聚合反应周期进料对分子量分布可控性分析

对聚合产品的分子量分布实现在线控制是保证高分子产品质量的重要任务。以实验室规模的乙烯基丁基醚管式阳离子聚合反应为研究对象,验证了单体、引发剂周期进料对分子量分布有加宽效应,并从混合平均分布的角度研究了周期进料对分子量分布的影响,从而分析了实现分子量分布控制的可行性。     

引发剂引发与热引发在苯乙烯本体聚合中的比较

考察了热引发方式和不同种类、浓度下的引发剂引发方式在苯乙烯的本体聚合中对聚合反应速率和产品的分子量及其分子量分布的影响。结果表明：引发剂用于苯乙烯的本体聚合可缩短反应停留时间、提高转化率或提高产品的分子量、使分子量分布变窄，双官能团引发剂的影响更为明显。     

基于粒子群优化算法的烯烃聚合反应动力学参数估计

聚合反应动力学参数估计是烯烃聚合过程建模与优化的重要环节和难点.针对Ziegler-Natta催化剂多活性中心特性、反应复杂、动力学参数多的问题,提出了基于粒子群优化(PSO)算法的烯烃聚合反应动力学参数估计方法.该方法以聚烯烃分子量分布(MWD)、短支链分布(SCB)、共聚组成分布(CCD)等微观链结构为目标,以动力...     

茚基钠/甲苯体系引发丙烯腈聚合的研究

本文采用茚基钠作为引发剂,对丙烯腈在甲苯中的聚合进行了研究,考察了引发剂用量、单体浓度、反应时间及反应温度对丙烯腈聚合的影响。发现茚基钠/甲苯体系对丙烯腈聚合反应具有一定的引发活性,且随着引发剂用量增加聚合反应转化率增大,聚合产物的分子量下降;延长聚合反应时间,转化率和分子量都增大;温度对聚合反应转化率影响不大,但对聚合产物分子量有明显影响。用粘度法对聚合产物的粘均分子量进行了表征。     

环戊二烯钠／甲苯体系引发丙烯腈聚合反应研究

文章以环戊二烯钠为引发剂,对丙烯腈在甲苯中的聚合反应进行了研究,考察了引发剂用量、单体浓度、反应时间及反应温度对丙烯腈聚合的影响,并且用粘度法对聚合产物的粘均分子量进行了表征。发现环戊二烯钠／甲苯体系对丙烯腈聚合反应具有较高的引发活性。随着引发剂用量增加,聚合反应转化率增大,聚合产物的分子量下降;延长反应时间,转化率和分子量都增大;发现在0℃和引发剂与单体摩尔比为1／200时,聚合反应的转化率及聚合物产物粘均分子量均较高。     

茚基钠/四氢呋喃体系引发丙烯腈聚合的研究

以茚基钠为引发剂,对丙烯腈在四氢呋喃中的聚合反应进行了研究,考察了引发剂用量、单体与溶剂配比、反应时间及反应温度对丙烯腈聚合的影响,并用粘度法对聚合产物的粘均分子量进行了表征.结果发现茚基钠/四氢呋喃体系对丙烯腈聚合反应具有一定的引发活性,且随着引发剂用量增加聚合反应转化率增大,聚合产物的粘均分子量下降;当单体用量一定时,溶剂的量越多,聚合反应的转化率越低,而聚合产物的粘均分子量却越大;反应时间在1 h之内,延长反应时间,转化率和粘均分子量都增大;反应温度对聚合反应转化率影响不大,但对聚合产物粘均分子量有明显影响.     

振荡操作制备双峰聚乙烯的模拟

以流化床乙烯气相聚合工艺为例,提出了通过控制聚合反应条件的振荡操作,在单一反应器内实现制备双峰分子量分布聚乙烯的新工艺.通过模拟计算,分别考察了氢气、乙烯、共聚单体进料速率和反应温度的振荡操作对聚乙烯分子量分布的影响.计算结果表明,采取振荡操作后,聚乙烯树脂的分子量分布呈明显的双峰分布,表明在一个反应器里通过控制反应条件的振荡来制备双峰聚乙烯是可行的,而控制氢气进料速率的振荡操作是制备双峰聚乙烯最为有效的方法.     

以控制引发剂残存浓度比值的方法确定氯乙烯悬浮聚合反应引发剂体系问题的研究

对于已给定的聚合温度和所要求的聚合反应周期的氯乙烯悬浮聚合反应过程,控制引发剂残存浓度比值,是获得稳定而正常聚合反应过程很重要的技术关键。引发剂残存浓度比值,指的是在聚合反应周期te聚合转化率为85％左右时的引发剂的残存浓度与引发剂起始浓度的比值。 为了控制与计算引发剂残存浓度的比值,本文作者推导了有关动力学方程式。将其应用于悬浮PVC聚合反应工业生产时,取得了极为满意的结果。     

腈纶硫氰酸钠一步法低转化聚合过程中引发剂用量的经验公式

对于以硫氰酸钠(NaSCN)为溶剂,丙烯腈游离基型间歇聚合反应的动力学方程式可以从文献查到。一般认为间歇聚合中,反应速度与引发剂浓度的平方根成正比。但在工业化连续聚合过程中,由于聚合体不断引出,活性单体和分解成自由基的部分引发剂连续脱出并与新加入的单体一起混合回用,使情况变得很复杂。为了对连续聚合的工艺进行稳定控制。几年来,我们对低转化率情况下,     

甲基丙烯酸甲酯的RAFT微乳液聚合

该文合成了一种双官能团的RAFT试剂——S,S'-二(α,α'-二甲基-α″-乙酸)三硫代碳酸酯(BDAT)。以其为链转移剂,在微乳液体系中进行了甲基丙烯酸甲酯的RAFT聚合。分别讨论了聚合反应温度和链转移剂浓度对聚合反应的影响,并对相关的聚合反应动力学常数进行了计算。研究结果表明,在微乳液中进行的RAFT聚合具有显著的活性聚合的特征。聚合产物的相对分子质量(简称分子量,下同)随着转化率的提高而线性增加,同时聚合产物具有较窄的分子量分布,聚合过程随着链转移剂浓度的增加而逐渐可控。另外,利用透射电子显微镜对链转移剂浓度对微乳液粒子尺寸的影响也进行了考察,扫描电镜照片表明,微乳液聚合所得乳液粒子呈现单分散性状态,并且粒子尺寸随着链转移剂浓度的增加而逐渐增加。     

Dynamic optimization of a semi-batch reactor for polyurethane production

In this work, the dynamic optimization of a polyurethane copolymerization reactor is addressed. A kinetic-probabilistic model is used to describe the nonlinear step-growth polymerization of a mixture of low- and high-molecular-weight diols, and a low-molecular-weight diisocyanate. The dynamic optimization formulation gives rise to a highly complex and nonlinear differential-algebraic equation (DAE) system. The DAE optimization problem is solved using a simultaneous approach (SDO) wherein the differential and algebraic variables are fully discretized leading to a large-scale nonlinear programming (NLP) problem. The main reactor operation process control objective is the maximization of the molecular weight distribution (MWD) under a desired batch time, subject to a large set of operational constraints, while simultaneously avoiding the formation of polymer network (gel molecule). Typically, polyurethane formation is carried out using batch reactors. However, batch operation leads to attain relatively low MWD values and, if the process is not efficiently operated, there is always the possibility of obtaining a polymer network. In this work, it was found that process operation is greatly enhanced by the semi-batch addition of 1,4-butanediol and diamine, and the manipulation of the reactor temperature profile, allowing to obtain high molecular weights while avoiding the onset of the gelation point.     

Molecular Weight Distribution of Polystyrene Produced in a Starved Feed Reactor

A starved feed reactor (SFR) is a semi-batch polymerization reactor where initiator and monomer are fed slowly into a fixed amount of solvent. The polymerization is carried out isothermally at elevated temperatures, The added initiator decomposes instantaneously and the added monomer polymerizes immediately. The molecular weight (MW) and molecular weight distribution (MWD) of the product polymer can be effectively controlled by the feed ratio of monomer to initiator. This paper preaeats a study on the MWD of styrene polymerization in a SFR. The MWD model parameters are regressed with experimeatvJ data. Although the solids fraction in the SFR is high (higher than 50%), vlscceity is not too high and the “gel effect“ is weak due to the low molecular weight of the products. It is found that the termination rate constant is a power function of molecular weight, radicals terminate via 100% combination,the thermal iuitiation can be neglrcted even at high reaction temperature studied. And calculated results indicate that in the SFR, the validity of the long chain assumptinn becomes doubted. It appears that other alterative assumption should be found for an improved model.     

Optimal operating strategies for emulsion terpolymerisation

Optimal control policies for emulsion terpolymerisation of styrene, methyl methacrylate (MMA) and methyl acrylate (MA) were determined in a semi-batch reactor using the multi-objective dynamic optimisation method. A comprehensive dynamic model was used for the design of optimal control. The control vector parameterisation (CVP) approach was implemented for constrained optimisation for emulsion terpolymerisation reactors. The feed rates of styrene, MMA, MA, surfactant and initiator, and the temperature of the reactor were used as manipulating variables to produce terpolymers of desired composition, molecular weight distribution (MWD) and particle size distribution (PSD). The particle size polydispersity index (PSPI), molecular weight polydispersity index (MWPI) and the overall terpolymer composition ratios were incorporated in the objective functions to optimise the PSD, MWD and terpolymer composition, respectively. The optimised operational policies were validated with experiments via one stirred tank polymerisation reactor.     

基于分布函数矩的聚合物分子量分布预测控制

聚合物分子量分布（molecular weight distribution,MWD）是聚合产物重要的质量指标,由于无法在线测量,使得直接质量控制至今难以实现。在利用Legendre正交多项式组合神经网络建立聚合反应分子量分布灰箱模型的基础上,把MWD这个三维空间控制问题解构为以其矩向量为特征的二维时间域的控制问题,提出了通过控制分布的矩值实现分子量分布的预测控制方法。目标函数以矩值误差平方和为基础,考虑控制变量的约束条件,同时引入可测低阶矩的修正项,使得分子量分布的部分闭环反馈控制得以实现。该方法以实验室规模的苯乙烯聚合过程为对象进行了仿真建模与控制研究,获得良好的控制效果,证明了方法的有效性。     

Advanced modelling and optimal operating strategy in emulsion copolymerization: Application to styrene/MMA system

A model-based framework for advanced optimal operation of copolymerization processes was developed and tested experimentally in conjunction with a distributed control system (DCS) suitable for industrial application. A test case of emulsion copolymerization of styrene (Sty) and methyl-methacrylate (MMA) was investigated for predicting and optimizing key product properties including molecular weight distribution (MWD), particle size distribution (PSD), copolymer composition and conversion. The model equations include diffusion-controlled kinetics at high monomer conversions, where transition from a ‘zero-one’ to a ‘pseudo-bulk’ regime occurs. The reactor mass and energy balances describe the system transients for batch and semi-batch operations. Population balance equations, describe the particle evolution and comprise sets of integro-partial differential and nonlinear algebraic equations. The models were solved using an efficient numerical scheme suitable for on-line monitoring and control. The model predictions were found to be in good agreement with experimental results for measurements carried out with variable monomer feed rates, variable temperature and variable composition of styrene-MMA, from 25/75 to 75/25 proportions. The manipulation of these variables was found to affect the PSD significantly. The experimental results confirmed the accuracy of our optimization scheme for the desired conversion, MWD and PSD.     

Analysis of solution polybutadiene polymerizations performed with a neodymium catalyst

This article is regarding the polymerization of 1,3‐butadiene with a neodymium catalyst activated by diisobutylaluminum‐hydride and diethylaluminum chloride (DEAC). The effects of the polymerization conditions (ratio between DEAC and neodymium molar concentrations, polymerization temperature, catalyst concentration, and butadiene concentration) on the polymer yield and molecular weight distribution (MWD) of polybutadiene (PB) samples were evaluated. It is shown that the DEAC/Nd ratio and the polymerization temperature are the reaction variables that influence the MWD and the catalyst performance most significantly. PBs with broad and sometimes bimodal MWD were produced at the analyzed reaction conditions. For this reason, the MWD of the obtained polymer materials was deconvoluted with the help of the Flory most probable distribution, indicating that three or more catalyst sites are required to explain the final MWD of the polymer samples. Finally, it was observed that the analyzed neodymium catalyst is able to produce branched PBs at mild reaction conditions and that the branching frequency depends on the polymerization conditions, which may be useful for development of operation policies at plant site and production of materials with improved performances. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Inferential closed‐loop control of particle size and molecular weight distribution in emulsion polymerization of styrene

In this work, simultaneous inferential control of particle size distribution (PSD) and molecular weight distribution (MWD) in a semi‐batch emulsion polymerization reactor of styrene has been addressed. Using a comprehensive dynamic model for PSD and MWD predictions and performing a sensitivity analysis, it has been revealed that free surfactant and chain transfer agent (CTA) concentrations in the reactor are the most suitable candidates for inferential control of PSD and MWD, respectively. To control concentrations of these species in the reactor, their inlet feed flow rates are used as manipulated variables. It is assumed that the concentration of CTA is measured infrequently and therefore an open‐looped observer, based on the reaction calorimetry, has been designed to estimate the CTA concentration. The infrequent measurements of CTA concentration are used to correct its estimation. As the online measuring of the ionic free surfactant concentration is also difficult, solution conductivity which is a good indication of free surfactant concentration is used for control purposes. Simulation results show that the performance of the proposed control scheme is satisfactory even in the presence of model mismatch. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

The influence of reactor type and operating conditions on the molecular weight distribution in vinyl acetate polymerization

The vinyl acetate polymerization system was investigated with respect to the breadth of the molecular weight distribution (MWD) in batch, continuous segregated, and continuous micromixed reactors. Models were developed employing a complex kinetic scheme including polymer transfer and terminal double bond polymerization, without neglecting initiation and termination steps. Inclusion of a gel effect for terminal double bond polymerization gave better agreement with experimental molecular weight data in suspension polymerization. Simulation results showed the MWD order in the three reactor types is not fixed, but a function of reactant concentrations and the importance of chain branching. In some cases changing the initiator type and concentration will change the MWD order.     

聚合物生产分子量分布建模与控制研究

分子量分布是关系聚合物性质的重要性能指标 ,针对聚合过程分子量分布的建模和控制关键技术进行了分析和综述 ,指出各自的优缺点 ,给出了这一领域今后的研究方向     

Control of molecular weight distribution and tensile strength in a free radical styrene polymerization process

A new method is presented for modeling and controlling polymer molecular weight distribution (MWD) and tensile strength in a batch suspension polymerization of styrene. The molecular weight distribution is modeled by computing the weight fraction of the polymer in different chain length intervals. Tensile strength is then related to the modeled molecular weight distribution using a correlation available in the literature and based on the concept of a threshold molecular weight. This method enables the design of operating conditions for a batch suspension polymerization reactor, which will theoretically yield amorphous polystyrene with a desired tensile strength. Two numerical examples are presented to illustrate the feasibility of the proposed method. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1017–1026, 1998