
Govindarajan Sankar A. Sultan Nasar 《Journal of polymer science. Part A, Polymer chemistry》2007,45(8):1557-1570
A series of substituted N‐methylaniline‐blocked polyisocyanates based on 4,4′‐methylenebis(phenyl isocyanate) and poly(tetrahydrofuran) were prepared and characterized thoroughly with FTIR, 1H NMR, and 13C NMR spectroscopy methods. Compared with unsubstituted N‐methylaniline, a blocking agent with an electron‐releasing substituent at the para position took a shorter time, whereas those with an electron‐releasing substituent at the ortho position or an electron‐withdrawing substituent at the ortho and para positions took longer times for the blocking reaction. The thermal dissociation reactions of blocked polyisocyanates were carried out with an FTIR spectrophotometer attached to hot‐stage accessories under dynamic and isothermal conditions. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate the deblocking kinetics and activation parameters. The cure times of blocked polyisocyanates with hydroxyl‐terminated polybutadiene were also determined. The deblocking temperatures, the results of cure‐time studies, and the kinetic parameters revealed that the thermal dissociation of the N‐methylaniline‐blocked polyisocyanates was retarded by electron‐donating substituents and facilitated by electron‐withdrawing substituents. The action of N‐methylanilines as blocking agents for isocyanate was explained by the formation of a four‐center, intramolecularly hydrogen‐bonded ring structure during the thermal dissociation of the blocked polyisocyanates. The formation of such a hydrogen‐bonded ring structure was confirmed and supported by variable‐temperature 1H NMR studies and entropy parameters, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1557–1570, 2007 相似文献
42.
V. V. AntiĆ M. P. AntiĆ M. N. Govedarica P. R. DvorniĆ 《Journal of polymer science. Part A, Polymer chemistry》2007,45(11):2246-2258
The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10−6 to 3.1 × 10−5 mol Pt/mol CHCH2. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10−6 mol of Pt per mol of CHCH2, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH2 groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007 相似文献
43.
陈明旦 《厦门大学学报(自然科学版)》1996,35(1):86-89
采用快速BASIC及其工具库编写一个用途广泛的引导程序,它具有将各类不同程序的运行或变换溶为一体对用户十分友好的界面,在计算化学和计算机文献检索中得到实际应用. 相似文献
44.
45.
分析了用自适应滤波器进行故障诊断的方法.针对该方法在计算上要花费大量时间、难于完成实时诊断任务的缺点,提出了用神经网络自适应滤波器来完成故障诊断的方法.神经网络有极快的运行速度,能很好地完成实时诊断任务. 相似文献
46.
用“多化一”最小二乘法建立吸附动力学方程 总被引:1,自引:0,他引:1
樊恒鑫 《西北大学学报(自然科学版)》1995,25(4):289-292
用若干个一元最小二乘法,建立多元经验公式;以吸附动力学方程为例,取得了预期的结果。 相似文献
47.
研究了由Subramamian为求解互补问题提出的阻尼Gauss-Newton方法的收敛性质,在较弱的条件下,给出了一个全局收敛效果,这个结果是Subramanian PK (1993)和(1997)中相应结果的一个推广。 相似文献
48.
本文利用Fourier级数讨论具有常系数的任意阶中立型泛函微分方程的周期解,除一种特殊情况外,我们得到了用有限代数方程组描述的周期解存在唯一性的充要条件,对这种特例,我们也得到了若干实用结果. 相似文献
49.
50.
该文对具梯度耦合噪声的随机Benjamin-Ono 方程(以下简记为B-O方程)的初值问题导出了解得积分表达式,并将它应用于河口区域生物分布问题,得到了一维空间的分布表达式。 相似文献