Steady State Simulation of Ethylene Polymerization Using Multiple-Site Coordination Catalysts

Summary: Simulation models are important tools for the development and optimization of polymerization processes because they can describe catalyst performance and polymer properties as a function of polymerization kinetics and process conditions. As the polyolefin industry moves towards the production of resins with more complex microstructures, these models become essential for process understanding and product design. A simulation model has been developed for the polymerization of ethylene in a process with n reactors working in series. The model can predict raw material conversions and product properties like the molecular weight distribution (MWD) coupled with short chain branching distribution (SCBD), melt index, density and fluff morphology. Model parameters have been obtained from laboratory data. The model predictions are in good agreement with experimental results.     

Transetherification polycondensation: The roles of the catalyst,monomer structure,and polymerization conditions

A detailed study of the novel melt transetherification polycondensation process, which was recently developed in our laboratory, is presented. The efficacy of different catalysts, such as p‐toluenesulfonic acid (PTSA), camphorsulfonic acid, and their pyridinium salts, was examined. The pyridinium salts, especially pyridinium camphorsulfonate (PCS), outperformed PTSA both in terms of the polymer molecular weights (the polydispersity) and the extent of discoloration of the polymer. The evolution of the molecular weight with the polymerization time was monitored with two different catalysts, PTSA and PCS, and these studies demonstrated that, while PTSA yielded polymers with a broad molecular weight distribution, the use of PCS curtailed possible side reactions that led to this broadening. Model reactions suggested that one possible reason for this broadening could be the formation of macrocyclics facilitated by an ether–ether exchange reaction, which was shown to occur much more rapidly when PTSA was used. A further interesting and rather unprecedented feature, which became apparent while the effect of the acid–catalyst concentration was being examined, was the dual role played by the acid, which acted both beneficially as a catalyst and detrimentally, defunctionalizing the chain end and terminating polymer growth. This conclusion was based on the observed decrease in the molecular weight of the polymer at very high catalyst concentrations, which suggested that there existed an optimum catalyst concentration at which a balance was struck between the molecular weight of the polymer formed and the polymerization time. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 102–111, 2004     

Molecular Weight Control in Emulsion Polymerization by Catalytic Chain Transfer: A Reaction Engineering Approach

Summary: For the application of catalytic chain transfer in (mini)emulsion polymerization, catalyst partitioning and deactivation are key parameters that govern the actual catalyst concentration at the locus of polymerization and consequently the final molecular weight distribution. A global model, based on the Mayo equation, catalyst partitioning and deactivation was developed. The influence of several reaction parameters on the instantaneous number average molecular weight was quantified.     

Preparation of bimodal HDPEs with metallocene on Cr‐montmorillonite support

Previously described Cr‐montmorillonite (Cr‐MMT) was found to retain reactivity in the ethylene polymerization reaction regardless of which alkyl‐metal was used for workup in the preparation process, as long as alkylaluminium was used as a cocatalyst in the actual polymerization reaction. Introduction of hydrogen pressure was found to regulate the polymerization to give the product polymer with a narrower weight distribution, albeit with a somewhat smaller average molecular weight. Supporting metallocene onto Cr‐MMT produced a binuclear catalyst system which gave rise to bimodal polyethylene (PE). Polymer composition of the produced high density polyethylenes (HDPEs) could be controlled by changing factors such as the polymerization conditions and the identity of the metallocene compounds. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3722–3728, 2010     

Influence of the synthesis conditions on the structure and composition of the titanium–magnesium nanocatalyst and on its activity in isoprene polymerization

Synthesis of titanium–magnesium nanocatalyst in a high-pressure reactor under the conditions modeling the industrial conditions was studied. A laboratory scale plant including the units for the product synthesis, washing, and filtration was developed. The effect of elevated pressure (10–90 atm) on the process course, on the properties of the catalyst formed, and on the isoprene polymerization was studied for the first time. An increase in pressure leads to an increase in titanium incorporation into the catalyst from 1.52 to 2–2.3 wt % and simultaneously to an increase in the trivalent titanium content to 81 wt %. The titanium–magnesium nanocatalyst with such properties exhibits enhanced performance in isoprene polymerization without deteriorating the polymer microstructure. The development of the catalyst synthesis procedure on the laboratory scale plant will allow pilot-scale modeling of this process in the future.     

Hybrid atom transfer radical polymerization system for balanced polymerization rate and polymer molecular weight control

A hybrid polymerization system that combines the fast reaction kinetics of conventional free radical polymerization and the control of molecular weight and distribution afforded by ATRP has been developed. High‐free radical initiator concentrations in the range of 0.1–0.2 M were used in combination with a low concentration of ATRP catalyst. Conversions higher than 90% were achieved with ATRP catalyst concentrations of less than 20 ppm within 2 h for the hybrid ATRP system as compared with ATRPs where achieving such conversions would take up to 24 h. These reaction conditions lead to living polymerizations where polymer molecular weight increases linearly with monomer conversion. As in living polymerization and despite the fast rates and low ATRP catalyst concentrations, the polydispersity of the produced polymer remained below 1.30. Chain extension experiments from a synthesized macroinitiator were successful, which demonstrate the living characteristics of the hybrid ATRP process. Catalyst concentrations as low as 16 ppm were found to effectively mediate the growth of over 100 polymer chains per catalytic center, whereas at the same time negating the need for post polymerization purification given the low‐catalyst concentration. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2294–2301, 2010     

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.     

Assessment of Microwave Effect on Polymerization Conducted under ARGET ATRP Conditions

A comprehensive kinetic model based on the method of moments is developed for understanding the kinetics of activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) under microwave irradiation. Both the experimental data and the simulation results show that the polymerization under microwave irradiation is much faster than the thermal polymerization. Simulation results indicate that the acceleration of polymerization can be attributed to the increase of propagation rate coefficient and the radical generation by microwave irradiation. Kinetic behaviors, such as the effect of catalyst concentration and initial initiator, are investigated in detail. Results show that the catalyst concentration has negligible influence on polymerization rate while the initiator concentration can affect both the molecular weight and the reaction rate. In conclusion, this work thoroughly investigates the kinetic mechanism of ARGET ATRP under microwave irradiation, providing both theoretic and experimental supports to improve the product property of polymer materials.     

甲基丙烯酸丁酯的反向ATRP“活性”/可控自由基聚合研究

自由基聚合以其可聚合的单体种类多、反应条件温和易控制、实现工业化生产容易等优点一直在高分子合成领域占有重要地位,而实现自由基“活性”/可控聚合更是高分子化学工作者孜孜以求的目标之一.然而由于自由基非常活泼,在反应过程中极易发生偶和、歧化终止和链转移等副反应,使自由基活性聚合的实现变得非常困难.1995年Matyjaszewski等[1]提出的原子转移自由基聚合(Atom transfer radical polymerization,ATRP)的概念为自由基活性聚合研究开辟了一条崭新的途径.ATRP反应过程如反应式1所示     

Products characterization of tung oil–phenol reactions based on analysis of a model reaction

A method of determining the molecular species composition distributions of products obtained by reaction of tung oil with various phenols in the presence of acid catalyst has been studied. Methyl α-eleostearate was used as a model substance in place of tung oil. The product composition analysis of methyl α-eleostearate reactions with phenols was done by HLC. From these results, the molecular weight distributions and molecular species composition distributions of the reaction products were calculated according to a statistical procedure. Good agreement was found between the calculated and experimental molecular weight distribution, which enabled prediction of the molecular species composition distribution.     

Nuclear magnetic resonance monitoring of chain‐end functionality in the atom transfer radical polymerization of styrene

The evolution of the bromine end functionality during the bulk atom transfer radical polymerization (ATRP) of styrene [in the presence of the catalyst CuBr/4,4′‐di‐(5‐nonyl)‐2,2′‐bipyridine] was monitored with 600‐MHz ¹H NMR. A decrease in the functionality versus the conversion was observed. The loss of functionality was especially significant at very high conversions (>90%). The experimental data were compared with a kinetic model of styrene ATRP. The latter indicated that the loss of chain‐end functionality was partly due to bimolecular terminations but was mainly due to β‐H elimination reactions induced by the copper(II) deactivator. These elimination reactions, which occurred later in the reaction, did not significantly affect the polymer molecular weights and the polydispersity. Therefore, a linear evolution of the molecular weights and low‐polydispersity polymers were still observed, despite a loss of functionality. Understanding these side reactions helped in the selection of the proper conditions for reducing the contribution of the elimination process and for preparing well‐defined polystyrene (number‐average molecular weight ～10,000 g mol^?1; weight‐average molecular weight/number‐average molecular weight ～1.1) with a high functionality (92%). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 897–910, 2005     

Inverse-microsuspension polymerization: Mechanism,kinetics and modelling

A mechanism has been developed for the inverse- microsuspension polymerization of acrylic water soluble monomers. This free-radical reaction scheme includes elementary reactions for polymerization in the aqueous and organic phases, nucleation in the monomer droplets and heterophase oligoradical precipitation. The latter being the dominant initiation process. A unimolecular termination reaction with interfacial species has also been elucidated and has been found to compete with and often dominate over the conventional biomolecular reaction. A kinetic model is developed which includes the influence of ionogenic monomers and polyelectrolytes and is able to predict the rate, molecular weight and composition data well for polymerizations of acrylamide and copolymerizations with quaternary ammonium cationic monomers. A categorization and systematic nomenclature for heterophase water-in-oil and oil-in-water polymerizations is also developed based on physical, chemical and colloidal criteria.     

Atom transfer radical polymerization of methyl methacrylate catalyzed by ion exchange resin immobilized Co(II) hybrid catalyst

Ion exchange resin immobilized Co(II) catalyst with a small amount of soluble CuCl₂/Me₆TREN catalyst was successfully applied to atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in DMF. Using this catalyst, a high conversion of MMA (>90%) was achieved. And poly(methyl methacrylate) (PMMA) with predicted molecular weight and narrow molecular weight distribution (M_w/M_n = 1.09–1.42) was obtained. The immobilized catalyst can be easily separated from the polymerization system by simple centrifugation after polymerization, resulting in the concentration of transition metal residues in polymer product was as low as 10 ppm. Both main catalytic activity and good controllability over the polymerization were retained by the recycled catalyst without any regeneration process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1416–1426, 2008     

Data Reconciliation and Control in Styrene-Butadiene Emulsion Polymerizations

Summary: A nonlinear model-based predictive control (NLMPC) method was developed using a First Principles model of an emulsion copolymerization of carboxylated styrene butadiene rubber (XSBR). Copolymer composition, conversion and average molecular weights of the copolymer were chosen as the controlled variables due to their influence on the final product properties and quality. These properties, however, are rarely measured in-line due to the operational difficulties associated with their measurement. For this reason a soft-sensor using reaction calorimetry techniques was developed and used to infer reaction conditions, rates, species concentrations and polymer properties in a industrial scale emulsion polymerization reactor.     

Atom-transfer radical polymerization of styrene with bifunctional and monofunctional initiators: Experimental and mathematical modeling results

Bulk atom transfer radical polymerization (ATRP) of styrene was carried out at 110 °C using benzal bromide as bifunctional initiator and 1-bromoethyl benzene as monofunctional initiator. CuBr/2,2′-bipyridyl was used as the ATRP catalyst. The polymerization kinetic data for styrene with both initiators was measured and compared with a mathematical model based on the method of moments and another one using Monte Carlo simulation. An empirical correlation was incorporated into the model to account for diffusion-controlled termination reactions. Both models can predict monomer conversion, polymer molecular weight averages, and polydispersity index. In addition, the Monte Carlo model can also predict the full molecular weight distribution of the polymer. Our experimental results agree with our model predictions that bifunctional initiators can produce polymers with higher molecular weights and narrower molecular weight distributions than monofunctional initiators. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2212–2224, 2007     

Accelerating research into bio-based FDCA-polyesters by using small scale parallel film reactors

High Throughput experimentation has been well established as a tool in early stage catalyst development and catalyst and process scale-up today. One of the more challenging areas of catalytic research is polymer catalysis. The main difference with most non-polymer catalytic conversions is the fact that the product is not a well defined molecule and the catalytic performance cannot be easily expressed only in terms of catalyst activity and selectivity. In polymerization reactions, polymer chains are formed that can have various lengths (resulting in a molecular weight distribution rather than a defined molecular weight), that can have different compositions (when random or block co-polymers are produced), that can have cross-linking (often significantly affecting physical properties), that can have different endgroups (often affecting subsequent processing steps) and several other variations. In addition, for polyolefins, mass and heat transfer, oxygen and moisture sensitivity, stereoregularity and many other intrinsic features make relevant high throughput screening in this field an incredible challenge. For polycondensation reactions performed in the melt often the viscosity becomes already high at modest molecular weights, which greatly influences mass transfer of the condensation product (often water or methanol). When reactions become mass transfer limited, catalyst performance comparison is often no longer relevant. This however does not mean that relevant experiments for these application areas cannot be performed on small scale. Relevant catalyst screening experiments for polycondensation reactions can be performed in very efficient small scale parallel equipment. Both transesterification and polycondensation as well as post condensation through solid-stating in parallel equipment have been developed. Next to polymer synthesis, polymer characterization also needs to be accelerated without making concessions to quality in order to draw relevant conclusions.     

Copper‐based supported catalysts for the atom transfer radical polymerization of methyl methacrylate: How can activity and control be tuned up?

This article is aimed at revisiting the synthesis of copper‐based catalysts immobilized onto crosslinked polystyrene (PS) resins carrying pyridinimine groups (PS–pyridinimine/CuBr). These supported catalytic systems were used for promoting the atom transfer radical polymerization of methyl methacrylate as initiated by ethyl‐2‐bromoisobutyrate. It was evidenced that the control over the polymerization reaction was strongly influenced by the coordination ability and extent of the transition‐metal salt on the supported pyridinimine ligands. For instance, increasing the ligand‐to‐catalyst molar ratio allowed for increasing the polymerization rate and improving the control over the molecular parameters of the synthesized poly(methyl)methacrylate (PMMA) in terms of the molar masses and molecular weight distributions. The PS–pyridinimine/CuBr supported catalyst was recycled and reused for further polymerization reactions. After two recycling steps, the reaction activity appeared to be preserved, and the control was improved in terms of the initiation efficiency. However, a slight increase in the polydispersity indices was observed. Interestingly, the introduction of a flexible polydimethylsiloxane spacer between the PS support and the catalytic sites led to some more improvement of the control over the molecular parameters of PMMA chains, which displayed narrower molecular weight distributions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 744–756, 2006     

无机/有机复合载体负载乙酰丙酮铁/双亚胺基吡啶催化剂及其乙烯聚合

采用溶胶-凝胶法,将苯乙烯-丙烯酸共聚物(PSA)包覆于955 Davison硅胶上得到无机/有机复合微球载体,并在2,6-二[1-(2-异丙基苯基亚胺基)乙基]吡啶/Fe(acac)3均相催化剂中浸渍后得到负载型双亚胺基吡啶铁催化剂.该催化剂在生产高结晶度(72%)聚乙烯的同时,还能生产一定量的α-烯烃.考察了不同膜材料以及聚合条件(不同助催化剂,压力,温度,Al/Fe摩尔比)对聚合活性以及聚合产物性能的影响,发现温度对聚合产物的α-烯烃与聚乙烯的质量比影响最大,助催化剂类型既影响催化剂的活性,也对最终产物的性质有着很大的影响.氯化镁处理的PSA作为膜材料时,负载2,6-二[1-(2-异丙基苯基亚胺基)乙基]吡啶/Fe(acac)3所得到聚乙烯分子量较低(Mw=11.9×104),结晶度较大(72%),熔融指数MI较高(2.35 g/10min),可作为双峰聚乙烯中的低分子量部分加以利用.     

Modeling of Ethylene Polymerization Kinetics over Supported Chromium Oxide Catalysts

Summary: Silica supported chromium oxide catalysts have been used for many years to manufacture polyethylene and they still account for more than 50% of world production of high‐density polyethylene. Along with its commercial success, the catalytic mechanism and polymerization kinetics of silica supported chromium oxide catalysts have been the subject of intense research. However, there is a lack of modeling effort for the quantitative prediction of polymerization rate and polymer molecular weight properties. The chromium oxide catalyzed ethylene polymerization is often characterized by the presence of an induction period followed by a steady increase in polymerization rate. The molecular weight distribution is also quite broad. In this paper, a two‐site kinetic model is developed for the modeling of ethylene polymerization over supported chromium oxide catalyst. To model the induction period, it is proposed that divalent chromium sites are deactivated by catalyst poison and the reactivation of the deactivated chromium sites is slow and rate controlling. To model the molecular weight distribution broadening, each active chromium site is assumed to have different monomer chain transfer ability. The experimental data of semibatch liquid slurry polymerization of ethylene is compared with the model simulations and a quite satisfactory agreement has been obtained for the polymerization conditions employed.

Polymerization rates at different reaction temperatures: symbols – data, lines – model simulations.     

Mechanism of lactide polymerization in the presence of stannous octoate: The effect of hydroxy and carboxylic acid substances

The effect of hydroxy and carboxylic acid substances on lactide polymerization in the presence of stannous octoate was investigated. A polymerization mechanism was postulated to attempt to explain the controversies existing in the literature and also to explain our experimental observations. Stannous alkoxide, a reaction product between stannous octoate and alcohol, is proposed as the substance initiating the polymerization through coordinative insertion of lactide. Alcohol can affect the polymerization through the reactions of initiator formation, chain transfer, and transesterfication. Carboxylic acid affects the polymerization through a deactivation reaction. Experiments showed that alcohol increased PLLA production rate while carboxylic acid decreased it. Both alcohol and carboxylic acid reduced PLLA final molecular weight. The higher the alcohol concentration, the lower the polymer molecular weight. However, the final molecular weight of PLLA was not sensitive to the carboxylic acid concentration. A polymerization induction period was observed at high carboxylic acid concentration, due to the deactivation reaction caused by carboxylic acid. © 1994 John Wiley & Sons, Inc.