不同分子量软链段的聚己内酯型聚氨酯扩链反应动力学研究

合成了一系列不同分子量的聚己内酯,进而制备异氰酸根封端的聚己内酯预聚体,用傅里叶变换红外光谱研究了不同分子量的聚己内酯预聚体与二元醇的扩链反应.扩链反应动力学研究结果表明:聚己内酯预聚体与二元醇的扩链反应均为二级反应;随着软链段反应物料分子量的增加,反应速率常数显著降低,但当分子量超过某一范围后,其对反应速率的影响逐渐减小,趋于不变.对于不同硬链段反应物料含量的扩链反应体系,硬链段反应物料含量越高,软链段反应物料分子量对反应速率的影响越明显,而且,当软链段反应物料分子量超过某一范围后,不同体系的反应速率常数间的差值趋于不变.Arrhenius方程中的指前因子(B)随软链段反应物料分子量的变化关系与速率常数对分子量的依赖关系相同;从反应速率常数对温度的依赖关系可见:表观活化能的直线斜率基本相同,扩链反应的活化能主要与官能团的反应活性相关.     

Alternating segment explicit-implicit scheme for nonlinear third-order KdV equation

A group of asymmetric difference schemes to approach the Korteweg-de Vries(KdV)equation is given here.According to such schemes,the full explicit difference scheme and the fun implicit one,an alternating segment explicit-implicit difference scheme for solving the KdV equation is constructed.The scheme is linear unconditionally stable by the analysis of linearization procedure,and is used directly on the parallel computer. The numerical experiments show that the method has high accuracy.     

对苯二甲酸丁二酯-ε-己内酯多嵌段共聚物中硬链段的受限结晶

用差示扫描量热法（DSC）,广角X射线衍射（WAXD）,傅立叶变换红外光谱（FTIR）等技术研究了对苯二甲酸丁二酯-ε-己内酯（PBT—PCL）多嵌段共聚物中硬链段的受限结晶。结果表明,PBT—PCL共聚酯中软硬链段在非晶区的混容性比较好,不同组成的样品均显示出一个玻璃化转变温度;对硬段含量超过50%的共聚酯来说,硬链段可以结晶,而软链段不能结晶;由于硬链段的受限特点,BT硬链段的结晶受软链段的影响和制约,其结晶能力随硬段序列长度的增加而逐渐增大。     

Solution properties of exocellular polysaccharides of rhizobium leguminosarum. Static and dynamic light-scattering: Characterization in dilute solution

Three polysaccharides, Rhizobium leguminosarum 8002 EPS(I), Rhizobium trifolii TA1-EPS (II), Rhizobium leguminosarum 127K87 EPS (III), produced by bacteria of Rhizobium genus have been investigated by static and dynamic light scattering combined with chirooptical measurements. All three polymers have the same backbone but differ in the length of the side chains and in the content of minor substituents. An isothermal conformational transition coil → helix was observed with I and II by adding salt (NaCl). The molecular parameters of the polysaccharides in the ordered state were determined by light-scattering data. Increasing the ionic strength a shrinking of the helix was observed accompanied by a corresponding decrease in the radius of gyration. An extraordinary chain stiffness in terms of Kuhn segment lengths was found in both cases, similar to that already observed for other microbial polysaccharides. In the case of III no disorder → order transition was induced by the salt, and the scattering behavior corresponds to that of a rather flexible polymer with a characteristic ratio C_∞ = 24. The incapability of III to form a helical structure is attributed to the effect of the very long side chain. The analysis of the time correlation functions revealed typical flexible chain behavior for all three polysaccharides. This behavior for the two ordered polymers is in agreement with a recent theory by Maggs and is due to bending modes of the rods. ©1995 John Wiley & Sons, Inc.     

等维递补灰色校正模型的研究及应用

灰色预测模型是中长期负荷预测的一种有效的方法,对E型规律发展的负荷有很好的拟合性,但对有转折点的S型增长趋势或增长处于饱和阶段的负荷进行预测误差较大。本文通过对历史数据的最优分段,提出了等维递补灰色校正模型,可以很好地解决这个问题。实例表明,此模型在中长期负荷预测中是适用的,尤其对于按S型曲线增长的情况,具有很高的预测精度。     

On the central limit theorem for the stationary Poisson process of compact sets

Stochastic geometry models based on a stationary Poisson point process of compact subsets of the Euclidean space are examined. Random measures on ?^d, derived from these processes using Hausdorff and projection measures are studied. The central limit theorem is formulated in a way which enables comparison of the various estimators of the intensity of the produced random measures. Approximate confidence intervals for the intensity are constructed. Their use is demonstrated in an example of length intensity estimation for the segment processes. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

MDI与TDI封端聚酯预聚物和扩链剂间反应速率的研究

用ＦＴＩＲ法系统地研究了不同硬段结构对聚酯型聚氨酯扩链反应动力学的影响，结果显示：不同类二异氰酸酯ＭＤＩ和ＴＤＩ形成的ＮＣＯ封端的聚酯预聚体与二元胺（ＭＯＣＡ）和三元醇（ＴＭＰ）的扩链反应均为二级反应，由ＭＤＩ形成ＮＣＯ封端的聚酯预聚体与胺或醇的扩链反应速度比ＴＤＩ类的要快，ＭＯＣＡ扩链比ＴＭＰ扩链反应活化能低，从基团反应活性不同体系扩链反速度的差别进行了讨论。     

Initial Segments of Recursive Linear Orders

We show that any -initial segment of a recursive linear order can be presented recursively.     

θ溶剂中树枝形均聚物的自洽场理论计算

树枝形大分子因其高度支化的特殊结构，在传感、载药、催化等众多领域有着广泛的应用潜力.运用高斯链模型推导了溶液体系中树枝形均聚物的自洽场方程组.并在不考虑体积排除作用的条件下，计算了θ溶液中分子的中心链节官能度f₀、支化点官能度f、间隔链段的聚合度P、以及总代数G对链节浓度分布及均方回转半径的影响.计算结果显示，链节浓度分布总是符合"dense-core"的模型，即在所有计算参数组合下，链节浓度总是沿径向单调下降，并随f₀、f和G的增加而单调增加.自洽场计算得到的树枝形均聚物的均方回转半径R与Rouse动力学模型的计算结果基本一致，在f₀、f和G的数值较大时，都能够得到<R²>≈GPa²的标度律关系.     

液晶性芳族共聚酯的DSC研究

<正> 近年来热致液晶性的全芳族共聚酯的研究受到了人们的极大的关注,某些具有刚性主链和主链上包含介晶段的聚酯能显示出热致液晶性,这种高聚物在熔融态表现出自发取向的倾向,通过简单熔融纺丝有希望制备出高强、高模纤维。