Abdulrahman Albeladi, Akhlaq Moman, Timothy F. L. McKenna
The impact of common process catalyst poisons on the performance of a 6th generation Ziegler–Natta catalysts during the gas phase polymerization of propylene are examined using two approaches: introducing propylene without purification, or with one or two sets of purification columns, and by introducing carbon dioxide (CO2), oxygen (O2), water (H2O), methanol (CH3OH), ethyl acetate (C4H8O2) and dimethyl sulfoxide (C2H6SO) during the polymerization. As expected, purification columns increases the catalyst activity significantly, slightly reduce catalyst decay. Injecting TiBA during the reaction leads to an activity increase. The addition of two full sets of columns substantially increased the repeatability of polymerization reactions. The power of deactivation of poisons injected during the polymerization reaction is: O2 > CO2 > CH3OH > C2H6SO > C4H8O2 > H2O. Adding CO2, O2, and CH3OH resulted in a progressive decrease in molecular weight while almost no effect is observed with H2O. However, C4H8O2, and C2H6SO resulted in a mild increase in molecular weight. Additionally, the effects on crystallinity and stereoregularity are similar where CO2, O2, H2O and CH3OH caused a progressive decrease while C4H8O2 and C2H6SO resulted in a mild increase, indicating some isotacticity control by these two poisons.
{"title":"Impact of Process Poisons on the Performance of Post-Phthalate Supported Ziegler–Natta Catalysts in Gas Phase Propylene Polymerization","authors":"Abdulrahman Albeladi, Akhlaq Moman, Timothy F. L. McKenna","doi":"10.1002/mren.202200049","DOIUrl":"10.1002/mren.202200049","url":null,"abstract":"<p>The impact of common process catalyst poisons on the performance of a 6th generation Ziegler–Natta catalysts during the gas phase polymerization of propylene are examined using two approaches: introducing propylene without purification, or with one or two sets of purification columns, and by introducing carbon dioxide (CO<sub>2</sub>), oxygen (O<sub>2</sub>), water (H<sub>2</sub>O), methanol (CH<sub>3</sub>OH), ethyl acetate (C<sub>4</sub>H<sub>8</sub>O<sub>2</sub>) and dimethyl sulfoxide (C<sub>2</sub>H<sub>6</sub>SO) during the polymerization. As expected, purification columns increases the catalyst activity significantly, slightly reduce catalyst decay. Injecting TiBA during the reaction leads to an activity increase. The addition of two full sets of columns substantially increased the repeatability of polymerization reactions. The power of deactivation of poisons injected during the polymerization reaction is: O<sub>2</sub> > CO<sub>2</sub> > CH<sub>3</sub>OH > C<sub>2</sub>H<sub>6</sub>SO > C<sub>4</sub>H<sub>8</sub>O<sub>2</sub> > H<sub>2</sub>O. Adding CO<sub>2</sub>, O<sub>2</sub>, and CH<sub>3</sub>OH resulted in a progressive decrease in molecular weight while almost no effect is observed with H<sub>2</sub>O. However, C<sub>4</sub>H<sub>8</sub>O<sub>2</sub>, and C<sub>2</sub>H<sub>6</sub>SO resulted in a mild increase in molecular weight. Additionally, the effects on crystallinity and stereoregularity are similar where CO<sub>2</sub>, O<sub>2</sub>, H<sub>2</sub>O and CH<sub>3</sub>OH caused a progressive decrease while C<sub>4</sub>H<sub>8</sub>O<sub>2</sub> and C<sub>2</sub>H<sub>6</sub>SO resulted in a mild increase, indicating some isotacticity control by these two poisons.</p>","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":null,"pages":null},"PeriodicalIF":1.5,"publicationDate":"2022-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43344524","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Marília Caroline C. de Sá, Teresa Córdova, Príamo Albuquerque Melo Jr., Ramón Díaz de León, José Carlos Pinto
The present work presents phenomenological models to describe the coordination polymerization of β-myrcene using the Ziegler–Natta catalyst system composed by neodymium versatate (NdV3), diisobutylaluminum hydride (DIBAH), and dimethyldichlorosilane. The kinetic parameters required to simulate the reactions are estimated, and the amount of DIBAH used as a chain transfer agent (CTA) is obtained by a data reconciliation strategy since it can participate in side reactions. Several experiments are performed at different conditions to evaluate the impact of key operation variables on the control of monomer conversion and average molar masses. It is shown that the initial NdV3, β-myrcene, and DIBAH concentrations exert strong influences on the course of the polymerization. The kinetic mechanism of Coordinative Chain Transfer Polymerization (CCTP) fits well with the data of final average molar masses and monomer conversion, while the dynamic trajectories of these variables are fitted better by kinetic mechanisms of more conventional coordination polymerizations, considering site deactivation and termination by chain transfer. In all cases, the proposed models are able to predict the experimental data well after successful parameter estimation and reconciliation of CTA concentrations, indicating that the kinetic mechanism can be characterized by different kinetic regimes.
{"title":"β-Myrcene Coordination Polymerization: Experimental and Kinetic Modeling Study","authors":"Marília Caroline C. de Sá, Teresa Córdova, Príamo Albuquerque Melo Jr., Ramón Díaz de León, José Carlos Pinto","doi":"10.1002/mren.202200041","DOIUrl":"10.1002/mren.202200041","url":null,"abstract":"<p>The present work presents phenomenological models to describe the coordination polymerization of β-myrcene using the Ziegler–Natta catalyst system composed by neodymium versatate (NdV<sub>3</sub>), diisobutylaluminum hydride (DIBAH), and dimethyldichlorosilane. The kinetic parameters required to simulate the reactions are estimated, and the amount of DIBAH used as a chain transfer agent (CTA) is obtained by a data reconciliation strategy since it can participate in side reactions. Several experiments are performed at different conditions to evaluate the impact of key operation variables on the control of monomer conversion and average molar masses. It is shown that the initial NdV<sub>3</sub>, β-myrcene, and DIBAH concentrations exert strong influences on the course of the polymerization. The kinetic mechanism of Coordinative Chain Transfer Polymerization (CCTP) fits well with the data of final average molar masses and monomer conversion, while the dynamic trajectories of these variables are fitted better by kinetic mechanisms of more conventional coordination polymerizations, considering site deactivation and termination by chain transfer. In all cases, the proposed models are able to predict the experimental data well after successful parameter estimation and reconciliation of CTA concentrations, indicating that the kinetic mechanism can be characterized by different kinetic regimes.</p>","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":null,"pages":null},"PeriodicalIF":1.5,"publicationDate":"2022-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42193924","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Front Cover: In article number 2200038, Miguel Rosales-Guzmán and co-workers investigate the effect of reaction temperature and carbon dioxide pressure on the simultaneous copolymerization of 1-octene and glycidyl methacrylate (GMA) in the absence of solvents or stabilizers. Emphasis is given to the molar composition of the obtained copolymers although other features are investigated such as the morphology and the post-polymerization hydrolysis of the epoxy moiety in GMA.