Article
Polymer Science
Daniel J. Eyckens, Jacqui L. Adcock, James P. Blinco, Kathryn E. Fairfull-Smith, Jessica Harris, Filip Vukovic, Siyuan He, Bhagya Dharmasiri, Tiffany R. Walsh, Paul S. Francis, Andreas Hendlmeier, Luke C. Henderson
Summary: Nitroxide groups grafted to carbon fibers as anchoring sites for TEMPO-terminated polymers have been used for surface modification. The surface-modified fibers show enhanced physical properties, including increased tensile strength, Young's modulus, and interfacial shear strength. However, polymer-grafted surfaces exhibit smaller increases in interfacial shear strength compared to surfaces modified with small molecules, possibly due to the lack of exposed chain ends.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Tomohiko Nishiuchi, Daisuke Ishii, Seito Aibara, Hiroyasu Sato, Takashi Kubo
Summary: In this study, a highly stable TAntM radical was successfully synthesized using a TIPS-ethynyl group, which effectively suppresses the reactivity of the radical. Chemical modification of the radical can be performed at room temperature, making it a versatile strategy for constructing unique spin-labelled molecules.
CHEMICAL COMMUNICATIONS
(2022)
Article
Polymer Science
Soumaya Kouki, Najeh Jaoued-Grayaa, Amira Anene, Emmanuel Beyou, Yves Chevalier, Souhaira Hbaieb
Summary: This study investigates the origin of the improved performance of Molecular Imprinted Polymers (MIPs) prepared by Nitroxide-Mediated Radical Deactivation Reversible Polymerization (NMRP) and by conventional Free Radical Polymerization (FRP). The study reveals that the enhanced adsorption of NMRP MIPs is due to a higher density of molecular imprints rather than a higher affinity. Additionally, hydrogen bonding between the MIP carboxylic acids and the target molecule is found to be the main contribution to adsorption.
Article
Polymer Science
Eleftherios G. Andriotis, Alexandros E. Koumbis, Dimitris S. Achilias
Summary: The incorporation of limonene in the polymer chains can reduce the average molecular weight, while acting as a radical scavenger to inhibit styrene thermal auto-polymerization at high temperatures. In the absence of styrene monomer, limonene can result in the functionalization of polystyrene. This functionalization can be extended to the synthesis of novel materials based on naturally occurring terpenes using NMP.
Article
Materials Science, Multidisciplinary
Ilona Wagner, Simon Spiegel, Julian Brueckel, Matthias Schwotzer, Alexander Welle, Martina H. H. Stenzel, Stefan Braese, Salma Begum, Manuel Tsotsalas
Summary: Surface engineering of MOF NPs using dynamic modification strategies enables the tailoring of PEG-grafted MOF NPs with improved colloidal stability and high dispersity, while maintaining their morphology and lattice crystallinity. The PEG-grafted MOF NPs show reduced adsorption of HSA protein compared to uncoated ones, indicating the potential for reducing nonspecific interactions and introducing targeting moieties for specific interactions. This approach expands the applications of colloidal MOF NPs in biologically relevant fields.
MACROMOLECULAR MATERIALS AND ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Mehdi Belqat, Xingyu Wu, Jason Morris, Karine Mougin, Tatiana Petithory, Laurent Pieuchot, Yohann Guillaneuf, Didier Gigmes, Jean-Louis Clement, Arnaud Spangenberg
Summary: Photoactivated Reversible Deactivation Radical Polymerization (RDRP) technologies have recently emerged in the field of 3D printing systems, specifically in vat-photopolymerization-based processes such as digital light processing (DLP). Unlike conventional free radical photopolymerization, photoRDRP in 3D printing allows for post-modification of 3D objects. This study develops a photoresist suitable for 3D direct laser writing (3D DLW) based on nitroxide mediated photopolymerization (NMP2) and demonstrates highly tunable, precise, and successive surface patterning of 2D and 3D multi-material microstructures.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Engineering, Chemical
Milan Maric
Summary: NMP, a type of reversible deactivation radical polymerization, has been developed in Canada and expanded to different polymer architectures and monomers. The introduction of second-generation alkoxyamine initiators greatly increased the range of monomers that can be polymerized in a controlled manner, leading to new applications and products in the field of polymer synthesis.
CANADIAN JOURNAL OF CHEMICAL ENGINEERING
(2021)
Article
Polymer Science
Laurence Pessoni, David Siniscalco, Anne Boussonniere, Anne-Sophie Castanet, Laurent Billon, Nicolas Delorme
Summary: In this study, a series of azopolymers were synthesized using Nitroxide Mediated Polymerization (NMP), and the photo-isomerization properties and photo-reversible solid-to-liquid transitions were investigated. The results showed that both the molecular weight and chemical structure of the azopolymers influenced the transition characteristics, with longer substituents or linkers leading to faster transitions. These findings contribute to a better understanding of the mechanism behind the photo-reversible solid-to-liquid transition and provide insights for the design of novel azopolymers.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Polymer Science
Xiaoguang Qiao, Xin Dong, Ge Shi, Yanjie He, Xinchang Pang
Summary: The primary focus of structurally tailored and engineered macromolecular (STEM) gels is the postsynthesis polymeric modifications by grafting from the active sites. Reversible-deactivation radical polymerization (RDRP) techniques have been employed to more precisely tailor and tune STEM gels. Compared with atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP) has the advantages of simple components and pure products.
JOURNAL OF POLYMER RESEARCH
(2023)
Article
Polymer Science
Hien The Ho, Trang N. T. Phan, Marine Bonnevide, Nicolas Malicki, Marc Couty, Jacques Jestin, Didier Gigmes
Summary: The study presents the synthesis of a new nitroxide-mediated polymerization (NMP) initiator with a photolabile ortho-nitrobenzyl (oNB) group for surface-initiated NMP preparation of well-defined photoresponsive polystyrene grafted on silica nanoparticles. The photocleavable and photoresponsive properties of the materials were demonstrated using small angle X-ray scattering (SAXS) characterization.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Polymer Science
Saeid Tajbakhsh, Milan Maric
Summary: In this study, SG1-based amphiphilic macroinitiators were used for the nitroxide mediated polymerization of IBOMA/C13MA in miniemulsion. The effects of surfactant, co-stabilizer, and temperature on polymerization kinetics and particle size were investigated. The thermal properties of the polymers prepared by these macroinitiators showed a T-g range of -44°C < T-g < 109°C.
JOURNAL OF POLYMER SCIENCE
(2021)
Article
Polymer Science
Majid Pakizeh, Ali Moradi, Toktam Ghassemi
Summary: Chitin-based materials are promising in biomedical applications. Waste shrimp shells can be chemically extracted to produce high-value chitosan products. Future research should focus on improving extraction and production techniques for chitin.
EUROPEAN POLYMER JOURNAL
(2021)
Review
Chemistry, Medicinal
Qizhou Chen, Yi Qi, Yuwei Jiang, Weiyan Quan, Hui Luo, Kefeng Wu, Sidong Li, Qianqian Ouyang
Summary: Chitosan, derived from chitin, is a natural material with excellent properties. Chemical modification of chitosan can improve its solubility and biological activity, expanding its application range. This review covers the various chemical modification methods of chitosan and its application research progress. The modified chitosan derivatives have shown promising prospects in various fields. The paper aims to explore the latest progress in chitosan chemical modification technologies and analyze its application in pharmaceuticals and textiles, providing a basis for further development and utilization of chitosan.
Article
Chemistry, Applied
Saeid Tajbakhsh, Faezeh Hajiali, Milan Maric
Summary: A series of copolymers of glycidyl methacrylate (GMA) and C13 methacrylates were synthesized using nitroxide mediated polymerization (NMP). Thermal analysis showed potential high flame retardancy and the possibility of micro-phase separation and weak gradient polymerization in the copolymers.
REACTIVE & FUNCTIONAL POLYMERS
(2021)
Article
Polymer Science
Kyoungho Kim, Jieun Lee, Hong Y. Cho, Eun Ho Lee, Seo-Hui Lee, Taihyun Chang, Heung Bae Jeon, Hyun-Jong Paik
Summary: Different types of polymer chains generated and separated during nitroxide-mediated polymerization of styrene were investigated for the first time, revealing distinct molecular weight distributions. Living and dead chains were distinguished based on the number of hydroxyl groups introduced onto different groups, showing narrow MWD for chains derived from one initiation path and broad MWD for other chains originating from a different initiation route.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Engineering, Chemical
Roberto Gonzalez-Blanco, Nelson Jimenez-Reyes, Michael F. Cunningham, Enrique Saldivar-Guerra
Summary: Stable polystyrene latexes with controlled molecular weight distribution are obtained by using efficient TEMPO oxidants in combination with nitroxides as initiators. Different concentrations of styrene lead to colloidal dispersions with adjustable particle size, conversion rates, and molecular weights.
MACROMOLECULAR REACTION ENGINEERING
(2021)
Article
Engineering, Chemical
Omar Garcia-Valdez, Pascale Champagne, Michael F. Cunningham
Summary: The development of reversible deactivation radical polymerization (RDRP) allows for the creation of unique macromolecular architectures with tailored properties, providing control over molecular weight distribution, morphology, composition, and functionality. Polymer grafting techniques on natural polymers such as chitosan and cellulose nanocrystals (CNC) via RDRP have shown promise for various applications, despite their hydrophilic nature limiting potential in non-polar systems.
CANADIAN JOURNAL OF CHEMICAL ENGINEERING
(2021)
Article
Engineering, Chemical
Vida A. Gabriel, Pascale Champagne, Michael F. Cunningham, Marc A. Dube
Summary: Nanocellulosic materials can be used as green materials for property modification in latex polymers, especially cellulose nanocrystals. It was found that the nanocrystals are sensitive to the ionic strength of the aqueous phase in latexes. By adjusting the surfactant-initiator systems, it is possible to successfully incorporate nanocrystals in-situ in emulsion polymerization for stable latex production.
CANADIAN JOURNAL OF CHEMICAL ENGINEERING
(2022)
Article
Engineering, Chemical
Joe Glasing, Jaime C. Cazotti, Alexander T. Fritz, Lilian S. Szych, Djalal Fakim, Niels M. B. Smeets, Michael F. Cunningham
Summary: In this study, Pickering miniemulsion polymerizations of styrene were conducted using starch nanoparticles modified with OSA and DSA. Low interfacial tension and a range of particle sizes were observed, with secondary nucleation observed when AIBN was used as an initiator. Modified SNP as PE resulted in relatively uniform latexes at low conversions.
CANADIAN JOURNAL OF CHEMICAL ENGINEERING
(2022)
Editorial Material
Engineering, Chemical
Michael F. Cunningham, Joao B. P. Soares
CANADIAN JOURNAL OF CHEMICAL ENGINEERING
(2022)
Review
Polymer Science
Amanda Rigg, Pascale Champagne, Michael F. Cunningham
Summary: Bio-based Pickering emulsifiers present a nontoxic alternative to surfactants in emulsion formulations and heterogeneous polymerizations, but the inherent hydrophilicity of polysaccharides and their nanoparticles limits efficiency and application range, necessitating surface modification for stability and functionality.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Engineering, Chemical
Olga Lidia Torres-Rocha, Sophie Campbell, Nicole Woodcock, Julien Pinaud, Patrick Lacroix-Desmazes, Pascale Champagne, Michael F. Cunningham
Summary: A simple method using block copolymers to functionalize the surface of cellulose nanocrystals (CNC) has been reported, altering the hydrophilicity of CNC and increasing their dispersibility in organic solvents. This approach is simpler and less expensive than current routes based on covalent modification.
MACROMOLECULAR REACTION ENGINEERING
(2022)
Article
Engineering, Chemical
Vida A. Gabriel, Mathieu N. Tousignant, Sean M. W. Wilson, Marie D. M. Faure, Emily D. Cranston, Michael F. Cunningham, Benoit H. Lessard, Marc A. Dube
Summary: Cellulose nanocrystals (CNCs) are a green alternative for producing polymer nanocomposites, providing significant matrix reinforcement. Films made with carboxylated CNCs (cCNCs) display higher peel strength, tack, and shear strength. Interestingly, omitting ultrasonication preserves cCNC-cCNC interactions, allowing them to behave like nanofibers and exhibit greater mechanical enhancements.
MACROMOLECULAR REACTION ENGINEERING
(2022)
Article
Polymer Science
Antonio Monroy-Alonso, Almendra Ordaz-Quintero, Jorge C. Ramirez, Enrique Saldivar-Guerra
Summary: A significantly improved thermal pyrolysis process for polystyrene is reported, which achieves higher styrene yield by optimizing the heating ramp during the initial stage of the process. The process was tested on samples of polystyrene synthesized via free-radical polymerization and nitroxide mediated polymerization, and the latter showed the highest styrene yield. The mathematical model used in this study corrects the errors of a previous model and provides further insight into the initial stages of the pyrolysis process.
Article
Engineering, Chemical
Angel Pablo-Morales, Maria Esther Trevino, Enrique Saldivar-Guerra
Summary: There is a need for sustainable materials to replace fossil-origin ones. Myrcene (Myr), a biobased terpene-type monomer, shows potential as a substitute for diene monomers in elastomer production. The copolymerization of Myr with glycidyl methacrylate (GMA) results in alternating copolymers with varying molecular weights and dispersities. Fourier transform infrared spectroscopy confirms the presence of GMA in the copolymer.
MACROMOLECULAR REACTION ENGINEERING
(2022)
Article
Polymer Science
Jose Alfredo Tenorio-Lopez, Juan Jose Benvenuta-Tapia, Norma Garcia-Navarro, Eduardo Vivaldo-Lima, Pascale Champagne, Enrique Saldivar-Guerra
Summary: A mathematical model for the RAFT copolymerization of GMA and St is developed, which can maintain narrow dispersities even at high conversions, and serves as an aid in industrial RAFT polymerization processes.
Article
Polymer Science
Ariadna Jimenez-Victoria, Rene D. Peralta-Rodriguez, Enrique Saldivar-Guerra, Gladis Y. Cortez-Mazatan, Lluvia de Abril A. Soriano-Melgar, Carlos Guerrero-Sanchez
Summary: This study investigates the use of an ionic liquid as a surfactant in emulsion polymerization. The selected amphiphile cationic oligoether performs similarly to the conventional surfactant and demonstrates the capability to stabilize the polymerization process.
Article
Polymer Science
Ipek Terzioglu, Carolina Ventura-Hunter, Jens Ulbrich, Enrique Saldivar-Guerra, Ulrich S. Schubert, Carlos Guerrero-Sanchez
Summary: This article discusses a dialysis method implemented in a commercially available automated parallel synthesizer. The method enables efficient removal of unreacted monomers from polymer synthesis, with up to 99% removal rate. The molar mass and distribution of the investigated polymers remain unchanged after purification. This method provides a good alternative for unattended and reliable purification of polymer libraries.
Article
Engineering, Chemical
Ivan Zapata-Gonzalez, Enrique Saldivar-Guerra
Summary: In the field of polymerization reaction engineering, the method of moments (MoM) has been widely used due to its simplicity in translating complex population balance equations (PBE) into a limited number of equations. This work provides an overview of the MoM, covering the derivation of moment equations in a basic kinetic mechanism and discussing various tools and strategies such as the binomial theorem, series expansion, pattern identification, and graphical summation inversion. The article also explains the application of MoM in different types of reactions and presents recent advancements including models with chain-length dependent termination and prediction of molecular weight distribution (MWD) using MoM.
CANADIAN JOURNAL OF CHEMICAL ENGINEERING
(2023)
Article
Polymer Science
Porfirio Lopez-Dominguez, Enrique Saldivar-Guerra, Maria Esther Trevino, Ivan Zapata-Gonzalez
Summary: A deterministic kinetic model was developed to simulate the particle size distribution (PSD) in emulsion polymerization (EP). The study compared the pseudo bulk (PB) model and the 0-1/0-1-2 model, and concluded that the PB model is not suitable for representing PSDs with steep fronts. There is also no generalized evidence to support the addition of a stochastic term in deterministic models to enhance PSD predictions.
Article
Polymer Science
Yuanzhang Jiang, Xuyi Wang, Yanting Han, Dakai Gong, Yingchun Gu, Lin Tan
Summary: In this study, FeCl3 and poly(acrylic acid) (PAA) were doped into waterborne polyurethanes (WPUs) to create multifunctional materials with self-healing and antimicrobial properties. WPU/Fe/PAA-5.5, containing 5.5 wt % PAA, exhibited excellent mechanical properties, strong self-healing capabilities, and an impressive antimicrobial rate of over 90%. These supramolecular films were also highly recyclable through hot-pressing.
Article
Polymer Science
Longyu Tian, Min Wang, Guangming Liao, Baoliang Liu, Sujuan Zhang, Yucheng Sun, Zhen Meng, Jintao Zhang, Zaijun Lu
Summary: Two kinds of benzoxazine monomers were synthesized and used to prepare polybenzoxazine anion exchange membranes (AEMs) with quaternary ammonium functionalization. The LQPBZ AEM exhibited better ion conductivity and alkaline stability.
Article
Polymer Science
Claire A. Lemarchand
Summary: This study investigates the shock behavior of three different polymers through molecular dynamics simulations. The results reveal specificities in the shock behavior of polymers, including deviations from the linear relation between shock velocity and particle velocity, as well as differences in shear stress relaxation behind the shock front. It is found that the deviation of the Hugoniot locus is related to the change in the relative contribution of bonding and non-bonding potential energies, while polymers with higher glass transition temperatures exhibit slower shear stress relaxation.
Article
Polymer Science
Zengquan Liu, Xiaochun Yin, He Zhang, Shuo Gao, Qinglin Kuang, Yanhong Feng
Summary: A powder solid-state extension (PSSE) technology was proposed to address the high melt viscosity issue of UHMWPE. By uniaxial extension and sintering in the solid state, a highly self-reinforced material was prepared. X-ray diffraction and scattering techniques were used to study the structural evolution during the PSSE process, and a solid-phase induced transformation model was established.
Article
Polymer Science
Zhike Li, Anyu Luo, Rui Zhou, Xin Li, Haiyan Li
Summary: A novel high temperature resistance IL@SiO2 nanocapsules were successfully prepared and their friction and wear properties in PA6 composites were studied. The addition of IL@SiO2 nanocapsules reduced the friction coefficient and wear rate without affecting the mechanical properties of PA6. The synergy between the IL core and SiO2 wall in the nanocapsules improved the self-lubricating performance of the PA6 composites.
Article
Polymer Science
Xin Liu, Xuhong Guo, Qi Liao
Summary: In this study, an algorithm for accurately estimating viscosity is developed using molecular dynamics simulations and the Green-Kubo formula. This algorithm can be applied to complex systems with long correlations, such as macromolecular and biological simulation systems.
Article
Polymer Science
Hao Pu, Yun-Lei Hou, Jing -Zhou Chen, Dong -Lin Zhao
Summary: The use of modified graphene improves the interfacial adherence of carbon fibers to epoxy resin, resulting in enhanced interfacial and bending properties of CF and matrix in CF/EP composites, as well as increased interlaminar shear strength and flexural strength.
Article
Polymer Science
Wei-Chung Ke, Jin-Wei Lin, Manohar Reddy Busireddy, Yueh-Hsing Lee, Jiun-Tai Chen, Chain-Shu Hsu
Summary: This study introduces a crosslinkable monomer, TAIC, to synthesize three crosslinked polyimide films, which exhibit improved thermal, mechanical, and dielectric properties. The introduction of TAIC enhances the tensile strength, reduces the dielectric constant and dielectric loss, and decreases the coefficient of thermal expansion of the polyimide films.
Article
Polymer Science
Alex Kwasi Kumi, Ruiling Fan, Ye Chen, Yumei Zhang
Summary: The difference in leaching of amylopectin from cellulose/amylopectin/1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) blends during regeneration in water and aqueous ethanol has been studied. Molecular dynamics simulations showed that the dissolution and regeneration mechanisms of amylopectin in [Bmim][Cl] are similar to cellulose in ionic liquids. Water regeneration leads to weak electrostatic interactions, resulting in high leaching of amylopectin. In contrast, ethanol-water interactions enhance electrostatic interactions among amylopectin chains, limiting amylopectin leaching in aqueous ethanol.
Article
Polymer Science
Xi Zeng, Junwei Zhou, Junbiao Peng, Chunsheng Zhang, Danling Wang, Yihu Song, Qiang Zheng
Summary: This study utilizes an oligomer deep eutectic solvent (DES) based on polyethylene glycol to regulate the vulcanization kinetics of rubber. The results show that the DES can accelerate vulcanization at low temperatures without affecting the crosslinking density and Mullins effect.
Article
Polymer Science
Qianqian Yue, Yongfei Peng, Xingjian Liu, Aihua He, Huarong Nie
Summary: The addition of metal deactivators can effectively suppress the aging of TBIR, prolong its lifespan, and have no negative effects on its physical and processing properties. These research findings are of great importance for improving the stability and aging resistance of polymers.
Article
Polymer Science
J. Gomez-Caturla, J. Ivorra-Martinez, R. Tejada-Oliveros, V Moreno, D. Garcia-Garcia, R. Balart
Summary: This work focuses on the development of environmentally friendly PLA formulations by using different esters derived from geraniol as plasticizers. The results show that these esters have good compatibility with PLA, and they can effectively enhance the elongation and plasticity of PLA, reduce its glass transition temperature, and slightly improve its water absorption capabilities.
Article
Polymer Science
Dandan Li, Zhaohui Lu, Zhao Ke, Ke Xu, Fengna Dai, Youhai Yu, Guangtao Qian, Chunhai Chen
Summary: In this study, cross-linked PI aerogel membranes with low dielectric constant and high moisture resistance were prepared by co-polymerization and scraping coating technology. The incorporation of fluorinated blocks and benzimidazole ring structures resulted in novel PI aerogel membranes with fascinating dielectric properties and outstanding moisture resistance.
Article
Polymer Science
Zhaoyang Chu, Qing Zhang, Haihua Luo, Han Zhou, Fapei Zhang, Wei Chen, Wenhua Zhang
Summary: Multi-physical fields solution processing strategy is a universal and facile method for preparing various conjugated polymer films and high-performance devices. In this study, we employed a combined microfluidic flow and ultrasonication strategy (FU) for processing CP solutions, and found a pronounced synergetic effect in promoting the pre-ordering of chains in solution. The conformation order and anisotropy of the solution were revealed through various characterizations. A non-classical nucleation model for polymer crystallization in non-equilibrium solution processing was confirmed. The roles of microfluidic flow and ultrasonication in chain aggregation and crystallization were addressed through multi-physical simulations. Compared to pristine solutions, the FU strategy showed improved solution anisotropy and crystallization kinetics, resulting in higher crystallinity in films and increased mobilities in OFET devices. The FU processing strategy provides a universal approach for regulating chain conformation and aggregation in conjugated polymer solutions.
