单官能团单体C存在下A_2-B_2型缩聚产物的分子量分布

分别以概率统计方法和Monte Carlo模拟获得了单官能团单体C存在下A_2-B_2型线型缩聚产物的分子量分布。Monte Carlo方法与统计计算得出一致的结果,表明建立的Monte Carlo模型是合理的。研究了单官能团单体C的反应活性对缩聚产物分子量分布的影响,对反应体系中存在的各种不同的分子类型的消长情况分别进行了动态模拟。     

ABg型单体缩聚反应的动力学分析

研究了ＡＢｇ型单体缩聚反应的动力学,导出了分子量分布函数以及数均和重均分子量。一些结果与Ｆｌｏｒｙ用统计方法得到的一致。数值计算结果表明,单体上Ｂ官能团越多,反应所得到的超支化聚合物的分子量分布越宽;多分散性随着Ａ基团转化率的增加而增加,且当反应接受完成时迅速增加,这个结论与Ｔｕｒｎｅｒ等的实验数据定性地一致。     

266nm激光光解间氟溴苯和对氟溴苯(英文)

采用 266 nm紫外激光对间氟溴苯和对氟溴苯进行了光解动力学研究，在多个角度探测了光解碎片 Br和 C6H4F的时间飞渡谱 (TOF).从光解碎片的平动能分布 P(Et)可以得到：间氟溴苯和对氟溴苯大约有 46.8％和 41.7％的可资用能分配到碎片的平动能，其余的分配到碎片的内能；且各向异性参数被确定为 0.7和－ 0.4.为了更好地解释实验结果，我们利用从头计算方法对反应体系进行了计算，并与实验结果吻合 .由此，我们提出了比较合理的光解机理且对氟原子的取代效应进行了讨论 .     

ATRP法合成结构对称的双羧基聚苯乙烯及其超分子的形成

从二甲苯出发,经过溴甲基化反应、氧化反应、酯化反应和溴代反应,合成了一种四官能团的引发剂,4,6-二(溴甲基)-1,3-苯二甲酸二甲酯.用该引发剂引发苯乙烯进行原子转移自由基聚合,实验结果表明聚合反应具有活性自由基聚合的特征.通过苯乙烯的本体聚合反应获得了分子量可控、双酯基位于聚合物链中间的聚苯乙烯.经过水解反应,使聚合物中的双酯基被水解成双羧基,从而得到了结构对称的两亲性聚合物,双羧基聚苯乙烯.利用该聚合物具有分子识别的特性,与十二烷胺形成了离子键超分子化合物.此工作为超分子星形聚合物的设计合成提供了简便快捷的方法.     

266nm激光光解间氟溴苯和对氟溴苯

采用266nm紫外激光对间氟溴苯和对氟溴苯进行了光解动力学研究,在多个角度探测了光解碎片Br和C6H4F的时间飞渡谱(TOF)。从光解碎片的平动能分布P(Et)可以得到：间氟溴苯和对氟溴苯大约有46.8%和41.7%的可资用能分配到碎片的平动能,其余的分配到碎片的内能;且各向异性参数被确定为0.7和-0.4。为了更好地解释实验结果,我们利用从头计算方法对反应体系进行了计算,并与实验结果吻合,由此,我们提出了比较合理的光解机理且对氟原子的取代效应进行了讨论。     

聚羧酸系高性能减水剂分子在稀溶液中尺寸及其在体积排除色谱表征中表观分子量的模型研究

针对被称为"第一代聚羧酸高性能减水剂"(以下简称为MPEG-type PCE)的甲基丙烯酸(MAA)/烯酸甲酯(MAA-MPEG)梳状共聚物分子,从高分子物理基础理论出发,构建等效自由连接链模型,结合前人的理论结果和实验数据,得到了MPEG-type PCE分子的回转半径、流体力学半径及其相应的支化参数的数学表达式.在此基础上,报道了以下三方面的工作:首先,将计算结果与文献中的实验结果进行比较,检验模型的合理性;其次,利用所建立的数学模型考察主链分子量、侧链分子量和侧链接枝密度对PCE分子的回转半径和流体力学半径的影响;最后,结合近年来发展的体积排除色谱分离理论,对PCE分子的真实分子量与其常规体积排除色谱"表观分子量"(又被称为GPC分子量)两者之间的差异进行了分析.本文所提出的计算模型和数学表达式没有不确定的指前因子,可用来估算MPEG-type PCE分子在稀水溶液中的尺寸以及根据其GPC分子量估算真实分子量.     

NAD(P)H辅酶模型物结构与反应性关系的研究3-位酰基的电子效应

合成了一系列３酰胺基氮取代的ＮＡＤ（Ｐ）Ｈ模型物，测定了其与５硝基异喹啉正离子的二级反应速率常数，并与模型物的氧化还原电势进行了比较．实验结果表明，模型物３位酰基氧一方面可离域二氢吡啶环上Ｎ的电子；另一方面负电性的３位酰基氧在反应过渡态中又可引起分子内和分子间的两种静电作用；３位酰基的电子效应对模型物动力学反应性的影响是这两种效应综合作用的结果     

甲基丙烯酸甲酯聚合动力学和分子量及分布的开放控制

在甲基丙烯酸甲酯聚合过程中 ,凝胶效应会导致转化率在短时间内出现突变 ,这对工业反应器非常危险 ,同时也导致分子量剧增、分子量分布加宽 .为了使聚合反应速度、分子量及分布同时得到控制 ,提出 3个控制目标 ,即热荷分布指数、预定分子量及变化、分子量分布指数 .在甲基丙烯酸甲酯半间歇聚合动力学和分子量模型的基础上 ,通过单体、溶剂和链转移剂 3种物料的流量和加料方式的仿真计算 ,对动力学、分子量及分布进行开放控制 ,并进行优化 ,得到热荷分布指数和分子量分布指数分别小于 2 0和 2 2的控制策略 ,且分子量达到预定要求 .选择两种优化策略进行实验验证 ,结果与开放控制仿真结果一致     

狭缝孔内甲烷蒸汽重整化学平衡的分子模拟

采用反应蒙特卡罗方法研究了狭缝孔内甲烷蒸汽重整反应的化学平衡. 模拟中将CH4, CO和H2均描述成球形LJ分子, H2O和CO2分子的势能分别采用TIP4P和EMP2模型计算. 狭缝孔壁与LJ点位之间的相互作用采用Steele的10-4-3模型计算. 由于没有狭缝孔内该反应的实验数据, 因此比较了用经典热力学预测与RCMC方法得到的主体相平衡组成. 两种方法得到的结果比较吻合, 表明采用RCMC方法预测孔内的化学平衡是可靠的. 讨论了其它工艺条件对孔内化学平衡的影响.     

3,5-二碘水杨醛缩乙二胺席夫碱配合物的合成、理论研究及其与ct-DNA的实验研究

合成了2种新型3,5-二碘水杨醛缩乙二胺席夫碱过渡金属配合物.经过元素分析、红外光谱和摩尔电导值分析,确定配合物的组成为M2L2(M=Co(Ⅱ)和Ni(Ⅱ)).用Gaussian09量子化学程序包,采用密度泛函理论(DFT)中的B3LYP方法,对配合物的几何构型、电荷分布、前线分子轨道及稳定性进行了量化计算.从理论计算角度分析比较了钴、镍配合物反应活性的强弱.通过紫外-可见光谱法、荧光发射光谱法、黏度法对配合物与ct-DNA的相互作用进行了实验研究.理论分析与实验结果都表明Co(Ⅱ)配合物反应活性强于Ni(Ⅱ)配合物,实验研究与理论计算结果相一致.     

A novel method to determine the molecular weight of the oligomers of biodegradable polymer

The biodegradable polymers used in controlled release applications are primarily insoluble polymers which undergo chemical or enzymatic hydrolysis to form soluble monomeric or oligomeric units. To determine the endurance of the polymer after implantation or injection into the body it is important to determine the rate of elimination of the intermediates formed upon the hydrolysis of the polymer. It is essential to identify these intermediates before its elimination rate can be determined. Identification of these intermediates is a problem because they are difficult to isolate, and are thermally and hydrolytically unstable. A new technique is proposed, taking advantage of the neighboring group effect on the hydrolysis of ionic and non-ionic oligomers, to determine the molecular weight of unknown species that are formed upon hydrolysis of the polymer. The technique involves the determination of the specific acid and base catalytic rate constants. To demonstrate the technique, a time sequence synthesis was carried out to synthesize several oligomers that would be forming upon the hydrolysis of poly(butylene tartrate). Hydrolysis studies were conducted with these oligomers and the samples were analyzed by liquid chromtography. The observed rate constant for the hydrolysis under acidic and alkaline pH medium were calculated from the terminal slopes of the first order plot. The observed rate constants were further utilized to calculate the specific acid and base catalytic rate constants. These specific rate constants, along with the micro-hydrogen and -hydroxyl ion catalytic rate constants, were used to determine the molecular weight of the intermediate species. The molecular weight obtained from the kinetic parameters was in excellent agreement with the results obtained from fast atom bombardment mass spectrometry. The same type of analysis can be extended to any multifunctional group compound which has repeat units and can undergo a specific reaction which can be accurately measured.     

Kinetic Modeling from Early Product Development to Polymerization Process Optimization

Summary: This contribution illustrates how kinetic modeling supports early product development stages under industrial constraints also for smaller scale products. Diisocyanate oligomerization is selected as an example. Data for model parameterization and validation are acquired in kinetic experiments with on-line IR monitoring. Based on these measured data and a proposed reaction scheme for the cyclo-oligomerization of diisocyanates with equal reactivity of both isocyanate groups, two kinetic models differing in level of detail are developed. All experimental trends are described correctly with these kinetic models. A functional group based model is used for parameterization and prediction of conversion profiles. This model version is also applied for assessing working hypotheses on the details of the catalytic cycle and for developing strategies for catalyst and process optimization. A second model takes into account full molecular weight distribution and thus enables prediction of individual oligomer concentrations. Fast assessment of process alternatives is possible with both models.     

Modeling the kinetics of step homopolymerization reactions--an assessment of different approaches

A critical analysis of two models used to describe the kinetics of step homopolymerization has been undertaken. The classical second-order kinetic model and the more widely adopted Mathew et al. oligomer precipitation model were tested against data published in the literature. The classical model, which predicts an identical molecular weight distribution to that obtained by Flory using a statistical approach, is based on a single rate constant and provided an excellent fit (R²>0.99) to the experimental data. Derived rate constants exhibited logical trends. The Mathew et al. oligomer precipitation model, on the other hand, requires three fitting parameters. This model also fitted the data well but in many cases yielded either negative rate constants for the purported termination step or illogical parametric trends. It was concluded that the classical model was superior to the precipitation model in describing the kinetics and reaction mechanisms of step homopolymerization.     

Reaction Mechanisms and Kinetics of the Melt Transesterification of Bisphenol‐A and Diphenyl Carbonate

The catalyzed and uncatalyzed reaction mechanisms of the melt transesterification process of bisphenol‐A and diphenyl carbonate are proposed based on nucleophilic substitution at the carbonyl group of the reactants. The reaction paths and energy barriers of the melt transesterification reaction were predicted and identified via density functional theory (DFT) calculations. The calculations reveal that the different oligomers with only one repeating unit are formed through different thermal processes. The theoretical evaluation further indicates that the basic hydroxide catalysts can reduce the energy barrier for the transesterification reaction, which allows subsequent nucleophilic attack to easily occur. Furthermore, the reaction kinetics of transesterification using tetraethyl ammonium hydroxide as a catalyst were investigated experimentally over a temperature range of 155–175°C. The reaction rate constants and equilibrium constants were determined based on the functional group model, and the equilibrium constants decreased with increasing reaction temperature. A detailed molecular species model with a specific repeating unit (n = 3) was developed and applied to predict the change in the reactants, oligomers, and phenol, and the experimental data and model calculation agree quite well. The standard curves of the oligomer were reversely derived, which provide intuitive insight into the concentration change of each oligomer. Both the DFT calculations and experimental results indicate that the C1 oligomer is first formed, and some of which are then converted to other types or higher molecular weight oligomers.     

Determination of kinetic constants of the cationic copolymerization of isobutylene with isoprene

A theoretical kinetic model has been developed for cationic isobutylene–isoprene copolymerization in methyl chloride with an AlCl₃ catalyst. Kinetic constants of this process have been derived from experimental data available on copolymerization kinetics (isobutylene conversion curve) and on molecular weight characteristics of the isobutylene–isoprene copolymer (butyl rubber). The adequacy of the theoretical kinetic model of the isobutylene–isoprene copolymerization process has been demonstrated by comparing the calculated molecular weight characteristics and degree of unsaturation of butyl rubber to the corresponding independent experimental data.     

PREPARATION AND CHARACTERIZATION OF NOVEL CHITOSAN DERIVATIVES:ADSORPTION EQUILIBRIUM OF IRON(Ⅲ)ION

The adsorption of Fe(Ⅲ)ions from aqueous solution by chitosan alpha-ketoglutaric acid(KCTS)and hydroxamated chitosan alpha-ketoglutaric acid(HKCTS)was studied in a batch adsorption system.Experiments were carried out as function of pH,temperature,agitation rate and concentration of Fe(Ⅲ)ions.The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and isotherm constants were determined.The Langmuir model agrees very well with experimental data.The pseudo-first-order and second-order kinetic models were used to describe the kinetic data and the rate constants were evaluated.The dynamical data fit well with the second-order kinetic model.The pseudo second-order kinetic model was indicated with the activation energy of 19.61 and 7.98 KJ/mol for KCTS and HKCTS,respectively.It is suggested that the overall rate of Fe(Ⅲ)adsorption is likely to be controlled by the chemical process.Results also showed that novel chitosan derivatives(KCTS and HKCTS)were favorable adsorbents.     

Modeling of the Microwave Initiated Emulsion Polymerization of Styrene

The emulsion polymerization of styrene, activated by microwave irradiation and conductive heating, was modeled using the Predici^® simulation package of CiT. Microwave activated initiation was modeled as adding a second conventional free‐radical chemical initiator, whose concentration is given by the intensity of microwave irradiation, and its “decomposition” kinetic rate constant is related to the ratio of monomer concentration to the rate of absorbed radiation. Most of the kinetic rate constants and model parameters used in the model were taken from the literature, in order to avoid unnecessary parameter estimation procedures. Model predictions of conversion, number and weight average molecular weights, for microwave and thermally activated systems, agree well with the experimental data reported in the literature, including experimental data previously reported by our own group.     

Preparation and reactivity of a primary amino group attached to the centre of a polymethylene chain

Polymethylenes with different chain lengths and having a central primary amino group were prepared. Rates of the reaction of the amines with 1,5-naphthalenedisulphonyl dichloride, a bifunctional fluorescent reagent, were measured by fluorometry in dilute solution. The rate constants obtained are equivalent to those for the reaction of two chain molecules having a functional group at each centre. Rates of the reactions of the amines with 5-dimethylamino-1-naphthalenesulphonyl chloride (a monofunctional fluorescent reagent), i.e. the reactions between a low molecular weight species and a functional group at the centre of a chain molecule, were also measured. Effects of chain length on reactivity of the central functional group, e.g. “local solvent medium effect” and “kinetic excluded volume effect,” are discussed briefly.     

Adsorption of acid dyes from aqueous solutions onto acid-activated bentonite

The adsorption of two dyes, namely, Acid Red 57 (AR57) and Acid Blue 294 (AB294), onto acid-activated bentonite in aqueous solution was studied in a batch system with respect to contact time, pH, and temperature. Acidic pH was favorable for the adsorption of these dyes. The surface characterization of acid-activated bentonite was performed using the FTIR technique. The pseudo-first-order and pseudo-second-order kinetic models and the intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamic data fitted the pseudo-second-order kinetic model well and also followed the intraparticle diffusion model up to 90 min, but diffusion is not the only rate controlling step. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were determined. The Freundlich model agrees very well with experimental data. The activation energies of adsorption were also evaluated for the adsorption of AR57 and AB294 onto activated bentonite.     

PREPARATION AND CHARACTERIZATION OF NOVEL CHITOSAN DERIVATIVES: ADSORPTION EQUILIBRIUM OF IRON(Ⅲ) ION

The adsorption of Fe(Ⅲ)ions from aqueous solution by chitosan alpha-ketoglutaric acid(KCTS)and hydroxamated chitosan alpha-ketoglutaric acid(HKCTS)was studied in a batch adsorption system.Experiments were carried out as function of pH,temperature,agitation rate and concentration of Fe(Ⅲ)ions.The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and isotherm constants were determined.The Langmuir model agrees very well with experimental data.The pseudo-first-order and second-order kinetic models were used to describe the kinetic data and the rate constants were evaluated.The dynamical data fit well with the second-order kinetic model.The pseudo second-order kinetic model was indicated with the activation energy of 19.61 and 7.98 kJ/mol for KCTS and HKCTS,respectively.It is suggested that the overall rate of Fe(Ⅲ)adsorption is likely to be controlled by the chemical process.Results also showed that novel chitosan derivatives(KCTS and HKCTS)were favorable adsorbents.