Special Issue "Living Polymerization"

A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (31 October 2017).

Special Issue Editor

Prof. Dr. Ivan Gitsov
Website
Guest Editor
Department of Chemistry, State University of New York - ESF, Syracuse, NY 13210, USA
Interests: synthesis and characterization of polymers with novel macromolecular architectures: linear, dendritic, linear-dendritic, star-dendritic, cyclo-dendritic, dendronized, hyperbranched and linear-hyperbranched; biocompatible and biodegradable polymers, novel polymeric systems for drug delivery and diagnosis (theranostics materials); “living” polymerization methods; macromolecular self-assembly and interfacial transport; polymer-supported biocatalysis and “green” chemistry, semi-artificial enzymes

Special Issue Information

Dear Colleagues,

In 1956, a short paper by Michael Szwarc, entitled “’Living’ Polymers”, appeared in Nature. This communication had a transformative effect on the field of polymer science, providing researchers with a powerful concept for the precise control of the molecular mass characteristics for different polymers, and a versatile tool for macromolecular engineering. The main prerequisites for ‘living’ polymerizations are: Rapid initiation (all active propagation centers created at once), propagation rate much slower than the rate of initiation and free of side reactions, lack of termination. Under these conditions, the active centers in the macromolecules should stay ‘alive’ and be able to add new monomers, comonomers and/or another fragment or polymer block with complimentary functional group(s). An important advantage of ‘living’ polymerizations is that they yield polymers with predictable molecular masses, narrow molecular mass distributions and well-defined end groups. While the initial success was achieved with vinyl monomers and anionic initiators, constant developments have generated methods and strategies, which involve cationic and ring-opening polymerizations. In addition to block copolymers, numerous new materials with different composition and macromolecular architecture have been created using ‘living’ polymerizations with promising potential in a broad array of current and future applications. The field continues to expand with important advances in radical polymerization and ring-opening metathesis, where, under certain favorable conditions, the processes could approach the characteristics of classic ‘living’ polymerizations.

This humble scope of this Special Issue of Polymers is to provide interested readers with a flavor of recent developments in this dynamic area and trace potential applications and further growth.

Prof. Ivan Gitsov
Guest Editor

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Keywords

  • ‘Living’ Polymerization
  • ‘Living’/Controlled Polymerization
  • Pseudo-Living Polymerization
  • Anionic Initiators
  • Cationic Initiators
  • Ring-Opening Polymerization
  • Ring-Opening Metathesis Polymerization
  • Block Copolymers

Published Papers (9 papers)

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Research

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Open AccessArticle
Accurately Determining the Extent of Coupling in Post Polymerization Reactions of Polystyrene
Polymers 2018, 10(1), 80; https://doi.org/10.3390/polym10010080 - 16 Jan 2018
Abstract
Polymers prepared by controlled radical polymerization (CRP) can be employed in subsequent chain-end joining reactions, yet accurately assessing the extent of coupling in mechanistically unique paths is not straightforward. Precisely known mixtures of polystyrene standards were prepared and analyzed by gel permeation chromatography [...] Read more.
Polymers prepared by controlled radical polymerization (CRP) can be employed in subsequent chain-end joining reactions, yet accurately assessing the extent of coupling in mechanistically unique paths is not straightforward. Precisely known mixtures of polystyrene standards were prepared and analyzed by gel permeation chromatography (GPC), mimicking the coupled product and precursor that could be present after a post-polymerization, chain-end joining reaction. The exactly known percentages of each polymer in the mixture allowed for comparison of the true “extent of coupling” (Xc) to that determined by a commonly used equation, which is based on number average molecular weights (Mn) of the precursor and coupled product. The results indicated that an improvement in accuracy could be achieved by instead using refractive index (RI) signal height ratios under the peak molecular weight (Mp) of each component, with all calculations being within 0.05 of the true Xc of the fabricated “product” mixture (compared to greater than 0.10 average error using the more established method) when the sample mixture had nominal molecular weights of 2500 and 5000 Da. Moreover, when “precursor” and “coupled” pairs mixed were not related as a simple doubling of molecular weight, the calculation method presented here remained effective at determining the content of the mixture, especially at higher Xc values (>0.45). This second case is important for experiments that may link polymer chains together with a spacer, such as a radical trap, a triazole, or even larger structure such as an oligomer. Full article
(This article belongs to the Special Issue Living Polymerization)
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Open AccessArticle
Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate) via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions
Polymers 2017, 9(12), 723; https://doi.org/10.3390/polym9120723 - 16 Dec 2017
Cited by 3
Abstract
Isotactic (it-) and syndiotactic (st-) poly(methyl methacrylate)s (PMMAs) form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b [...] Read more.
Isotactic (it-) and syndiotactic (st-) poly(methyl methacrylate)s (PMMAs) form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st-) PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl4 as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN3. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC) between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH3CN and was affected by the block lengths and ratios. Full article
(This article belongs to the Special Issue Living Polymerization)
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Open AccessArticle
Allylthioketone Mediated Free Radical Polymerization of Methacrylates
Polymers 2017, 9(11), 608; https://doi.org/10.3390/polym9110608 - 13 Nov 2017
Cited by 3
Abstract
By combination of high trapping free radical efficiency of the thioketone and resonance of the allylic radical, a new type of mediating agent, 1,3,3-triphenylprop-2-ene-1-thione (TPPT) has been successfully synthesized, and then is used to study controlled free radical polymerization of methacrylates. Very stable [...] Read more.
By combination of high trapping free radical efficiency of the thioketone and resonance of the allylic radical, a new type of mediating agent, 1,3,3-triphenylprop-2-ene-1-thione (TPPT) has been successfully synthesized, and then is used to study controlled free radical polymerization of methacrylates. Very stable TPPT radicals at the end of poly(methyl methacrylate) (PMMA) are detected in the polymerization of MMA using TPPT and AIBN as the control agent and initiator. The MALDI-TOF MS spectra are used to identify terminal groups of the resultant poly(glycidyl methacrylate) (PGMA), and major component of the obtained polymer has the structure, (CH3)2(CN)C-PGMA-C7H9O3. Chain extension reaction tests ascertain formation of the dead polymers during the polymer storage and purification process of the polymers. Owing to very slow fragmentation reaction of the TPPT-terminated polymethacrylate radical and addition reaction of this radical with a primary radical, the growing chain radicals are difficult to be regenerated, leading to an unobvious change of the molecular weight with monomer conversion. The molecular weights of polymers can be controlled by the ratios of monomer/initiator and TPPT/initiator. However, the first order kinetics of the polymerization and the polymers with narrow polydispersity are obtained, and these phenomena are discussed. This study provides useful information on how to design a better controlling agent. Full article
(This article belongs to the Special Issue Living Polymerization)
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Open AccessArticle
Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases
Polymers 2017, 9(10), 538; https://doi.org/10.3390/polym9100538 - 21 Oct 2017
Cited by 8
Abstract
The anionic polymerization of styrene and 1,3-butadiene in the presence of phosphazene bases (t-BuP4, t-BuP2 and t-BuP1), in benzene at room temperature, was studied. When t-BuP1 was used, the polymerization proceeded in a controlled manner, whereas the obtained homopolymers exhibited the desired molecular [...] Read more.
The anionic polymerization of styrene and 1,3-butadiene in the presence of phosphazene bases (t-BuP4, t-BuP2 and t-BuP1), in benzene at room temperature, was studied. When t-BuP1 was used, the polymerization proceeded in a controlled manner, whereas the obtained homopolymers exhibited the desired molecular weights and narrow polydispersity (Ð < 1.05). In the case of t-BuP2, homopolymers with higher than the theoretical molecular weights and relatively low polydispersity were obtained. On the other hand, in the presence of t-BuP4, the polymerization of styrene was uncontrolled due to the high reactivity of the formed carbanion. The kinetic studies from the polymerization of both monomers showed that the reaction rate follows the order of [t-BuP4]/[sec-BuLi] >>> [t-BuP2]/[sec-BuLi] >> [t-BuP1]/[sec-BuLi] > sec-BuLi. Furthermore, the addition of t-BuP2 and t-BuP1 prior the polymerization of 1,3-butadiene allowed the synthesis of polybutadiene with a high 1,2-microstructure (~45 wt %), due to the delocalization of the negative charge. Finally, the one pot synthesis of well-defined polyester-based copolymers [PS-b-PCL and PS-b-PLLA, PS: Polystyrene, PCL: Poly(ε-caprolactone) and PLLA: Poly(L-lactide)], with predictable molecular weights and a narrow molecular weight distribution (Ð < 1.2), was achieved by sequential copolymerization in the presence of t-BuP2 and t-BuP1. Full article
(This article belongs to the Special Issue Living Polymerization)
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Open AccessArticle
Thermoresponsive and Reducible Hyperbranched Polymers Synthesized by RAFT Polymerisation
Polymers 2017, 9(9), 443; https://doi.org/10.3390/polym9090443 - 13 Sep 2017
Cited by 6
Abstract
Here, we report the synthesis of new thermoresponsive hyperbranched polymers (HBPs) via one-pot reversible addition-fragmentation chain transfer (RAFT) copolymerisation of poly(ethylene glycol)methyl ether methacrylate (PEGMEMA, Mn = 475 g/mol), poly(propylene glycol)methacrylate (PPGMA, Mn = 375 g/mol), and disulfide diacrylate (DSDA) using [...] Read more.
Here, we report the synthesis of new thermoresponsive hyperbranched polymers (HBPs) via one-pot reversible addition-fragmentation chain transfer (RAFT) copolymerisation of poly(ethylene glycol)methyl ether methacrylate (PEGMEMA, Mn = 475 g/mol), poly(propylene glycol)methacrylate (PPGMA, Mn = 375 g/mol), and disulfide diacrylate (DSDA) using 2-cyanoprop-2-yl dithiobenzoate as a RAFT agent. DSDA was used as the branching agent and to afford the HBPs with reducible disulfide groups. The resulting HBPs were characterised by Nuclear Magnetic Resonance Spectroscopy (NMR) and Gel Permeation Chromatography (GPC). Differential Scanning Calorimetry (DSC) was used to determine lower critical solution temperatures (LCSTs) of these copolymers, which are in the range of 17–57 °C. Moreover, the studies on the reducibility of HBPs and swelling behaviours of hydrogels synthesized from these HBPs were conducted. The results demonstrated that we have successfully synthesized hyperbranched polymers with desired dual responsive (thermal and reducible) and crosslinkable (via thiol-ene click chemistry) properties. In addition, these new HBPs carry the multiplicity of reactive functionalities, such as RAFT agent moieties and multivinyl functional groups, which can afford them with the capacity for further bioconjugation and structure modifications. Full article
(This article belongs to the Special Issue Living Polymerization)
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Open AccessArticle
Study on the Mechanism of a Side Coupling Reaction during the Living Anionic Copolymerization of Styrene and 1-(Ethoxydimethylsilyphenyl)-1-phenylethylene (DPE-SiOEt)
Polymers 2017, 9(5), 171; https://doi.org/10.3390/polym9050171 - 11 May 2017
Cited by 3
Abstract
A 1,1-diphenylethylene (DPE) derivative with an alkoxysilyl group (DPE-SiOEt) was synthesized. It was end-capped with poly(styryl)lithium (PSLi) and then copolymerized with styrene via living anionic polymerization (LAP) in a non-polar solvent at room temperature. The observed side coupling reaction was carefully investigated by [...] Read more.
A 1,1-diphenylethylene (DPE) derivative with an alkoxysilyl group (DPE-SiOEt) was synthesized. It was end-capped with poly(styryl)lithium (PSLi) and then copolymerized with styrene via living anionic polymerization (LAP) in a non-polar solvent at room temperature. The observed side coupling reaction was carefully investigated by end-capping the polymer. Changes in molecular weight support the plausibility of a mechanism involving living anionic species (PSLi or lithiated DPE-end-capped polystyrene, PSDLi) and the alkoxysilyl groups. Through a series of copolymerizations with different feed ratios, the kinetics of the side coupling reaction were also studied. The results showed that the side reactions could be controlled using an excess feed of DPE-SiOEt, a potentially useful strategy for the synthesis and application of well-defined alkoxysilyl-functionalized polymers via LAP. Full article
(This article belongs to the Special Issue Living Polymerization)
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Review

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Open AccessFeature PaperReview
Metal Free Reversible-Deactivation Radical Polymerizations: Advances, Challenges, and Opportunities
Polymers 2018, 10(1), 35; https://doi.org/10.3390/polym10010035 - 29 Dec 2017
Cited by 16
Abstract
A considerable amount of the worldwide industrial production of synthetic polymers is currently based on radical polymerization methods. The steadily increasing demand on high performance plastics and tailored polymers which serve specialized applications is driven by the development of new techniques to enable [...] Read more.
A considerable amount of the worldwide industrial production of synthetic polymers is currently based on radical polymerization methods. The steadily increasing demand on high performance plastics and tailored polymers which serve specialized applications is driven by the development of new techniques to enable control of polymerization reactions on a molecular level. Contrary to conventional radical polymerization, reversible-deactivation radical polymerization (RDRP) techniques provide the possibility to prepare polymers with well-defined structures and functionalities. The review provides a comprehensive summary over the development of the three most important RDRP methods, which are nitroxide mediated radical polymerization, atom transfer radical polymerization and reversible addition fragmentation chain transfer polymerization. The focus thereby is set on the newest developments in transition metal free systems, which allow using these techniques for biological or biomedical applications. After each section selected examples from materials synthesis and application to biomedical materials are summarized. Full article
(This article belongs to the Special Issue Living Polymerization)
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Open AccessReview
Dormant Polymers and Their Role in Living and Controlled Polymerizations; Influence on Polymer Chemistry, Particularly on the Ring Opening Polymerization
Polymers 2017, 9(12), 646; https://doi.org/10.3390/polym9120646 - 25 Nov 2017
Cited by 2
Abstract
Living polymerization discovered by Professor Szwarc is known well to all chemists. Some of the living polymerizations involve dormancy, a process in which there is an equilibrium (or at least exchange) between two types of living polymers, namely active at the given moment [...] Read more.
Living polymerization discovered by Professor Szwarc is known well to all chemists. Some of the living polymerizations involve dormancy, a process in which there is an equilibrium (or at least exchange) between two types of living polymers, namely active at the given moment and dormant at this moment and becoming active in the process of activation. These processes are at least equally important although less known. This mini review is devoted to these particular living polymerizations, mostly polymerizations by the Ring-Opening Polymerization mechanisms (ROP) compared with some selected close to living vinyl polymerizations (the most spectacular is Atom Transfer Radical Polymerization (ATRP)) involving dormancy. Cationic polymerization of tetrahydrofuran was the first one, based on equilibrium between oxonium ions (active) and covalent (esters) dormant species, i.e., temporarily inactive, and is described in detail. The other systems discussed are polymerization of oxazolines and cyclic esters as well as controlled radical and cationic polymerizations of vinyl monomers. Full article
(This article belongs to the Special Issue Living Polymerization)
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Open AccessReview
Precise Synthesis of Macromolecular Architectures by Novel Iterative Methodology Combining Living Anionic Polymerization with Specially Designed Linking Chemistry
Polymers 2017, 9(10), 470; https://doi.org/10.3390/polym9100470 - 25 Sep 2017
Cited by 17
Abstract
This article reviews the development of a novel all-around iterative methodology combining living anionic polymerization with specially designed linking chemistry for macromolecular architecture syntheses. The methodology is designed in such a way that the same reaction site is always regenerated after the polymer [...] Read more.
This article reviews the development of a novel all-around iterative methodology combining living anionic polymerization with specially designed linking chemistry for macromolecular architecture syntheses. The methodology is designed in such a way that the same reaction site is always regenerated after the polymer chain is introduced in each reaction sequence, and this “polymer chain introduction and regeneration of the same reaction site” sequence is repeatable. Accordingly, the polymer chain can be successively and, in principle, limitlessly introduced to construct macromolecular architectures. With this iterative methodology, a variety of synthetically difficult macromolecular architectures, i.e., multicomponent μ-star polymers, high generation dendrimer-like hyperbranched polymers, exactly defined graft polymers, and multiblock polymers having more than three blocks, were successfully synthesized. Full article
(This article belongs to the Special Issue Living Polymerization)
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