利用离散正交多项式组合神经网络建立聚合物分子量分布灰箱模型

聚合物分子量分布（MWD）是反映产品性能最重要的指标之一,它是典型的二元建模对象,聚合物分子量分布（MWD）是反映产品性能最重要的指标之一,它是典型的二元建模对象,采用组合神经网络对MWD的空间和时间变量进行分解建模。首先利用离散正交多项式神经网络在链长空间上建立分布与链长的模型,然后将MWD与时间变量的关系转换为网络权向量与输入变量之间的函数,利用递归神经网络建立两者之间的模型,最后组合两个网络达到建模目标。分布函数的模型表达式可写成状态方程形式,为进一步设计控制策略提供了基础。在链长空间上建立模型时,实现了神经网络的权向量与MWD相应阶次矩值之间的等价关系,网络权向量由单纯的拟合数据转变为有意义的物理量,实现了神经网络模型的灰箱化,为精确预测网络隐层节点数问题提供了解决途径。提出的方法应用于实验室规模的苯乙烯聚合过程,证明了建模方法的可行性,同时网络权值与矩值的等价关系也得到验证。     

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。     

利用B样条神经网络实现聚合反应分子量分布的建模与控制

介绍了以B样条函数作为基函数的神经网络的基本结构和特性,提出了利用B样条神经网络建立聚合物分子量分布（MWD）模型的方法和拓扑结构,以及基于模型预估的控制MWD的新方法.根据预估的分子量分布数据和事先确定的性能指标,使用最优化方法,计算出控制序列,使过程输出达到给定的理想分布.以某实验室规模的苯乙烯聚合反应为仿真对象,研究了此方法的建模与控制实现,证明了方法的可行性.     

利用温度分布控制管式聚合反应的分子量分布

阐述了如何利用管式反应器内的温度分布控制聚合反应的分子量分布(MWD)这样一个新课题。文章包括这个基本思想的可行性研究,即温度分布与终端产品的分子量分布的关系及可控性问题;系统的控制变量(进料流量和反应物比率)和输出变量(温度分布及分子量分布)之间的灵敏度分析;控制策略包括模式识别和专家系统的应用等,还介绍了基于这种思想的计算机仿真结果及分析讨论意见。     

凝胶渗透色谱法测定聚合物分子量的现状

综述了近年来凝胶渗透色谱法在聚合物分子量测定方面的进展。主要讨论了色谱条件的改变对聚合物分子量测定结果的影响,以及凝胶渗透色谱与不同检测器的联用情况,同时对如何改善分离效果和提高测定结果准确性进行了讨论,并且对凝胶渗透色谱法在其他领域的应用进行了总结。     

用于聚合物分子量分布求解的图形处理器并行求解方法

本发明公开了一种用于聚合物分子量分布求解的图形处理器并行求解方法。该方法建立一个自由基聚合反应动态模拟的机理模型来求解聚合物分子量分布,通过解耦方法将该机理模型分解为一个小规模自由基聚合反应模型和     

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     

基于系统输出分布的建模和控制方法及应用

提出了依据系统输出分布的特征变量选取方法,并提出了依据该项信息的建模和控制方法.仿真结果令人满意.在一个实验性二元精馏塔上用IBM-PC机进行试验亦获成功.简化模型能较好地近似精馏塔的逐板模型,控制策略优于常规PI控制策略.     

分子量分布对聚乙烯性能的影响及控制方法

通过分析分子量分布对聚乙烯产品性能的影响,阐述了分子量分布的控制方法,改变工艺流程、催化剂种类和催化剂加入反应器的状态能控制聚乙烯的分子量分布。     

聚丙烯酰胺类水溶性聚合物制备中分子量的控制

聚丙烯酰胺类水溶性聚合物在油气开采过程中有着十分广泛的应用,其分子量的大小决定着产品的性能和用途。该类聚合物的合成一般采用自由基聚合,聚合反应中通过控制单体浓度、引发剂浓度、聚合反应温度可以调节聚合物的分子量。另外,通过选择引发体系、聚合工艺、适度交联以及添加链转移剂也可以达到控制聚丙烯酰胺类水溶性聚合物分子量的目的。     

Dynamic optimization for grade transition processes using orthogonal collocation on molecular weight distribution

To meet the demands of a competitive market, an industrial plant often produces several grades of polymer product through the same process in an economical way. As molecular weight distribution (MWD) is a crucial quality index of polymers, dynamic optimization for grade transition based on MWD is highly important, but challenging. This study considers the development of optimization models for MWD-based grade transition. An MWD reconstruction method using orthogonal collocation in two dimensions is developed to capture the dynamic feature of MWD in time and the distributive feature in chain length. The simultaneous collocation approach is adopted to discretize the model. Two optimization formulations are proposed to describe minimizing the transition time as well as off-spec production. Both formulations inherit the advantages of the simultaneous collocation approach. The numerical results show that the proposed methods can efficiently solve the grade transition problem with MWD specification, and obtain high performance control profiles to reduce the production cost. © 2019 American Institute of Chemical Engineers AIChE J, 65: 1198–1210, 2019     

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     

An alternative neural network approach to calculate the molecular weight distribution from dynamic rheological properties of i‐PP resins

The calculation of the molecular weight distribution (MWD) of a polymer from its rheological properties is an attractive method since rheological measurements are comparatively faster and cheaper than the classical gel permeation chromatography technique (GPC). The calculation, however, still has some drawbacks, such as the sensitivity of the mathematical solution involved (ill‐posed problem) and the limited frequency range covered by commercial rheometers, which can be especially critical for crystalline polymers, for which the time–temperature superposition is of limited worth. In this article, a new approach for evaluating the MWD from the storage modulus and the relaxation modulus curves is proposed. The method, based on the use of a neural network model, was employed to evaluate MWD from rheological data obtained with different isotactic polypropylene resins. The results show that this approach can be successfully used to compute MWD curves and should expand the range of application of the rheological technique. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1416–1423, 2000     

Effects of molecular weight and molecular weight distribution on creep properties of polypropylene homopolymer

The molecular weights of the industrial-grade isotactic polypropylene (i-PP) homopolymers samples were determined by the melt-state rheological method and effects of molecular weight and molecular weight distribution on solid and melt state creep properties were investigated in detail. The melt-state creep test results showed that the creep resistance of the samples increased by M_w due to the increased chain entanglements, while variations in the polydispersity index (PDI) values did not cause a considerable change in the creep strain values. Moreover, the solid-state creep test results showed that creep strain values increased by M_w and PDI due to the decreasing amount of crystalline structure in the polymer. The results also showed that the amount of crystalline segment was more effective than chain entanglements that were caused by long polymer chains on the creep resistance of the polymers. Modeling the solid-state viscoelastic structure of the samples by the Burger model revealed that the weight of the viscous strain in the total creep strain increased with M_w and PDI, which meant that the differences in the creep strain values of the samples would be more pronounced at extended periods of time.     

Comparison of molecular weight distribution models for polymers characterized by g.p.c.

A semi-empirical model which employs polynomials based on general free radical polymerization kinetics, is developed to describe the molecular weight distribution data as well as to evaluate the average molecular weights of a variety of commercial thermoplastics including polystyrene, poly(methyl methacrylate) and low density polyethylene. These novel expressions are equally applicable to a natural rubber sample with a bimodal distribution. Least-squares methods for the classical Schulz and Flory distribution functions are introduced to handle the g.p.c. data of the above polymers. Comparison of the results collected from various analyses indicates clearly that the polynomial model is the most versatile one in the sense that it can be utilized to smooth out satisfactorily the molecular weight distribution data of many polymers. In general, the Wesslau distribution function is particularly good for the highly branched polyolefin and the Schulz model is fairly effective for the addition polymers of moderately sharp molecular weight distribution, presumably with $\text{M}\text{?}{}_{\mathrm{<mtext>w</mtext>}}\text{M}\text{?}{}_{\mathrm{<mtext>n</mtext>}}\text{=3.0}$. However, the Flory and Tung distributions are found to be rather inferior in the present studies. On the basis of the current findings, a new procedure is suggested to facilitate the computations of the true average molecular weights from g.p.c. data directly.     

聚丙烯熔体流动指数与分子量及其分布的关系

研究了聚丙烯(PP)的熔体流动指数(MI)与聚合物不同分子量之间的关联性,对于分子量分布较窄的PP,数均分子量(Mn)、重均分子量(Mw)和粘均分子量(Mv)均能较好的关联;反之,MI与Mn关联性下降,而MI与Mn和Mv的关联性仍很好,尤其是MI与Mv的关联性受分子量分布的影响很小;MI与Z均分子量的关联性很差。同时．确定了MI与各种分子量之间的关联式,该式用于本体PP工艺反应器内氢气浓度的计算和MI的预测,与实验测量结果吻合良好。     

Determining molecular weight scale and molecular weight distribution of ethylene-tetrafluoroethylene alternating copolymer via a rheological technique

A self-scaling rheology-based technique was developed to determine the molecular weight (MW) and molecular weight distribution (MWD) of ethylene-tetrafluoroethylene alternating copolymer (ETFE). The self-scaling technique makes determining MW and MWD with isolated completely rheological method possible. Moreover, the two key parameters (the plateau modulus and zero-shear viscosity) were obtained by more robust numerical technique, which let determining MW and MWD via rheological method initiated by Tuminello [Macromolecules 1993, 26, 499] being building on more robust and rigid basis. Our case overcomes the shortage of Tuminello's method and gives more practical and simply mean to analyze the MW scale and MWD in the production and application of ETFE. It is found that the peak MW of a ETFE (commercial grade: EP541) is 1.73 × 10⁵ g/mol, the MWD curve is a pattern with a slightly raised “shoulder” at high-molecular mass end, and a high peak on the median and the polydispersity is broad (the polydispersity index is near to 10.3). The wide polydispersity indicates the commercial ETFE combining good processability of relative lower MW molecules with physical properties of high MW ones. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The molecular weight distribution of oligomers

It is shown that the relation $\text{P}{}_{\mathrm{w}}\text{P}{}_{\mathrm{n}}\text{= 2}$ or the nonuniformity U = 1 is only a limiting case for high degrees of polymerization, is no more valid for oligomers. Two new relations are derived, one including and one excluding monomers. For the oligomer part of cationically produced polystyrenes the second relation is in good agreement with experiments.