Macromolecular Reaction Engineering最新文献

{"title":"Calorimetric Analysis of Free-Radical Polymerization Kinetics of Methyl Methacrylate: Effect of TSI-POSS","authors":"David Victoria-Valenzuela,&nbsp;Ana Beatriz Morales-Cepeda,&nbsp;Xóchitl Guadalupe Román-López","doi":"10.1002/mren.70028","DOIUrl":"https://doi.org/10.1002/mren.70028","url":null,"abstract":"<div>\u0000 \u0000 <p>The free-radical polymerization behavior of methyl methacrylate (MMA) is investigated in the presence and absence of trisilanol isobutyl polyhedral oligomeric silsesquioxane (TSI-POSS) at 70°C and 80°C using a calorimetric approach based on continuous temperature monitoring. The reaction temperature is experimentally recorded, and the corresponding heat flow is estimated from an energy balance, enabling the calculation of monomer conversion and polymerization rate (<i>R_p</i>) as functions of time. The experimental data are further analyzed to estimate the <i>k_t/k_p²</i> ratio (ratio of the termination to the squared propagation rate coefficients), which serves as a comparative indicator of changes in the balance between termination and propagation. The results reveal a non-monotonic evolution of the <i>k_t/k_p²</i> ratio, characterized by an initial decrease followed by an increase and a subsequent decline, suggesting behavior consistent with diffusion-controlled polymerization regimes. The presence of TSI-POSS is associated with a decrease in the polymerization rate and an increase in the <i>k_t/k_p²</i> ratio, suggesting the influence of diffusion-related limitations on the polymerization process. These observations are qualitatively consistent with diffusion-related effects, although independent characterization would be required to confirm the underlying mechanisms.</p>\u0000 </div>","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":"20 5","pages":""},"PeriodicalIF":1.3,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177701","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}

{"title":"Issue Information: Macromol. React. Eng. 5/2026","authors":"","doi":"10.1002/mren.70031","DOIUrl":"https://doi.org/10.1002/mren.70031","url":null,"abstract":"","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":"20 5","pages":""},"PeriodicalIF":1.3,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mren.70031","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Balancing Chain Transfer Agent Transport and Reaction in Emulsion Polymerization","authors":"F. Joseph Schork","doi":"10.1002/mren.70026","DOIUrl":"https://doi.org/10.1002/mren.70026","url":null,"abstract":"<p>The interrelationship between chain transfer agent (CTA) mass transfer and reaction in emulsion polymerization is examined. Three dimensionless parameters describing these phenomena are proposed. The Damkohler Number (<i>Da_cta</i>) is defined as the maximum rate of CTA consumption divided by the maximum rate of CTA transfer from the monomer droplets to the polymerizing polymer particles. The probability of mass transfer- rather than reaction-limitation for each CTA-monomer pair is assessed. <i>S^D</i> is the <i>maximum</i> instantaneous rate of consumption of CTA by reaction, divided by the <i>desired</i> instantaneous rate of consumption of CTA, assuming no mass-transfer limitation on CTA. <i>S^D</i> is defined so that it has a value of one when the CTA is consumed at the correct rate in order to control molecular weight and minimize branching and crosslinking over the entire polymerization. It is demonstrated that the desired value of <i>S^D</i> in emulsion polymerization is different from that in homogeneous polymerization. <i>S</i> is defined as the maximum rate of CTA mass transfer divided by the desired rate of CTA consumption and is useful if CTA mass transfer is used to “meter” the CTA into the polymerizing polymer particles. Proper selection of CTA, and polymerizer operation are discussed in light of these three dimensionless parameters.</p>","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":"20 5","pages":""},"PeriodicalIF":1.3,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mren.70026","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the Strengths and Limitations of Polymer Chemistry Informed Neural Networks","authors":"Shaghayegh Hamzehlou,&nbsp;Nicholas Ballard,&nbsp;José M. Asua","doi":"10.1002/mren.70009","DOIUrl":"https://doi.org/10.1002/mren.70009","url":null,"abstract":"<p>Kinetic models are essential tools for providing a fundamental understanding of polymerization processes. However, they are constrained by the current level of understanding of the system under study and often rely on numerous unknown parameters that are difficult to measure experimentally or estimate reliably. To address these challenges, polymer chemistry-informed neural networks (PCINNs) have been developed in which the domain knowledge embedded in these kinetic models is combined with data-driven machine learning tools. Herein, we investigate the robustness and limitations of this methodology through an in-silico investigation in which an imperfect kinetic model is combined with small datasets. As a case study, high-temperature solution polymerization of methyl methacrylate was considered. It is demonstrated that PCINNs are able to utilize imperfect kinetic models in order to reach high levels of predictive performance, with reliable extrapolation at reaction temperatures significantly beyond the range of the original dataset. Integrating domain knowledge was found to substantially reduce variance in the outcomes of the final model when using a relatively small dataset. Finally, it is shown that PCINNs can be used to provide insights into the causes of poor predictive performance of kinetic models, offering the ability to use data-driven learning to inform first-principles approaches.</p>","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":"20 4","pages":""},"PeriodicalIF":1.3,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mren.70009","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148783586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Advancing Polymer Reaction Engineering for a Sustainable and Data-Driven Future","authors":"Ivan A. Konstantinov,&nbsp;Michael C. Grady,&nbsp;Kristina M. Zentel","doi":"10.1002/mren.70025","DOIUrl":"https://doi.org/10.1002/mren.70025","url":null,"abstract":"&lt;p&gt;Polymer Reaction Engineering (PRE) stands at the intersection of fundamental science, process engineering, and societal need [&lt;span&gt;1&lt;/span&gt;]. Polymers continue to be omnipresent in our modern life [&lt;span&gt;2&lt;/span&gt;]. They enable applications ranging from healthcare and energy to packaging and infrastructure [&lt;span&gt;3&lt;/span&gt;]. They are also key in various applications for enhancing sustainability, such as batteries, solar panels, wind turbines, packaging, infrastructure, and building materials, etc. Nevertheless, the challenges associated with their manufacture, performance, and end-of-life have never been more pressing. These include the energy and raw-material demand for the processes [&lt;span&gt;4, 5&lt;/span&gt;], advanced process control [&lt;span&gt;6&lt;/span&gt;] and modelling approaches [&lt;span&gt;7-15&lt;/span&gt;] as well as suitable design-for-recycling concepts and recycling routes [&lt;span&gt;16-19&lt;/span&gt;]. New processes [&lt;span&gt;20, 21&lt;/span&gt;], new materials [&lt;span&gt;22, 23&lt;/span&gt;], and a thorough understanding of (co-)polymerization kinetics [&lt;span&gt;24-26&lt;/span&gt;], structure-property relationships [&lt;span&gt;27, 28&lt;/span&gt;], as well as polymer characterization [&lt;span&gt;29&lt;/span&gt;] are essential to overcome these challenges.&lt;/p&gt;&lt;p&gt;This special edition of Macromolecular Reaction Engineering is devoted to showcasing recent advances in PRE, inspired by the themes and scientific momentum of the 12th International Conference on Polymer Reaction Engineering (PRE XII, June 1–6, 2025, Clearwater Beach, Florida), the premier global forum for this field. Held every three years, the PRE conference series has long provided a unique platform for engineering scientists and practitioners to exchange ideas and debate emerging challenges. The twelfth edition continues this tradition by focusing on the fundamentals and tools required to address problems central to the manufacture and use of polymers in today's society. The contributions in this special issue showcase a dynamic, rigorous, and industrially relevant field.&lt;/p&gt;&lt;p&gt;Polymer Reaction Engineering is focused on understanding and controlling the complex interplay between chemistry, transport phenomena, and process design. Several papers in this issue summarize and advance the state of the art in polymerization kinetics encompassing a wide range of materials (Hutchinson et al.; Leiza et al.; Storti, Sponchioni et al.; Konstantinov et al.). Improved kinetic models, supported by robust workflows for the analysis of advanced materials (D'hooge et al.), are essential for predicting molecular weight distributions, copolymer composition, and branching. The complex and unique microstructures ultimately determine the material's performance.&lt;/p&gt;&lt;p&gt;Reactor modeling and simulation remain central themes of PRE. This special edition highlights significant progress in this area (Wulkow; Valaei et al.; Busch et al,; Drache, Zentel et al.). From “counter”-centric and Kinetic Monte Carlo models to Computational Fluid Dynamics, authors demonstrate how modern comp","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":"20 4","pages":""},"PeriodicalIF":1.3,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mren.70025","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A PLP-SEC Investigation of Di(Ethylene Glycol) Methyl Ether Methacrylate Radical Polymerization Propagation Kinetics in Solution","authors":"Fatemeh Salarhosseini,&nbsp;Robin A. Hutchinson","doi":"10.1002/mren.70005","DOIUrl":"https://doi.org/10.1002/mren.70005","url":null,"abstract":"<p>The pulsed laser polymerization size exclusion chromatography (PLP-SEC) technique is used to explore the impact of solvent polarity and composition—from bulk to ethanol (EtOH) /water mixtures to aqueous solutions and dimethyl sulfoxide (DMSO)—on the homopropagation kinetics of di(ethylene glycol) methyl ether methacrylate (DEGMEMA) between 30 and 90°C. The variation in the propagation rate coefficient (<i>k</i>_p) is attributed to entropic factors, as the activation energy remains approximately constant across all solvent mixtures at a value characteristic of other methacrylates (∼ 21 kJ·mol⁻¹). The exception to this generalization is for EtOH, where activation energy is lowered by 3–4 kJ·mol⁻¹, and the <i>k</i>_p for a solution containing 50 wt.% DEGMEMA is lower than the bulk values. DEGMEMA <i>k</i>_p values increase as monomer content is decreased from 50 to 10 wt.% in DMSO, EtOH, and EtOH/H₂O solvents. Most notably, the <i>k</i>_p of 5 wt.% DEGMEMA in water (close to its solubility limit) is higher by a factor of 12 compared to the bulk system. These new results for a member of the PEGylated monomer family also provide insight into the increase in chain-growth rates expected for non-functional methacrylates between bulk (i.e., particle) and aqueous phases in emulsion polymerization systems.</p>","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":"20 4","pages":""},"PeriodicalIF":1.3,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mren.70005","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148785039","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reaction-Related Observables In Polymer Reaction Kinetics","authors":"Michael Wulkow","doi":"10.1002/mren.70017","DOIUrl":"https://doi.org/10.1002/mren.70017","url":null,"abstract":"<div>\u0000 \u0000 <p>Polymer reaction kinetics link chemical mechanisms to the evolving polymer microstructure, but describing structural statistics efficiently remains challenging: population-balance models may become intractable, while chain-based Monte Carlo (MC) simulations can be computationally demanding. We review and formalize <i>reaction-related observables</i> (RROs), implemented as cumulative <i>counters</i>—massless, non-chemical entities that record reaction events such as monomer incorporation, branching, scission, and network-forming steps without affecting the mass balances. RROs extend deterministic rate-equation models by embedding event statistics directly into the kinetic framework, providing compact, interpretable observables and enabling reduced descriptions that remain easy to extend across model variants. We illustrate how counter-based evaluations can be used to construct derived structural indicators and heuristic structure–property relations, including examples for crosslinking networks.</p>\u0000 </div>","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":"20 4","pages":""},"PeriodicalIF":1.3,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148783628","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}

{"title":"Identifying Challenges in Size Exclusion Chromatography Calibration and Its Coupling with Software Analysis","authors":"D. Shestakova,&nbsp;I. Efimov,&nbsp;F. L. Figueira,&nbsp;A. D. Trigilio,&nbsp;P. Reyes,&nbsp;F. A. Lugo,&nbsp;Y. W. Marien,&nbsp;P. H. M. Van Steenberge,&nbsp;M. Edeleva,&nbsp;D. R. D'hooge","doi":"10.1002/mren.70012","DOIUrl":"https://doi.org/10.1002/mren.70012","url":null,"abstract":"<div>\u0000 \u0000 <p>Size-exclusion chromatography (SEC) analysis of polymers with nontrivial architectures presents specific challenges, seeing its separation of macromolecules by variations in hydrodynamic volume rather than true molar mass. Care should thus be taken with respect to calibration and detection strategies, with a coupling to (i) other higher scale experimental tools (e.g. rheology), and (ii) modeling techniques worthwhile in view of a detailed molecular characterization at the distributed level. We here formulate a first set of guidelines for improving SEC-based characterization, putting forward the relevance of detailed experimental data recording and error analysis as well as in silico characterization support. We consider both linear homopolymers, copolymers, branched and crosslinked polymers, and highlight that within the polymer community we should further work on the even better embedding of multi-detector approaches and advanced modeling techniques such as kinetic Monte Carlo. Overall this work supports the development of robust workflows for the analysis of advanced polymer materials, bridging the worlds of experimentalists and modelers.</p>\u0000 </div>","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":"20 4","pages":""},"PeriodicalIF":1.3,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784549","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}

{"title":"Novel Si-Based Chain Transfer Agents for LDPE Molecular Architecture Control","authors":"Ivan Konstantinov,&nbsp;Hayley Brown,&nbsp;Arkady Krasovskiy,&nbsp;Christopher Eddy","doi":"10.1002/mren.70013","DOIUrl":"https://doi.org/10.1002/mren.70013","url":null,"abstract":"<div>\u0000 \u0000 <p>In this work, we present a new class of silane chain-transfer agents (CTAs) for the molecular weight and the molecular weight distribution control during the production of low-density polyethylene (LDPE). These silanes exhibit a wide range of chain-transfer propensity as measured by their <i>C</i>_s values (the ratio of the rate coefficient for hydrogen abstraction and ethylene propagation, <i>k</i>_h/<i>k</i>_p) with the best performers being tris(trimethylsilyl)silane (<i>C</i>_s = 16.0) and trimethylsilylsilane (<i>C</i>_s = 15.7). Density functional theory (DFT) calculations were used to estimate the <i>C</i>_s values. The quantum chemical calculations were validated by pilot-plant experiments for triethylsilane (<i>C</i>_s = 0.22) and tris(trimethylsilyl)silane (<i>C</i>_s = 36.5). Given the expected variability in the pilot-plant data, an excellent agreement between theory and experiment was achieved. Furthermore, a model utilizing the DFT calculated Mulliken charge on the silicon atom to predict the C_s value was developed to facilitate silane screening in the future.</p>\u0000 </div>","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":"20 4","pages":""},"PeriodicalIF":1.3,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784608","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}

{"title":"Dynamic VLE-Coupled Kinetic Modeling of Bulk Propylene Polymerization, Calibrated via Reactor Pressure Decay","authors":"Fatemeh Yahyaeian Balouchi,&nbsp;Saeed Mardani,&nbsp;Kaisa Lamminpaa,&nbsp;Jukka Niskanen,&nbsp;Sina Valaei","doi":"10.1002/mren.70027","DOIUrl":"https://doi.org/10.1002/mren.70027","url":null,"abstract":"<div>\u0000 \u0000 <p>This work presents a dynamic, model-based kinetic measurement method that couples vapor-liquid-equilibrium with reaction kinetics for the bulk-phase polymerization of propylene in a bench-scale reactor. This model couples Peng-Robinson‑based flash calculations with a simplified kinetic scheme (activation, propagation, deactivation). Reactor pressure-time trajectories from polymerizations (at 20°C–30°C) are used as model input. The novelty of this approach lies in explicitly embedding vapor-liquid equilibrium into the dynamic pressure‑based calibration of polymerization kinetics under bulk pre‑polymerization conditions. Through the process of parameter tuning, the simulated and measured reactor pressure drop caused by conversion of liquid propylene to polypropylene in a multi-component mixture are aligned, yielding the simulated polymerization rate and the elementary reaction rate constants. The model reproduces the characteristic pressure decrease and end-point yields within acceptable deviations and demonstrates instantaneous catalyst activity profiles, the activity decay over reaction time, and the temperature response of the catalyst. This approach enables access to detailed catalytic polymerization kinetics of propylene at mild temperatures which are typically used under industrial pre-polymerization reactors.</p>\u0000 </div>","PeriodicalId":18052,"journal":{"name":"Macromolecular Reaction Engineering","volume":"20 4","pages":""},"PeriodicalIF":1.3,"publicationDate":"2026-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148783501","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}