Catalytic chain transfer polymerization of isobutylene: The role of nucleophilic impurities

Fast polymerization of isobutylene (IB) initiated by tert‐butyl chloride using ethylaluminum dichloride·bis(2‐chloroethyl) ether complex (T. Rajasekhar, J. Emert, R. Faust, Polym. Chem. 2017, 8, 2852) was drastically slowed down in the presence of impurities, such as propionic acid, acetone, methanol, and acetonitrile. The effect of impurities on the polymerization rate was neutralized by using two different approaches. First, addition of a small amount of iron trichloride (FeCl₃) scavenged the impurity and formed an insoluble · impurity complex in hexanes. The polymerization rate and exo‐olefin content were virtually identical to that obtained in the absence of impurities. Heterogeneous phase scavenger (FeCl₃) exhibited better performance than homogenous phase scavengers. In the second approach, conducting the polymerization in wet hexanes, the fast polymerization of IB was retained in the presence of impurities with a slight decrease in exo‐olefin content. ¹H NMR studies suggest that nucleophilic impurities are protonated in the presence of water, and thereby neutralized. Mechanistic studies suggest that the rate constant of activation (k_a), rate constant of propagation (k_p), and rate constant of β‐proton elimination (k_tr) are not affected by the presence of impurities. To account for the retardation of polymerization in the presence of impurities, delay of proton transfer to monomer in the chain transfer step is proposed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3697–3704     

Effect of chain structure on the glass transition temperature and viscoelastic property of cis‐1,4‐polybutadiene via molecular simulation

In this work, by adopting the united atom model of cis‐1,4‐poly(butadiene) (PB), we systemically investigate the effect of the chain structure on the glass transition temperature (T_g) and the viscoelastic property of PB system. First, we analyze the atom translational mobility, bond reorientation dynamics, torsional dynamics, conformational transition rate, and dynamic heterogeneity of the PB chains with different chain structures in detail by determining the corresponding T_g. In addition, our results clearly indicate that with the decrease of the amount of the free end atoms of PB via the end‐linking method, the mobility of the PB chains quickly decreases. As a result, the T_g of the PB chains gradually increases. Depending on the chain structure and the calculation method, the T_g of the PB chains varies from 154 to 240 K. In addition, the temperature dependence of the dynamic properties has different Arrhenius behaviors above and below T_g. The calculated activation energy varies from 7.37 to 16.37 KJ/mol for different chain structures above T_g, which can be compared with those for other polymers. In addition, through the end‐linking approach the strong interaction between the PB chains improves the storage modulus G′ and the loss modulus . Meanwhile, the immobility of the free end atoms effectively reduces the friction loss of the chains under the shear field, which is reflected by the low loss factor . In summary, this work can further help to understand the effect of the chain structure on the dynamic properties of the PB chains. Meanwhile, it provides an effective approach to reduce the energy loss during the dynamic periodic deformation, which can cut the fuel consumption via the end‐linking method. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1005–1016     

不确定需求与产出供应链回购契约决策

针对市场需求的不确定性和供应商产出产品合格率的不确定性,提出供应商产出量小于销售商订购量时需再生产满足销售商的订购,以及供应商生产过量和回购的产品通过折扣市场出售,建立以供应链期望利润为目标函数,以回购单价为决策变量的供应链回购契约决策模型.通过模型的分析,证明了模型存在最优的期望利润,给出了最优回购单价满足的方程;同时,也证明了最优订购量,最优生产量和销售商最优期望利润是回购单价的增函数.最后,通过算例验证了模型的有效性.     

基于严格α-双链对角占优矩阵的非奇H-矩阵的判定准则

研究了非奇H-矩阵的判定问题.先给出了几个判定严格α-双链对角占优矩阵的充要条件,进一步利用矩阵对角占优理论得到了判定非奇H-矩阵的一些充分条件,推广和改进了已有的相关结果,并用数值算例说明了这些判定方法的有效性.     

非齐次树上m重非齐次马氏链的一类强偏差定理

研究给出了非齐次树上m重非齐次马氏链的一类强偏差定理.     

数量折扣契约下基于成本分担的供应链突发事件协调应对

突发事件会增加供应链成本,如何进行成本分担是决定供应链能否协调应对突发事件的重要因素.用参数分别描述市场需求剧增时增加的生产成本和市场需求剧减时发生的多余产品处理成本,在数量折扣契约基础上,研究突发事件发生后制造商的最优批发价格和零售商的最优订货量,分析其影响因素比较突发事件发生前后包括市场剧增与市场剧减两种情况下的差异,并给出了数值算例.结果表明,成本分担系数和市场需求分布及其变化都会影响最优批发价格和最优订货量,只要根据市场需求变化相应调整契约参数并合理分担由突发事件增加的成本,通过数量折扣契约供应链就能够协调应对突发事件.     

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A Markov observation model with dividend is defined and the interpretation of the practical significance is given. We try to use an irreducible and homogeneous discrete-time Markov chain to modulate the inter-observation times and embed a dividend strategy. In the Markov observation model with dividend, a system of liner equations for the expected discounted value of dividends until ruin time is derived. Moreover, an explicit expression is obtained and proved. Finally, some interesting properties are illustrated by numerical analysis and by comparing with the complete compound binomial model with dividend.     

Option Pricing and Hedging under a Markov Switching Lévy Process Model

In this paper,we consider a Markov switching Lévy process model in which the underlying risky assets are driven by the stochastic exponential of Markov switching Lévy process and then apply the model to option pricing and hedging.In this model,the market interest rate,the volatility of the underlying risky assets and the N-state compensator,depend on unobservable states of the economy which are modeled by a continuous-time Hidden Markov process.We use the MEMM(minimal entropy martingale measure) as the equivalent martingale measure.The option price using this model is obtained by the Fourier transform method.We obtain a closed-form solution for the hedge ratio by applying the local risk minimizing hedging.     

基于改进的GM(1,1)-Markov链组合模型广东省单位GDP能耗预测

本文以灰色系统理论的GM(1,1)模型和随机过程理论的Markov链模型为基础构建了一个动态GM(1,1)-Markov链组合预测模型。该模型同时利用了GM(1,1)模型对序列趋势因素良好的拟合能力和Markov链模型对残差序列信息的提取能力。为进一步提高该模型的预测精度,用泰勒(Taylor)近似方法和新信息优先的思想对该模型进行了改进。最后,以1991-2014年广东省单位GDP能耗数据实证了该模型的预测效果。